CN101605825B

CN101605825B - Polyolefin compositions and articles prepared therefrom, and methods for making the same

Info

Publication number: CN101605825B
Application number: CN2007800513621A
Authority: CN
Inventors: 帕特里夏·安塞姆斯; 阿希什·巴特拉; 劳拉·B·韦弗; 劳伦斯·J·埃弗勒; H·C·西尔维斯; 哈梅德·莱克劳特; 劳拉·K·默根哈根
Original assignee: Dow Global Technologies LLC
Current assignee: Dow Global Technologies LLC
Priority date: 2006-12-21
Filing date: 2007-12-21
Publication date: 2012-09-26
Anticipated expiration: 2027-12-21
Also published as: CN101605825A; CN101605824A; CN101605824B

Abstract

The invention provides a composition comprising at least one olefin multi-block interpolymer; at least one functionalized olefin-based polymer; and optionally at least one thermoplastic polyurethane. The invention also provides for articles prepared from the inventive compositions and for methods for making the same.

Description

Polyolefin compositions and by the goods of its preparation and their preparation method

The cross reference of related application

For patent practice; The application requires following U.S. Provisional Application No. and incorporates the content of following U.S. Provisional Application into this paper with its integral body through reference: 60/876287 of submission on December 21st, 2006; 60/952272 of submission on July 27th, 2007; On August 13,60/952425,2007 of submitting on July 27th, 2007 60/955464, and submitted on July 27th, 2007 60/952271.

Technical field

The present invention provides the compsn that comprises following material: a) the many block interpolymers of at least a alkene; B) at least a functionalized polymkeric substance based on alkene; And optional c) at least a thermoplastic polyurethane.

Background technology

Polyolefine is as one type of material, and the adhesivity and the consistency of the polymer materials that itself and polarity are bigger are relative mistakes.When most situation, need independent tackiness agent polyolefine is adhered to polar substrates such as polyester, polymeric amide, urethane etc.Similarly, usually must use the 3rd component expanding material to prepare the melt blended material of the bigger thermoplastics of gratifying polyolefine and other polarity.Yet the expanding material that usually needs a great deal of keeps the intimate blending of polyolefine and urethane.

In the North America, about 25000000 pounds of soft PVCs (f-PVC) become the thermoset sheet material that automobile is used, for example test board or door face board.Such sheet material is a decorative pattern, and with other inner assembly color-match.The sheet material that automobile is used must satisfy several kinds of end-use requirements.Crucial end-use requires to comprise low-luster, high surperficial scrath resistance/anti-damage property, high thermotolerance and good low temperature shock-resistance.In addition, sheet material also must have and any intermediary urethane (PU) foam layer good adhesion property of (for example being used for providing to car panel the foam layer of softening or shock absorption).

Polymer sheet or crust must be flashes of light low gloss or low, if especially this sheet material is for example placed under the window under test board (IP), front window at automobile.In addition, material must keep low gloss in the time limit of service of vehicle.The gloss of material normally through the regulation the measurement of angle reflected light measure, and common experimental measurement 60 the degree carry out.Reflection measurement is converted into glossiness, and these values are less than or equal to 2 usually for automotive applications.Soft or plastized polyvinyl chloride has high glossiness usually.Reduce to the level that can be suitable for automotive applications for the glossiness that makes soft PVC, spread the liquid PU finish paint usually.

TPO (TPO) sheet material also can be used for automotive applications.Compare with soft PVC, TPO sheet material or crust not only have lower glossiness usually, improve surperficial scrath resistance/anti-damage property but also be coated with to be mainly used in by the urethane face, and the less important benefit that reduces glossiness of bringing.Yet new surface texturing technology (for example, in extrusion, giving extrusion sheet little decorative pattern by the roller surface of decorative pattern) is top-uped and is revealed, and it will allow various decorative pattern styles are carried out consistent gloss control.Can predict these new technology and will eliminate the needs that polyolefine is coated with the PU face, said polyolefine has an amount of scrath resistance/anti-damage property to satisfy application requiring.The case description of this type of new technology is in USP 5,902,854, and it incorporates this paper by reference into.

It is that sheet material (f-PVC or TPO) needs to stand the upper limit working temperature that automotive interior (especially under the high temperature in summer) bears that another end-use requires.Current Standard is: sheet material can be stood oven ageing 120 ℃ of temperature above 500 hours; Keep 50% original elongation (ISO 188/ASTM E145 simultaneously; Type II A, in the time of 120 ℃ 500 hours), and not fusion, be out of shape, be clamminess or other physical change occurs.Be that sheet material provides good shock resistance during as-40 ℃ at low temperature with this requirement requires simultaneously.(passenger safety in the winter time the time during the airbag deployment is very important when this based sheet is used to form seamless gasbag; Standard is not have flying chip), this performance is even more important.The second-order transition temperature of plastized polyvinyl chloride (Tg) is normally-20 ℃ to-30 ℃, so the low-temperature impact resistance of this polymkeric substance when being lower than the temperature of its Tg weakens to some extent.Yet, to compare with SE, TPO has lower second-order transition temperature usually, thereby has the good low-temperature shock resistance.TPO is generally especially in microthermal climate the alternative materials of unfolded seamless gasbag and other safety equipment during the vehicle collision.

Compare with soft PVC, TPO also has long-term durability preferably, and rheology and/or mechanical properties change less illustrated during as 120 ℃ of thermal ageings.In the time of 120 ℃, SE ordinary loss softening agent, thereby loss extensibility (elasticity) become fragile and then easy of crack.

Thermoplastic olefin (TPO) sheet material is used for Soft Roll day by day and covers test board and door face board.Common assembly method requires in moulding technology through forming urethane foam between two-layer below the flexible thermoplastic polyolefine crust and the hard surface base material of thermoforming to be linked together.The hard surface base material comprises TPO, acrylonitrile-butadiene-styrene copolymer (ABS) or acrylonitrile-butadiene-styrene copolymer/polycarbonate (ABS/PC) blend usually.In test board was used, the hard TPO with filler reinforcement replaced ABS and ABS/PC base material usually.Polyurethane precursor mixture (liquid isocyanate, the pure and mild catalyzer of liquid polyhydric) is injected between TPO crust and the hard surface, and reaction forms the middle layer of foamed then.

Unfortunately, TPO is because of the general adhesion that lacks polar material such as urethane of its nonpolar person's character.Therefore, with priming paint (primer) solution that contains one or more polar compounds flexible thermoplastic olefin sheet material is carried out surface treatment usually, thereby improve adhesion polyurethane surface.Common primer solution comprises chlorination maleation polyolefine.Such surface treatment requires: big draught area, and its assembling is used for operating sheet material through intaglio printing; Priming paint spreads device, for example steeping vat; And make water and the quick-drying drywall tool of other solvent carrier.In addition, flexible thermoplastic olefin crust must adhere to urethane foam, and does not have space and other visible defects.Urethane foam must adhere to the TPO surface, and is not having layering (perhaps adhesion failure) at the interface.Discontinuous the spreading of primer solution can cause in having the zone of priming paint, between thermoplastic olefin crust and urethane foam, not forming the space.Surface void causes expensive cost problem for trolley part manufacturer, and this is can not be used for the automobile assembling because have the parts of surface void, abrades on the contrary.

International Publication WO 00/63293 has disclosed the blend of a kind of thermoplastic polyurethane/alkene-graftomer and optional compatible polymer.Said compatible polymer is the polyolefine that is selected from following modification: the ionomer, block olefin polymer and the grafting olefin polymer that in main chain or side chain, have unsaturated organic compound.

European application 0347794A1 has disclosed a kind of thermoplasticity consistency blended composition, and it comprises: (A) polyolefine of 15～60wt%; (B) thermoplastic polyurethane of 30～70wt%; And (C) at least a modified polyolefin of 10～35wt%; Said at least a modified polyolefin is defined as random block or grafting olefin copolymer, on its main chain or side chain, has to be selected from following functional group: carboxylic acid, carboxylicesters, carboxylic acid anhydride, carboxylate salt, acid amides, epoxy, hydroxyl or acyloxy.

USP 6251982 has disclosed a kind of compounding rubber combination that comprises following component: the urethane based on hydrogenant polydiene glycol that (a) has the hard segment content more than 10%; (b) the nonpolar extending oil of 10～400phr; And/or (c) one or more thermoplastic resins of 5～100phr.

USP 5578680 has disclosed a kind of absorption of vibrations elastic composite; It comprises: (A) at least a thermoplastic resin that is selected from down group olefin polymer, ethene-unsaturated ester multipolymer and tree elastomer of 10-60wt%; And (B) urethane resin of 90-40wt%, said urethane resin prepares through POLYMETHYLENE POLYPHENYLISOCYANATE and polyvalent alcohol reaction in molten thermoplastic resin (A).The nitrogen atom content of said urethane (B) is 3wt% at least, and its SP is higher than the SP at least 2.5 of said thermoplastic resin, and the Tan δ of wherein said matrix material in the time of 20 ℃ is at least 1.0.

USP 4883837 has disclosed the compatible blend composition of a kind of thermoplasticity; It comprises the polyolefine of about 15～60wt%; The thermoplastic polyurethane of about 30～70wt%; And the polyolefine of at least a modification of about 10～35wt%, the polyolefine of said modification is defined as has random, block or the grafting olefin copolymer that is selected from following functional group in its main chain or side chain: carboxylic acid, carboxylicesters, carboxylic acid anhydride, carboxylate salt, acid amides, epoxy, hydroxyl and acyloxy.

USP 4198327 has disclosed a kind of to the adherent compsn of polar material; It comprises following ingredients: a) crystalline polyolefin of the modification of 99～70 weight parts; Grafting is selected from the monomer of unsaturated carboxylic acid and acid anhydrides, ester, acid amides, imide and metal-salt on said crystalline polyolefin; And wherein said crystalline polyolefin has at least 25% percent crystallinity (recording through X-ray analysis), and its amount that comprises grafted monomer is counted 0.0001～3wt% by the gross weight of crystalline polyolefin and grafted monomer; And b) hydrocarbon elastomer of 1～30 weight part.

USP 5705565 has disclosed a kind of thermoplastic polymer blend; It comprises one or more thermoplastic polymers; And being grafted with linear ethylene polymer basically at least about the unsaturated organic compound of 0.01wt%, said unsaturated organic compound comprises the unsaturated position of at least one olefinic and at least one carbonyl.Said thermoplastic polymer optional from urethane, polycarbonate, PS, polyester, epoxide, polymeric amide, the polyolefine that comprises polar group, acrylonitrile-butadiene-styrene copolymer, and composition thereof.

European patent application 0657502A1 has disclosed a kind of thermoplastic compounds; It comprises the mixture of following component: (a) segmented polyetherester, block polyetheramides and/or urethane; (b) with (a) inconsistent thermoplastic homopolymer, multipolymer or ter-polymers, and (c) expanding material.Said expanding material is selected according to the character of component (b).The reactive group that it will have the preferred identical main chain compatible with component (b) and act on perhaps mutually mutually with component (a).Said reactive group can with contain at least a α-or the grafted monomer of β-ethylenically unsaturated carboxylic acids and acid anhydrides and verivate thereof it is grafted on this main chain.

USP 6414081 has disclosed a kind of blend of compatibilized, and it comprises following component: the apolar thermoplastic elastomer that a) comprises TPO homopolymer or multipolymer and fully crosslinked or partial cross-linked olefinic rubber; And b) is selected from the polar thermoplastic polymer of thermoplastic polyurethane (TPU), chlorine-containing polymer, fluoropolymer, polyester, acrylonitrile-butadiene-styrene copolymer, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, polyacetal, polycarbonate or ppe; And be selected from following c) expanding material: the condensation polymerization copolymer that i) forms by polymeric amide by the functionalized olefin polymer of the gross weight 10～90wt% of functionalized polymeric and polymeric amide and 90～10wt%; The perhaps ii) blend of functionalized olefin polymer and polymeric amide, perhaps iii) (i) and (ii) mixture.

USP 6469099 has disclosed the blend of a kind of polymerized hydrocarbons and thermoplastic polyurethane, and it is with the polymerized hydrocarbons increase-volume of the isocyanate-reactive group that contains lower concentration.This expanding material can be through making polymer-modified and oxyamine, diamines or the polyethers monoamine prepared in reaction that contains the amine reactivity side group or incorporate the amine reactive group into.The blend of increase-volume also can comprise non-TPU engineering thermoplasties to form polymerized hydrocarbons and non-TPU engineering thermoplasties's compatible blend.

International Publication WO 00/63293 has disclosed a kind of polymer compsn; It comprises the thermoplastic polyurethane and the first alkene graftomer; Said graftomer comprises at least one first grafting part and at least one second grafting part; Said first grafting partly is to promote grafting elastomerics crosslinked silane moiety under moisture, and said second grafting partly is the unsaturated organic compound that before grafting, comprises at least one olefinic unsaturated and promotion alkene and thermoplastic carbamate's compatible polar functional group.

USP 5902854 has disclosed and has comprised interpretation for example line style or the ethene interpretation of line style and the compsn of YSR 3286 basically.Said composition also comprises with maleic anhydride or Succinic anhydried group grafted Alathon or interpretation.Said composition has good wearability and does not but sacrifice frictional coefficient.

USP 4397916 has disclosed a kind of layer and has closed multilayered structure, and it comprises: (A) one deck with the ethenoid resin of the graft modification of unsaturated carboxylic acid or its functionality derivatives graft and (B) with layer (A) contacted polar resin layer or a metal level that contains oxygen or nitrogen.Be it is made up of following material the characteristic of layer (A): (i) ethenoid resin of the said graft modification of 1～100wt%, the ethenoid resin of said graft modification come from least a ethene polymers that contains the terminal olefin of 3～30 carbon atoms as comonomer that comprises 0～15mol%; And the (ii) unmodified ethene polymers of 99～0wt%, said unmodified ethene polymers comprises at least a terminal olefin that contains 3～30 carbon atoms of 0～50mol% as comonomer.

International Publication WO 96/27622 has disclosed a kind of through making the polymkeric substance of being with Electron Affinities functional group and the diamine reactant that contains the amino end group of differential responses property prepare the amine-functionalized polyolefinic method of Electron Affinities.The amine-functionalized polyolefine of said Electron Affinities has following composition: polyolefine-X-R ₁-NHR ₂, wherein X is selected from imide, acid amides, sulphonamide or amine groups, R ₁Be divalent organic group, R ₂Be H or alkyl.But but the amine-functionalized polyolefine of said Electron Affinities can be used as expanding material, tackiness agent coloring material and dyeability modifier.

International Publication WO 93/02113 has disclosed the graftomer that comprises reactive amines functional group, and it prepares through following method: a) provide to comprise at least one and be enough to the thermoplastic polymer with the Electron Affinities functional group of primary amino reaction; And b) with comprise the compound frit reaction of a primary amine and a secondary amine, the reactivity of said secondary amine is substantially equal to or less than said primary amine.Comprise the compound of selected diamines through use, avoided crosslinked formation basically.This graftomer has been described as the properties-correcting agent of polymer compsn and the purposes of expanding material.

International Publication WO 03/008681 has disclosed the fiber that when high temperature, has improved wet fastness; It comprises at least two kinds of elastomeric polymers: but a kind of polymkeric substance of thermal-setting and another kind of heat-stable polymkeric substance, and said heat-stable polymkeric substance constitutes outside surface at least a portion of said fiber.This fiber has two components and/or two composition core/sheath form usually.Usually, said core comprises the flexible thermoplastic carbamate, and said sheath comprises the preferred evenly polymkeric substance of linear ethylene basically of branching of the polyolefine of even branching.Fibre fractionation can comprise functional polyethylene.(also can referring to WO 03/008680).

The instance that contains other compsn of functionality component is disclosed in US 5623019, US 6054533, US 5578680, EP1672046, EP0734419B1 and EP0657502A1.Other functionalized polymeric and/or compsn are disclosed in International Publication WO 99/02603 and disclose 2004/0106744 with the U.S..

The low-cost polyolefin compositions that still need can be used as the good tackiness agent of the base material that polar substrates is for example formed by urethane, polycarbonate or polymeric amide.Further need can be used for that the lamination injection moulding is used and provide improved adherent this based composition of polar substrates.These demands have obtained satisfying through following invention with other demand.

Also still need so low-cost polyolefin compositions, it can also comprise urethane and/or comprise the low-level expanding material that preferably is lower than 10wt%.If said composition can be used as the good tackiness agent of the base material that polar substrates is for example formed by urethane, polycarbonate or polymeric amide, then is more favourable.Having high surface energy and good adhering goods for example sheet material and film if can process, then is also more favourable.Also need compatible cheaply compsn in addition, it has improved heat aging performance, and is particularly suited for bearing high as 120 ℃ of interior application of pyritous cars.Further need can be used for that the lamination injection moulding is used and provide improved adherent this based composition of polar substrates.The application of other potentially useful comprises uses (thermoforming crust) in the car, and it provides one or more following character: luxurious sense, lower gloss and the desired decorative pattern of improved negative pressure thermoforming process duplicate.These demands have obtained satisfying through following invention with other demand.

Also need develop such polyolefin compositions, it comprises polyurethane component, and the stablizer of expanding material or other type that needs minimum stable with the polymer phase that keeps compsn, and has high surface energy and good adhesivity.These demands have obtained satisfying through following invention with other demand.

Still need the improved compsn of polyolefin/polyurethane cheaply, it comprises the expanding material of low-level (preferably the gross weight by compsn is lower than 10wt%); And it can be used for goods for example sheet material and film; And it has high surface energy (being preferably greater than 30dyn/cm) and good adhesivity.Also need compatible cheaply compsn in addition, it has improved heat aging performance, and is particularly suited for bearing high as 120 ℃ of interior application of pyritous cars.Further need can be used for using in the car such compsn of (thermoforming crust), it provides one or more following character: luxurious sense, lower gloss and the desired decorative pattern of improved negative pressure thermoforming process duplicate.

Also need suitable thermoplastic polyolefin composition in addition, said compsn can be used for forming such sheet material, and its urethane face that need not to be used for gloss or to swipe control is coated with and urethane foam is had good adhesion.Also need develop weatherable, low gloss and/or the good anti-anti-sheet material that decreases of scraping, said sheet material has the good adhesion property to PU foams, PU tackiness agent and coating.These demands have obtained satisfying through following invention with other demand.

Summary of the invention

The present invention provides a kind of compsn that comprises following component:

A) the many block interpolymers of at least a alkene;

B) at least a functionalized polymkeric substance based on alkene; And

C) at least a thermoplastic polyurethane of choosing wantonly.

Description of drawings

Fig. 1 shows the curve of the fusing point of several kinds of many block interpolymers of ethylene/alpha-olefin (polymkeric substance of the present invention) and comparative polymer (common random copolymers and Ziegler-Natta) as the function of density.

Fig. 2 shows the curve of several kinds of polymkeric substance " DSC Tm-CrystafTc " as the function of melting heat.

Fig. 3 has shown that density is to by the influence with the elastic recovery rate of the non-oriented film of some common random copolymerss preparations of some alkene many block interpolymers.

Fig. 4 shows the co-monomer content of several kinds of random ethylenes/1-octene copolymer and many blocks ethene/1-octene copolymer and the relation of TREF eluting temperature.

Fig. 5 shows segmented copolymer (embodiment 5) and correlated multipolymer (embodiment F ^*) TREF curve and the relation of co-monomer content.

Fig. 6 shows the curve of the storage modulus of several kinds of segmented copolymers (polymkeric substance of the present invention) and correlated random copolymers as the function of temperature.

Fig. 7 shows segmented copolymer (polymkeric substance of the present invention) and some Comparative Examples (Versify ^TM, ethylene/styrene multipolymer, Affinity ^TM) TMA (thermo-mechanical analysis) data and the relation of modulus in flexure data.

Fig. 8 is the schematic representation of apparatus that is used to adhere to test.

Embodiment

General introduction

As stated, the present invention provides a kind of compsn that comprises following component:

A) the many block interpolymers of at least a alkene;

B) at least a functionalized polymkeric substance based on alkene; And optional

C) at least a thermoplastic polyurethane.

In one embodiment, the said at least a functionalized polymkeric substance based on alkene also refers to the polyolefine that the organic cpds by polyolefine and at least a being selected from " amine-containing compound ", " hydroxy-containing compounds ", " containing imide compound ", " compound that contains acid anhydride " or " compound that contains carboxylic acid " forms.

In another kind of embodiment, the many block interpolymers of said alkene are the many block interpolymers of ethylene/alpha-olefin with characteristic below one or more:

(1) have average block index greater than 0 and about at the most 1.0, and greater than about 1.3 molecular weight distribution mw/mn; Perhaps

(2) when utilizing TREF to carry out fractionation, have at least a between 40 ℃ and 130 ℃ the molecule cut of wash-out, it is characterized in that this cut has at least 0.5 and about at the most 1 blockiness index; Perhaps

(3) have about 1.7 to about 3.5 Mw/Mn, at least one in degree centigrade fusing point Tm and in the density d of gram/cubic centimetre, wherein the numerical value of Tm and d meets following relational expression:

T _m＞-2002.9+4538.5 (d)-2422.2 (d) ², perhaps

(4) has about 1.7 to about 3.5 Mw/Mn; And relational expression below the numerical value that it is characterized in that Δ T and Δ H satisfies; Wherein Δ H is the melting heat in J/g, Δ T be in degree centigrade increment, this increment is defined as the highest DSC peak and the peak-to-peak temperature head of the highest CRYSTAF:

When Δ H greater than 0 and at the most during 130J/g, Δ T＞-0.1299 (Δ H)+62.81,

As Δ H during greater than 130J/g, Δ T >=48 ℃,

Wherein said CRYSTAF peak utilizes at least 5% cumulative polymer determination, if having discernible CRYSTAF peak less than 5% polymkeric substance, then the CRYSTAF temperature is 30 ℃; Perhaps

(5) it is characterized in that not containing crosslinked phase time basically when ethylene/alpha-olefin interpolymers; Relational expression below the numerical value of Re and d satisfies; Wherein Re is the elastic recovery rate percentage ratio that under 300% strain and 1 cycle, records to the compression moulding film of ethylene/alpha-olefin interpolymers, and d is the density in gram/cubic centimetre:

Re＞1481-1629 (d); Perhaps

(6) when utilizing TREF to carry out fractionation; Molecule cut with wash-out between 40 ℃ and 130 ℃; The comonomer molar content height at least 5% that it is characterized in that comonomer molar content ratio equal random ethylene interpretation cut of wash-out that this cut has in the uniform temp interval; Wherein this equal random ethylene interpretation has the comonomer identical with said ethylene/alpha-olefin interpolymers, and its melt index, density and based on the comonomer molar content of whole polymkeric substance all drop on said ethylene/alpha-olefin interpolymers ± 10% scope in; Perhaps

(7) it is characterized in that storage modulus G ' (25 ℃) and the storage modulus G ' in the time of 100 ℃ (100 ℃) in the time of 25 ℃, wherein G ' (25 ℃) is about 1: 1 to about 9: 1 with the ratio of G ' (100 ℃).

In another kind of embodiment, the said compound that contains acid anhydride is a maleic anhydride.

In another kind of embodiment, the amount of said at least a functionalized polymkeric substance based on alkene is less than or equal to 20wt% by the gross weight of compsn.In another kind of embodiment, the amount of said at least a functionalized polymkeric substance based on alkene is less than or equal to 10wt% by the gross weight of compsn.In another kind of embodiment, the amount of said at least a functionalized polymeric is less than or equal to 5wt% by the gross weight of compsn.

In another kind of embodiment, the amount of said at least a functionalized polymkeric substance based on alkene by the gross weight of compsn more than or equal to 20wt%.In another kind of embodiment, the amount of said at least a functionalized polymkeric substance based on alkene by the gross weight of compsn more than or equal to 30wt%.In another kind of embodiment, the amount of said at least a functionalized polymkeric substance based on alkene by the gross weight of compsn more than or equal to 40wt%.

In another kind of embodiment, the density of said at least a functionalized polymkeric substance based on alkene is about 0.85～0.91g/cc.In another kind of embodiment, the density of said at least a functionalized polymkeric substance based on alkene is about 0.84～0.93g/cc.In another kind of embodiment, the density of said at least a functionalized polymkeric substance based on alkene is about 0.85g/cc～0.93g/cc.In another kind of embodiment, the density of said at least a functionalized polymkeric substance based on alkene is about 0.84～0.90g/cc.

In another kind of embodiment, the melt index (I2) of said at least a functionalized polymkeric substance based on alkene is 0.1g/10 minute to 100g/10 minute.In another kind of embodiment, the melt index (I2) of said at least a functionalized polymkeric substance based on alkene is 1g/10 minute to 50g/10 minute.In another kind of embodiment, the melt index (I2) of said at least a functionalized polymkeric substance based on alkene is 1g/10 minute to 10g/10 minute.In another kind of embodiment, the melt index of said at least a functionalised polyolefin (I2) is 1g/10 minute to 20g/10 minute.

In another kind of embodiment, said at least a functionalized polymkeric substance based on alkene is by the polymer formation based on ethene.In a kind of further embodiment, said polymkeric substance based on ethene is an ethylene/alpha-olefin interpolymers.In another kind of embodiment, said terminal olefin is C ₃-C ₂₀Terminal olefin is preferably C ₃-C ₁₀Terminal olefin.In a kind of further embodiment, said terminal olefin is selected from down group: 1-propylene, 1-butylene, 1-hexene and 1-octene, and preferred 1-butylene and 1-octene.In another kind of embodiment, the ethylene/alpha-olefin interpolymers that is used to form said functionalized polymkeric substance based on alkene also comprises diene.In another kind of embodiment, the density of said ethylene/alpha-olefin interpolymers is 0.85～0.93g/cc.In another kind of embodiment, the melt index of said ethylene/alpha-olefin interpolymers (I2) is 0.01～1500g/10 minute.

In another embodiment, the ethylene/alpha-olefin interpolymers that is used to form said functionalized polymkeric substance based on alkene is the line style interpretation of even branching or the even interpretation of line style basically of branching.In another embodiment, the ethylene/alpha-olefin interpolymers that is used to form said functionalized polymkeric substance based on alkene is the interpretation of line style basically of even branching.

In another kind of embodiment, said at least a functionalized polymkeric substance based on alkene is by the polymer formation based on propylene.In another kind of embodiment, said polymkeric substance based on propylene is propylene/ethylene interpretation or propylene/alpha-olefins interpretation.In another kind of embodiment, said polymkeric substance based on propylene is the propylene/alpha-olefins interpretation, and wherein said terminal olefin is C ₄-C ₂₀Terminal olefin and preferred C ₄-C ₁₀Terminal olefin.In another kind of embodiment, said terminal olefin is selected from down group: 1-butylene, 1-hexene and 1-octene.In another kind of embodiment, the density of said propylene/alpha-olefins interpretation is 0.85～0.93g/cc.In another kind of embodiment, the melt index of said propylene/alpha-olefins interpretation (I2) is 0.01g/10 minute to 1500g/10 minute.In another kind of embodiment, said polymkeric substance based on propylene is the propylene/ethylene interpretation.In a kind of further embodiment, the density of said propylene/ethylene interpretation is 0.85～0.93g/cc.In another kind of embodiment, the melt index of said propylene/ethylene interpretation is 0.01g/10 minute to 1500g/10 minute.

In another kind of embodiment, said at least a functionalised polyolefin is formed by the many block interpolymers of alkene.

In another kind of embodiment, said compsn also comprises at least a thermoplastic polyurethane.Said at least a thermoplastic polyurethane can contain the chemical unit that comes from (1) polyester and (2) aromatic diisocyanate or aliphatic vulcabond.In another kind of embodiment, said at least a thermoplastic polyurethane contains the chemical unit that comes from polyester and at least a aromatic diisocyanate.In another kind of embodiment, said at least a thermoplastic polyurethane contains the chemical unit that comes from polyester and at least a aliphatic vulcabond.In another kind of embodiment, said at least a thermoplastic polyurethane comprises and comes from polyester and 1, two (isocyanato methyl) hexanaphthenes and 1 of 3-, the chemical unit of the mixture of 4-pair of (isocyanato methyl) hexanaphthenes.In a kind of further embodiment, said 1, two (isocyanato methyl) hexanaphthenes of 3-are with said 1, and the weight ratio of 4-pair of (isocyanato methyl) hexanaphthenes is about 1: 1.

In another kind of embodiment, said urethane is by comprising the monomeric unit that comes from diol, derivatives, and the polyester that this diol, derivatives comes from the N-octylpyrrolidone forms.In another kind of embodiment, said urethane is formed by the polyester that comprises the monomeric unit that comes from polytetramethylene ether diol.In another kind of embodiment, said urethane is formed by the polyester that comprises the monomeric unit that comes from polyethers.In another kind of embodiment, said thermoplastic polyurethane is PELLETHANE ^TMUrethane.

In a kind of further embodiment, said polyester is formed by caprolactone.In another kind of embodiment, the density of said at least a thermoplastic polyurethane is 0.90～1.3g/cc.In another embodiment, the melt index of at least a thermoplastic polyurethane (I2) is 1g/10 minute to 100g/10 minute.In another embodiment, the melt index of said at least a thermoplastic polyurethane (I2) is 1g/10 minute to 10g/10 minute.

In another embodiment, said thermoplastic polyurethane comprises the monomeric unit that comes from diol, derivatives, and this diol, derivatives comes from the N-octylpyrrolidone.In another embodiment, said thermoplastic polyurethane comprises the monomeric unit that comes from polytetramethylene ether diol.In a kind of further embodiment, said thermoplastic polyurethane comprises the monomeric unit that comes from polyethers.

In another kind of embodiment, said compsn also comprises one or more additives.

In another kind of embodiment, the said at least a functionalized polymkeric substance based on alkene is to be processed by the method that comprises the following steps:

1) at least a compound that comprises at least one " amine is reactive " group of grafting on based on the main chain of the polymkeric substance of alkene is to form the polymkeric substance of grafted based on alkene;

2) make of polymkeric substance and the primary-secondary diamine reaction of said grafted based on alkene; And

3) step 2 wherein) after step 1), carry out and do not separate the polymkeric substance of said grafted based on alkene, and step 1) and 2 wherein) all carry out with fusant reaction.

In a kind of further embodiment, said primary-secondary diamine is selected from down group: N-ethylethylenediamine, N-phenylethylenediamine, N-phenyl-1,2-phenylenediamine, N-phenyl-1,4-phenylenediamine and N-(2-hydroxyethyl)-quadrol.

In another kind of embodiment, the said at least a functionalized polymkeric substance based on alkene comprises and this following functional group based on the main chain covalent linkage knot of the polymkeric substance of alkene:

" NR wherein ₁NHR ₂" can come from the primary-secondary diamine that is selected from following structure (I) compound:

H ₂N-R ₁-NH-R ₂(I)，

R wherein ₁Be bivalent hydrocarbon radical, be preferably selected from alkylidene group, phenylene and more preferably-CH ₂CH ₂-,-to phenylene-,-adjacent phenylene-; R ₂For containing at least two carbon atoms and optional can be contained the substituted monovalence alkyl of heteroatom group, preferred alkyl or aryl and more preferably ethyl or phenyl.

1) with at least a functionalized said polymkeric substance of compound that comprises at least one " amine is reactive " group, to form the polymkeric substance of grafted based on alkene based on alkene;

2) with said grafted based on the polymkeric substance of alkene with solid-state non-fusion form and at least a primary-secondary diamine blend;

3) said primary-secondary diamine is sucked in the polymkeric substance of said grafted based on alkene;

4) make said primary-secondary diamine and said grafted polymer reaction, to form the functionalized polymkeric substance of imide based on alkene based on alkene.

In one embodiment, said suction step is carried out when room temperature.In another kind of embodiment, said blend step is carried out when room temperature.

2) make of polymkeric substance and the alkanolamine reaction of said grafted based on alkene; And

Step 2 wherein) after step 1), carry out and do not separate the polymkeric substance of grafted based on alkene, and step 1) and 2 wherein) all carry out with fusant reaction.

In a kind of further embodiment, said alkanolamine is selected from down group: 2-monoethanolamine, 2-amino-1-propyl alcohol, 3-amino-1-propyl alcohol, 2-amino-1-butanols, 2-(2-amino ethoxy)-ethanol and 2-amino-benzene methyl alcohol.

" NR wherein ₁OH " can come from the alkanolamine that is selected from following structure (II) compound:

H ₂N-R ₁-OH(II)，

R wherein ₁Be bivalent hydrocarbon radical, preferred R ₁For replacing or unsubstituted alkylidene group, more preferably R ₁Be selected from down group: ethylidene, propylidene, butylidene and be selected from alkoxyl group and the substituted alkylidene group of phenyl groups, and more preferably R by one or more ₁For-CH (OCH ₂CH ₂Me) CH ₂-or/and-adjacent phenylene-CH ₂-.

In another kind of embodiment, the said at least a functionalized polymkeric substance based on alkene is formed by the method that may further comprise the steps:

1) in fusant reaction, the compound of at least a following formula of grafting (IV) on based on the main chain of the polymkeric substance of alkene, to form the polymkeric substance of grafted based on alkene:

(IV), and

2) the said grafted of thermal treatment is based on the polymkeric substance of alkene, forming the functionalized polymkeric substance of imide based on alkene, and R wherein ₁And R ₂Be the C of hydrogen or straight or branched independently ₁-C ₂₀Alkyl; R ₃C for hydrogen or straight or branched ₁-C ₂₀Alkyl; R ₄Bivalent hydrocarbon radical for straight or branched; X is OH or NHR ₅, R wherein ₅Alkyl or hydroxyethyl for straight or branched.

In a kind of further embodiment, R ₁And R ₂Be hydrogen or C independently ₁-C ₁₀Alkyl.In another kind of embodiment, R ₃Be hydrogen or C ₁-C ₁₀Alkyl, and R wherein ₄Be divalence C ₁-C ₂₀Alkyl.

In another kind of embodiment, the said at least a functionalized polymkeric substance based on alkene comprises the following functional group with the main chain covalent linkage knot of said polymkeric substance based on alkene:

R wherein ₁And R ₂Be the C of hydrogen or straight or branched independently ₁-C ₂₀Alkyl; R ₄Bivalent hydrocarbon radical for straight or branched; X is OH or NHR ₅, R wherein ₅Alkyl or hydroxyethyl for straight or branched.

In a kind of further embodiment, R ₁And R ₂Be hydrogen or C independently ₁-C ₁₀Alkyl.In another kind of embodiment, R ₄Be divalence C ₁-C ₂₀Alkyl.

Compsn of the present invention also can comprise one or more additives.For example, compsn of the present invention also can comprise at least a filler.In another kind of embodiment, said filler is talcum or has used at least a amine silane surface modified talcum.In another kind of embodiment, compsn of the present invention can comprise the polar polymer that is selected from down group: polyester, polymeric amide, polyethers, polyetherimide, Z 150PH, polycarbonate, urethane, POLYACTIC ACID, polyesteramide and combination thereof.

In another kind of embodiment, the surface energy of said compsn is more than or equal to 35 dynes per centimeter.

Compsn of the present invention can comprise the combination of two kinds or more kinds of embodiments as herein described.

The present invention also provides a kind of goods that comprise at least one assembly that is formed by compsn of the present invention.In a kind of further embodiment, said goods be thin slice, carpet, tackiness agent, line sheath, cable, vest, trolley part, footwear component, coating, foam layer zoarium, lamination injection-molded item, automobile crust, awning, oilcloth, leatherware, roof building goods, bearing circle, powder coating, powder slush moulding thing, durable consumer goods, handle, handle, computer module, band, attach ornaments, shoe assembly, travelling belt or Timing Belt or fabric.

In another kind of embodiment, said goods are the tack coat between the extrusion sheet, the tack coat between the extruded film; Tack coat between the extrusion profile, the tack coat between the cast-sheet, the tack coat between the casting films; Tack coat between the curtain coating section bar, the tack coat between the perhaps aforesaid combination.

The present invention also provides a kind of film that comprises the layer that one deck at least forms by compsn of the present invention.In another kind of embodiment, the present invention provides a kind of and comprises two-layer at least film, and wherein at least one deck form by compsn of the present invention.In another kind of embodiment, the moisture transmission rates of film of the present invention (moisture vapor transmission rate) is 7g/hr/ft at least ²

The present invention also provides a kind of extrusion sheet that is formed by compsn of the present invention.In a kind of further embodiment, the surface energy of said sheet material is more than or equal to 30 dynes per centimeter, be preferably greater than or equal 33 dynes per centimeter, more preferably greater than or equal 35 dynes per centimeter.In another kind of embodiment, the thickness of said sheet material is 10～1000 mils, preferred 15～500 mils, and more preferably 20～100 mils.In another kind of embodiment, said sheet material thermal ageing in the time of 120 ℃ keeps at least 50% of its initial elongation after 500 hours, preferably at least 60% (ASTM D-882-02).

The present invention also provides the paint substrates coated, and wherein said base material is formed by compsn of the present invention.In one embodiment, said paint (paint) comprises at least a additive that is selected from down group: acrylic polymers, Synolac, cellulose material, melamine resin, urethane resin (urethane resin), carbamate resins, vibrin, vinyl acetate resin, epoxide, polyvalent alcohol and/or alcohols.In another embodiment, this paint is the paint based on water.In another embodiment, this paint is the paint based on organic solvent.

The present invention also provides a kind of dispersion-s that comprises compsn of the present invention.In another kind of embodiment, said dispersion-s also comprises at least a additive that is selected from down group: acrylic polymers, Synolac, cellulose material, melamine resin, urethane resin, carbamate resins, vibrin, vinyl acetate resin, epoxide, polyvalent alcohol and combination thereof.In another kind of embodiment, said dispersion-s is the dispersion-s based on water.In another kind of embodiment, said dispersion-s is the dispersion-s based on organic solvent.

The present invention also provides a kind of injection-molded item that comprises at least one integral part that is formed by compsn of the present invention.

The present invention also provides a kind of radio frequency welding goods that comprise at least one integral part that is formed by compsn of the present invention.

The present invention also provides a kind of lamination injection-molded item, and it comprises: the base material that (a) is formed by the compsn that comprises polar polymer, and the moulding veneer (overlay) that (b) is formed by compsn of the present invention.In one embodiment, said polar polymer is polycarbonate (PC), ABS, PC/ABS or nylon.The present invention also provides a kind of lamination injection-molded item, and it comprises: the base material that (a) is formed by compsn of the present invention, and the moulding veneer that (b) is formed by the compsn that comprises polar polymer.In one embodiment, said goods are the form of handle, handle or band.

The present invention also provides a kind of laminate structures that comprises the first layer and the second layer, and wherein said the first layer is formed by compsn of the present invention, and the wherein said second layer is to be formed by the compsn that comprises polar polymer.In another kind of embodiment, the one deck in the said layer is foam forms.In another kind of embodiment, the one deck in the said layer is form of fabric.In another kind of embodiment, said laminate structures is the form of awning, oilcloth or automobile crust or bearing circle.In another kind of embodiment, the said second layer is to be formed by the component that comprises polycarbonate.

The present invention also provides a kind of moulded parts that comprises first integral part and second integral part, and wherein said first integral part is to be formed by the compsn that comprises polar polymer, and wherein said second integral part is formed by compsn of the present invention.In another kind of embodiment, said goods are the automobile crust, attach ornaments, the form of shoe assembly, travelling belt, Timing Belt or durable consumer goods.

The present invention also provides footwear product, and it comprises at least one integral part that is formed by compsn of the present invention.In a kind of further embodiment; These goods are selected from down group: at the bottom of footwear outer bottom, sole middle level, the footwear list, lamination injection-molded item, natural leather goods, synthetic leather goods, vamp, laminate, clad products, boots, sandals, overshoes, plastic shoes, and their combination.

The present invention also provides a kind of thermoforming sheet material that comprises the layer that one deck at least forms by compsn of the present invention.

The present invention also provides a kind of trolley part that comprises the layer that one deck at least forms by compsn of the present invention.The present invention also provides a kind of trolley part that is formed by compsn of the present invention for example test board or door face board.

The present invention also provides the leatheroid that comprises at least one integral part that is formed by compsn of the present invention.

The present invention also provides the artificial turf that comprises at least one integral part that is formed by compsn of the present invention.

The present invention also provides a kind of tackiness agent that comprises at least one component that is formed by compsn of the present invention.The present invention also provides a kind of coated substrate that comprises tackiness agent of the present invention and at least one component that is formed by Kevlar.

The present invention also provides a kind of goods that formed by compsn of the present invention, and the surface energy of wherein said goods is more than or equal to 35 dynes per centimeter.

Goods of the present invention can comprise the combination of two kinds or more kinds of embodiments as herein described.

The present invention also provides a kind of preparation method for compositions of the present invention, and said method comprises melting mixing component A, B and C.In one embodiment, the mixing of required component is simultaneously.In another kind of embodiment, the mixing of required component is in succession, with any order.In another kind of embodiment, said melting mixing is carried out in forcing machine.In another kind of embodiment, said melting mixing is carried out with " online (in-line) " compounding technology.

Method of the present invention can comprise the combination of two kinds or more kinds of suitable embodiments as herein described.

Compsn of the present invention can comprise the combination of two kinds or more kinds of suitable embodiments as herein described.

Goods of the present invention can comprise the combination of two kinds or more kinds of suitable embodiments as herein described.

Functionalized polymkeric substance based on alkene

1. general introduction

The functionalized polymkeric substance based on alkene includes but not limited to the functionalized polymkeric substance based on alkene of carboxylic acid, acid anhydride, alcohol, amine, epoxy, halogen, isocyanic ester, other group and their combination.Functionalized can be along main chain based on the polymkeric substance of alkene, on the end of the chain,, and/or carry out as side chain as block segments.

In one embodiment, the said functionalized polymkeric substance based on alkene is the functionalized polymkeric substance based on ethene, and preferred functionalized ethylene/alpha-olefin interpolymers, its melt index (I ₂) utilize ASTMD-1238 (190 ℃, 2.16kg load) to measure more than or equal to 0.5g/10 minute, be preferably greater than or equal 1g/10 minute, and more preferably greater than or equal 2g/10 minute.In another kind of embodiment, the said functionalized polymkeric substance based on alkene is the functionalized polymkeric substance based on ethene, and preferred functionalized ethylene/alpha-olefin interpolymers, its melt index (I ₂) utilize ASTM D-1238 (190 ℃, 2.16kg load) to measure to be less than or equal to 50g/10 minute, preferably to be less than or equal to 20g/10 minute, and be more preferably less than or equal 10g/10 minute.

In another kind of embodiment, the said functionalized polymkeric substance based on alkene is the functionalized polymkeric substance based on ethene, and preferred functionalized ethylene/alpha-olefin interpolymers, its melt index (I ₂) utilize ASTM1 D-1238 (190 ℃, 2.16kg load) to be determined as 0.5g/10 minute to 50g/10 minute, preferred 1g/10 minute to 20g/10 minute, and more preferably 2g/10 minute to 10g/10 minute.Comprise here and disclose 0.5g/10 minute to 50g/10 minute all independent value and sub-range.

In another kind of embodiment; The said functionalized polymkeric substance based on alkene is the functionalized polymkeric substance based on ethene, and preferred functionalized ethylene/alpha-olefin interpolymers, and its density is more than or equal to 0.84g/cc; Be preferably greater than or equal 0.85g/cc, and more preferably greater than 0.86g/cc.In another kind of embodiment; The said functionalized polymkeric substance based on alkene is the functionalized polymkeric substance based on ethene; And preferred functionalized ethylene/alpha-olefin interpolymers; Its density preferably is less than or equal to 0.90g/cc for being less than or equal to 0.91g/cc, and is more preferably less than or equals 0.89g/cc.

In another kind of embodiment; The said functionalized polymkeric substance based on alkene is the functionalized polymkeric substance based on ethene, and preferred functionalized ethylene/alpha-olefin interpolymers, and its density is 0.84～0.91g/cc; Preferred 0.85～0.90g/cc, and more preferably 0.86～0.89g/cc.Comprise and disclose all independent value and the sub-range of 0.84g/cc to 0.91g/cc here.

In another kind of embodiment, the said functionalized polymkeric substance based on alkene is the amine-functionalized polymkeric substance based on alkene, the polymkeric substance based on ethene that preferred amines is functionalized, and more preferably amine-functionalized ethylene/alpha-olefin interpolymers.In a kind of further embodiment, said terminal olefin is C ₃-C ₂₀Terminal olefin, preferred C ₃-C ₁₀Terminal olefin, and more preferably propylene, 1-butylene, 1-hexene or 1-butylene.

In another kind of embodiment, the said functionalized polymkeric substance based on alkene is the polymkeric substance based on alkene of hydroxy-functional, the polymkeric substance based on ethene of preferred hydroxy-functional, and the more preferably ethylene/alpha-olefin interpolymers of hydroxy-functional.In a kind of further embodiment, said terminal olefin is C ₃-C ₂₀Terminal olefin, preferred C ₃-C ₁₀Terminal olefin, and more preferably propylene, 1-butylene, 1-hexene or 1-butylene.

In one embodiment, the said functionalized polymkeric substance based on ethene is the functionalized polymkeric substance based on ethene of acid anhydride, and the preferred functionalized ethylene/alpha-olefin interpolymers of acid anhydride, its melt index (I ₂) utilize ASTM D-1238 (190 ℃, 2.16kg load) to be determined as more than or equal to 0.1g/10 minute, be preferably greater than or equal 0.5g/10 minute, and more preferably greater than or equal 1g/10 minute.In another kind of embodiment, the said functionalized polymkeric substance based on ethene is the functionalized polymkeric substance based on ethene of acid anhydride, and the preferred functionalized ethylene/alpha-olefin interpolymers of acid anhydride, its melt index (I ₂) utilize ASTM D-1238 (190 ℃, 2.16kg load) to be determined as to be less than or equal to 50g/10 minute, preferably to be less than or equal to 20g/10 minute, and be more preferably less than or equal 10g/10 minute.

In another kind of embodiment; The said functionalized polymkeric substance based on ethene is the functionalized polymkeric substance based on ethene of acid anhydride; And the preferred functionalized ethylene/alpha-olefin interpolymers of acid anhydride; Its density is more than or equal to 0.84g/cc, is preferably greater than or equals 0.85g/cc, and more preferably greater than 0.86g/cc.In another kind of embodiment; The said functionalized polymkeric substance based on ethene is the functionalized polymkeric substance based on ethene of acid anhydride; And the preferred functionalized ethylene/alpha-olefin interpolymers of acid anhydride; Its density preferably is less than or equal to 0.90g/cc for being less than or equal to 0.91g/cc, and is more preferably less than or equals 0.89g/cc.

In another kind of embodiment; The said functionalized polymkeric substance based on ethene is the functionalized polymkeric substance based on ethene of acid anhydride, and the preferred functionalized ethylene/alpha-olefin interpolymers of acid anhydride, and its density is 0.84～0.91g/cc; Preferred 0.85～0.90g/cc, and more preferably 0.86～0.89g/cc.Comprise and disclose all independent value and the sub-range of 0.84g/cc to 0.91g/cc here.

2. as the polyolefin polymer of the stock polymer of functionalized polymkeric substance based on alkene

Comprise high density polyethylene(HDPE) (HDPE), new LDPE (film grade) (LDPE), LLDPE (LLDPE), linear ethylene/alpha-olefin interpolymers, linear ethylene/alpha-olefin interpolymers or the many block interpolymers of alkene basically based on the instance of the polymkeric substance of alkene.

The proper raw material polymkeric substance also comprises HPP homopolymer polypropylene and propylene copolymer, and other based on the polymkeric substance of alkene for example those by one or more C ₄-C ₂₀The polymkeric substance that terminal olefin forms.But said conjugated diolefine, non-conjugated diene and/or the vinyl monomer that can randomly comprise copolymerization based on the polymkeric substance of alkene.

I) be used for the polymkeric substance based on ethene of functionalized polymkeric substance based on alkene

The polymkeric substance of preferred maleic anhydride graft comprises can be from the Amplify of Dow Chemical Company acquisition ^TMPolymkeric substance.Other instance comprises FUSABOND (can obtain from DuPont), EXXELOR (can obtain from ExxonMobil) and POLYBOND (can obtain from Chemtura).

In one embodiment, the polymkeric substance of said maleic anhydride graft comprises the grafted maleic anhydride of 0.3wt% to 1.5wt% by the gross weight of graftomer.In a kind of further embodiment, the polymkeric substance of said maleic anhydride graft is the polymkeric substance based on ethene of maleic anhydride graft.In a kind of further embodiment, the polymkeric substance of said maleic anhydride graft is the ethylene/alpha-olefin interpolymers of maleic anhydride graft.

As stated; The suitable polymkeric substance based on ethene for example comprises, the linear ethylene polymkeric substance of high density polyethylene(HDPE) (HDPE), LLDPE (LLDPE), ultra-low density polyethylene (ULDPE), even branching, the polymkeric substance of linear ethylene basically (being the long chain branching ethene polymers of even branching) and the ethene or the many block interpolymers of alkene of even branching.

The density that is used as the high density polyethylene(HDPE) (HDPE) of polyolefin resin is generally about 0.94～0.97g/cc.The commercial embodiments of HDPE is easy to buy from market.Other suitable ethene polymers comprises new LDPE (film grade) (LDPE), LLDPE (LLDPE) and linear extra-low density Vilaterm (VLDPE).New LDPE (film grade) (LDPE) under high pressure utilizes the preparation of radical polymerization condition usually.The density of new LDPE (film grade) is for being generally 0.91～0.94g/cc.

Form contrast with the LDPE of routine, LLDPE (LLDPE) is characterised in that if any also long chain branches seldom.The method for preparing LLDPE is well known in the art, and the class of trade of this polyolefin resin is obtainable.Generally speaking, LLDPE utilizes the Ziegler-Natta catalyst systems produce in gas-phase fluidized-bed reactor or liquid solution processing reactor.

LLDPE (LLDPE), ultra-low density polyethylene (ULDPE), evenly branching the linear ethylene interpretation, evenly branching the interpretation of linear ethylene basically or the many block interpolymers of alkene usually wherein polymerization at least a terminal olefin.Term used herein " interpretation " is meant that this polymkeric substance can be multipolymer, terpolymer or have any polymkeric substance more than a kind of polymerization single polymerization monomer.The useful monomers for preparing interpretation with ethylene copolymer comprises C ₃-C ₂₀Terminal olefin, more preferably C ₃-C ₁₀Terminal olefin specifically is propylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-heptene and 1-octene.Concrete preferred comonomer comprises propylene, 1-butylene, 1-hexene and 1-octene.

Generally speaking, suitable polyvinyl melt index I ₂Measurement is less than or equal to 1500 grams/10 minutes according to 190 ℃/2.16kg of ASTM 1238 conditions; Preferably be less than or equal to 1000 grams/10 minutes; Be more preferably less than or equal 500 the gram/10 minutes, even be more preferably less than or equal 100 the gram/10 minutes, and most preferably be less than or equal to 50 the gram/10 minutes.

The commercial embodiments of suitable interpretation based on ethene comprises all the ENGAGE that can obtain from The Dow ChemicalCompany ^TM, ATTANE ^TM, AFFINITY ^TM, DOWLEX ^TM, ELITE ^TMCan be from the EXCEED of Exxon Chemical Company acquisition ^TMAnd EXACT ^TMAnd can be from the TAFMER of the Mitsui Chemical Company acquisition ^TMPolymkeric substance.

" evenly " with " the even branching of having used term when relating to ethylene/alpha-olefin interpolymers ", wherein the alpha-olefin comonomer random distribution is in given polymer molecule, and all basically polymer molecules have the ratio of identical ethene and comonomer.The ethene interpretation that can be used for the even branching that the present invention implements comprises linear ethylene interpretation and linear ethylene interpretation basically.

Evenly the linear ethylene interpretation of branching is comprising there not being long chain branches but have short chain ramose ethene polymers; Said short chain branch comes from polymerization and introduces the comonomer in the interpretation, and said short chain branch is evenly distributed in the identical polymer chain and between the different polymer chain.That is to say that evenly the linear ethylene interpretation of branching does not have long chain branches, as the linear, low density polyethylene polymerization thing that utilizes homogeneous branching distribution polymerization prepared or the situation of line style high density polyethylene polyethylene polymers.Evenly the commercial embodiments of the linear ethylene/alpha-olefin interpolymers of branching comprises the TAFMER that is provided by Mitsui ChemicalCompany ^TMPolymkeric substance, and the EXACT that provides by ExxonMobil Chemical Company ^TMPolymkeric substance.

Be used for the interpretation of linear ethylene basically of the present invention and be described in USP 5272236,5278272,6054544,6335410 and 6723810; Complete content is separately all incorporated this paper into through reference.The said interpretation of linear ethylene basically is such ethene interpretation, and wherein the comonomer random distribution is in given interpretation intramolecularly, and in this interpretation basically all interpretation molecules all have identical ethene/comonomer ratio.In addition, the said interpretation of linear ethylene basically is the ethene interpretation with even branching of long chain branches.Long chain branches has the comonomer distribution identical with main polymer chain, and can have the length with the main polymer chain same length." line style basically " typically refers to polymkeric substance and on average is substituted with 0.01～3 long chain branches/1000 carbon atom.The short chain ramose carbon length that the length of long chain branches forms than incorporating main polymer chain into by a kind of comonomer is long.

Some polymkeric substance can be substituted with 0.01～1 long chain branches/1000 carbon atom, or 0.05～1 long chain branches/1000 carbon atom, specifically be 0.3～1 long chain branches/1000 carbon atoms.Basically the commercial embodiments of simple linear polymer comprises ENGAGE ^TMPolymkeric substance and AFFINITY ^TMPolymkeric substance (both all can obtain from The Dow Chemical Company).

The said interpretation of linear ethylene basically forms the ethene polymers of one type of unique even branching.They quite are different from the linear ethylene interpretation of Elston in the even branching of well-known that type routine described in the USP 3645992; In addition, they are not similar with the linear ethylene polymkeric substance of the Ziegler-Natta catalyst catalyzed polymerization of conventional non-homogeneous branching (for example utilizing ultra-low density polyethylene (ULDPE), LLDPE (LLDPE) or the high density polyethylene(HDPE) (HDPE) of people's disclosed method preparation in USP 4076698 such as Anderson for example); They neither be similar with the highly branched Vilaterm (for example new LDPE (film grade) (LDPE), ethylene-acrylic acid (EAA) multipolymer and ethane-acetic acid ethyenyl ester (EVA) multipolymer) of high-pressure free radical initiation.

The interpretation of linear ethylene basically that can be used for even branching of the present invention has excellent workability, also is like this even it has narrow relatively MWD.Unexpectedly, the said interpretation of linear ethylene basically according to the melt flow of ASTM D 1238 than (melt flow ratio, I ₁₀/ I ₂But) variation of wide region ground, and be independent of MWD (M basically _w/ M _nOr MWD).This unexpected behavior is fully opposite with the Ziegler-Natta polymeric linear polyethylene interpretation of linear ethylene interpretation of conventional even branching (for example Elston is at described in the U.S.3645992 those) and conventional non-homogeneous branching (for example people such as Anderson is at described in the U.S.4076698 those).Different with linear ethylene interpretation basically is, the rheological property that linear ethylene interpretation (no matter even or non-homogeneous branching) has makes I ₁₀/ I ₂Value increases along with MWD increases also.

" long chain branches (LCB) " can be through known routine techniques in the industry for example ¹³The C nucleus magnetic resonance ( ¹³CNMR) (for example utilizing, Randall (Rev.Micromole.Chem.Phys., C29 (2&3), method p.285-297)) measures spectrum.Two kinds of other methods are gel permeation chromatography-maller angle laser light scattering detector coupling (GPC-LALLS) and gel permeation chromatography-differential viscometer detector coupling (GPC-DV).Use these technology to be used for that long chain branches detects and basic theory is recorded in document well.Referring to for example Zimm, B.H. and Stockmayer, the J.Chem.Phys. of W.H.; 17,1301 (1949) and Rudin, the Modern Methods of Polymer Characterization of A.; JohnWiley & Sons, New York (1991) pp.103-112.

Compare with " linear ethylene polymkeric substance basically ", " linear ethylene polymkeric substance " is meant that this polymkeric substance does not have measurable or tangible long chain branches, that is to say, said polymkeric substance is substituted with on average less than 0.01 long chain branches/1000 carbon atom.

Different with the linear ethylene polymkeric substance of non-homogeneous branching; The ethene polymers that can be used for even branching of the present invention will preferably have single melting peak (utilizing dsc (DSC) to measure), and the linear ethylene polymkeric substance of said non-homogeneous branching is owing to the wide branching distribution of non-homogeneous branched polymer has 2 or more a plurality of melting peak.

Evenly the linear ethylene interpretation of branching is the known polymkeric substance of kind, and it has the simple linear polymer main chain, does not have measurable long chain branches, and has narrow MWD.Such polymkeric substance is the interpretation of the alpha-olefin comonomer of ethene and at least a 3～20 carbon atoms, and optimal ethylene and C ₃-C ₂₀The multipolymer of terminal olefin, the more preferably multipolymer of ethene and propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene or 1-octene, even the more preferably multipolymer of ethene and propylene, 1-butylene, 1-hexene or 1-octene.

This base polymer is disclosed in the for example USP 3645992 of Elston, and has developed the follow-up method of utilizing metalloscene catalyst to prepare such polymkeric substance, and for example, at EP 0 129 368, EP 0,260 999, USP 4701432; USP 4937301; USP 4935397; USP 5055438; And shown in the WO 90/07526 (they separately through with reference to incorporating this paper into) etc.Said polymkeric substance can prepare through conventional polymerization technique (for example vapor phase process, slurry process, solution method and high-pressure process).

In a kind of preferred embodiment of the present invention, will be used as the stock polymer in the graft reaction based on the interpretation of ethene.In a kind of further embodiment, said interpretation based on ethene is the ethylene/alpha-olefin interpolymers that comprises at least a terminal olefin.In another embodiment, said interpretation also comprises at least a diene.

In one embodiment, the MWD (M of said ethylene/alpha-olefin interpolymers _w/ M _n) be less than or equal to 10, preferably be less than or equal to 5.More preferably the MWD of said ethylene/alpha-olefin interpolymers is 1.1～5, again more preferably from about 1.5～4 or 1.5～3.Comprise here and disclose about 1～5 all independent value and sub-range.In a kind of further embodiment, said ethylene/alpha-olefin interpolymers is the linear ethylene/alpha-olefin interpolymers of even branching or the linear ethylene/alpha-olefin interpolymers basically of even branching.

Comonomer includes but not limited to propylene, iso-butylene, 1-butylene, 1-amylene, 1-hexene; The 3-Methyl-1-pentene, 4-methyl-1-pentene, 1-octene, unconjugated diene, polyenoid; Divinyl, isoprene, pentadiene, hexadiene (for example 1,4-hexadiene); Octadiene, vinylbenzene, halogenated styrenes, the substituted vinylbenzene of alkyl, tetrafluoroethylene; Vinyl benzo cyclobutene, naphthenics (naphthenics), cyclenes (for example cyclopentenes, tetrahydrobenzene, cyclooctene), and their mixture.Common and preferred, ethene and a kind of C ₃-C ₂₀Alpha-olefin copolymer.Preferred comonomer comprises propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene and 1-octene, more preferably comprises propylene, 1-butylene, 1-hexene and 1-octene.

Exemplary terminal olefin comprises propylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene and 1-decene.Said terminal olefin is suitably C ₃-C ₁₀Terminal olefin.Preferably, said terminal olefin is propylene, 1-butylene, 1-hexene or 1-octene.Exemplary interpretation comprises ethylene/propene (EP) multipolymer; Ethylene/butylene (EB) multipolymer; Ethylene/hexene (EH) multipolymer; Ethylene/octene (EO) multipolymer, (EAODM) interpretation of ethylene/alpha-olefin/diene modification (for example (EPDM) interpretation of ethylene/propylene/diene modification), and ethylene/propylene/octene terpolymer.Preferred multipolymer comprises EP, EB, EH and EO polymkeric substance.

Suitable diene and triolefin comonomer comprise: 7-methyl isophthalic acid, 6-octadiene, 3,7-dimethyl--1,6-octadiene, 5,7-dimethyl--1,6-octadiene, 3; 7,11-trimethylammonium-1,6, the 10-sarohornene (3,7,11-trimethyl-1,6,10-octatriene), the 6-methyl isophthalic acid; The 5-heptadiene, 1,3-butadiene, 1,6-heptadiene, 1,7-octadiene, 1; The 8-nonadiene, 1,9-decadiene, 1,10-11 carbon diene, norbornylene, tetracyclododecane, or their mixture; And preferred divinyl, hexadiene, and octadiene; And most preferably 1,4-hexadiene, 1,9-decadiene, 4-methyl isophthalic acid, 4-hexadiene, 5-methyl isophthalic acid, 4-hexadiene, NSC 7352, and 5-ethylidene-2-norbornylene (ENB).

Other unsaturated comonomer comprises: 1,3-butadiene, 1,3-pentadiene, norbornadiene and NSC 7352; C _8-40Vinyl aromatic compounds, it comprises vinylbenzene, adjacent-,-and p-methylstyrene, Vinylstyrene, vinyl biphenyl, vinyl naphthalene (vinylnapthalene); And halo C _8-40Vinyl aromatic compounds, for example chlorostyrene and fluorostyrene.

In another kind of embodiment, the melt index (I of said ethylene/alpha-olefin interpolymers ₂) utilize (190 ℃ of ASTM D-1238; 2.16kg load) be determined as 0.01 the gram/10 minutes to 1500 the gram/10 minutes; Preferred 0.1 the gram/10 minutes to 1000 the gram/10 minutes, more preferably 0.5 the gram/10 minutes to 500 the gram/10 minutes, perhaps 1 the gram/10 minutes to 100 the gram/10 minutes.Comprise here and disclose 0.01 and restrain/10 minutes to 1500 grams/10 minutes all independent value and sub-range.

In another kind of embodiment, the crystallinity percentage of said ethylene/alpha-olefin interpolymers is less than or equal to 60% through dsc measurement, preferably is less than or equal to 50%, is more preferably less than or equals 40%.Preferably, these crystallinity of polymer percentage ratios are 2%～60%, comprise 2%～60% all independent value and sub-range.Above-mentioned independent value and sub-range are disclosed in this.

In another kind of embodiment, the density of said ethylene/alpha-olefin interpolymers is less than or equal to 0.93g/cc, preferably is less than or equal to 0.92g/cc, is more preferably less than or equals 0.91g/cc.In another kind of embodiment, the density of said ethylene/alpha-olefin interpolymers is more than or equal to 0.85g/cc, be preferably greater than or equal 0.86g/cc, more preferably greater than or equal 0.87g/cc.

In another kind of embodiment, the density of said ethylene/alpha-olefin interpolymers is 0.85～0.93g/cm ³, preferred 0.86～0.92g/cm ³, more preferably 0.87～0.91g/cm ³Comprise here and disclose 0.85～0.93g/cm ³All independent value and sub-range.

In another kind of embodiment, the PRR of said ethylene/alpha-olefin interpolymers is described below more than or equal to 4, is preferably greater than or equals 8.

To moor (dyne-second/square centimeter (d-sec/cm ²)) the interpretation viscosity of meter can measure as follows easily: with the velocity of shear in scope 0.1～100 radian per second (rad/s), utilizing under the nitrogen atmosphere under the dynamic scan pattern of dynamic mechanical spectrometer (for example from Rheometrics RMS-800 or ARES) at 0.1～100rad/s in 190 ℃ and to measure.Viscosity at 0.1rad/s and 100rad/s is expressed as V respectively _0.1And V ₁₀₀, the ratio of the two is referred to as RR and is expressed as V _0.1/ V ₁₀₀

Through computes PRR value:

[3.82-interpretation mooney viscosity is (at 125 ℃ ML for PRR=RR+ ₁₊₄)] x0.3

In USP 6680361, described the mensuration of PRR, it incorporates this paper into fully through reference.

In one embodiment, the PRR of said ethylene/alpha-olefin interpolymers is 1～70 or 4～70.In another kind of embodiment, the PRR of said ethylene/alpha-olefin interpolymers is 4～70 or 8～70.In another kind of embodiment, the PRR of said ethylene/alpha-olefin interpolymers is 12～60, and is preferred 15～55, and most preferably 18～50.The PRR value of present business-like ethylene/alpha-olefin interpolymers of LCB with normal level is usually less than 3.In another kind of embodiment, the PRR of said ethylene/alpha-olefin interpolymers is less than 3, and preferably less than 2.In another kind of embodiment, the PRR of said ethylene/alpha-olefin interpolymers is-1 to 3, and is preferred 0.5 to 3, more preferably 1 to 3.Comprise here and disclose all independent PRR value and sub-ranges of-1 to 70.

T-type branching obtains through ethene or other terminal olefin and the copolymerization under suitable reactor condition of the undersaturated macromonomer of the end of the chain in the presence of how much defined catalysts usually; For example at WO00/26268 and described in the of equal value U.S.6680361 those, these patents are through with reference to incorporating this paper fully into.Such as in WO 00/26268 discussion, along with T-type branching level increases, the efficient of ME or turnout significantly reduce until production become infeasible economically till.T-type LCB polymkeric substance can not have measurable gel, but have very high-caliber T-type LCB through the metalloscene catalyst preparation.Because the polymkeric substance intrachain macromonomer of incorporating in the growth only has a unsaturated site of activity, the polymkeric substance of gained only comprises along the side chain of main polymer chain with the variable-length of different interval.

H-type branching usually through ethene or other terminal olefin with in polymerization technique, obtain with the diene copolymerization with two two keys of non-metallocene type catalyst reaction.Such as title hint, diene makes a polymer molecule link to each other through the diene bridge with another polymer molecule, the polymer molecule picture " H " of gained, this be described as with it long chain branching not as good as be described as crosslinked.When H-type branching is extremely adopted in expectation during high-caliber branching usually.If used too much diene; Then polymer molecule can form too much branching or crosslinked; Cause polymer molecule to become and be insoluble to (in solution process) in the reaction solvent, thereby make polymer molecule break away from solution, thereby cause in polymkeric substance, forming gel particle.

In addition, but the use passive metal cyclopentadienyl catalyst of H-type branching agent and reduce the efficient of catalyzer.Therefore, when using H-type branching agent, used catalyzer is not metalloscene catalyst usually.The catalyzer that in US6372847, is used to prepare H-type branched polymer is a vanadium type catalyzer.

In USP 5272236, described T-type LCB polymkeric substance, wherein the degree of LCB is a 0.01～3LCB/1000 carbon atom, and wherein catalyzer is how much defined catalysts.According to P.Doerpinghaus and D.Baird at The Journal of Rheology; 47 (3); " Separating the Effects of Sparse Long-Chain Branching onRheology from Those Due to Molecular Weight in Polyethylenes " among 2003 5/6 month pp 717-736, free radical method (for example being used to prepare those methods of new LDPE (film grade) (LDPE)) produces the polymkeric substance with high horizontal LCB.For example, the resin NA952 in the Table I of Doerpinghaus and Baird is that it comprises 3.9 a LCB/1000 carbon atom according to Table II through the LDPE of free radical method preparation.Can be from The Dow ChemicalCompany (Midland; Michigan; USA) ethylene/alpha-olefin copolymer (ethylene-octene copolymer) that being considered to of obtaining contained the LCB of M.L. comprises Resin A ffinity PL1880 and the Affinity PL1840 of Table I and II, and they comprise 0.018 a LCB/1000 carbon atom and 0.057LCB/1000 carbon atom respectively.

In one embodiment of the present invention, the T-type LCB level that has of ethylene/alpha-olefin copolymer component substantially exceeds the T-type LCB level of the ethylene/alpha-olefin copolymer that present commerce can get.Table 1A has listed the various LCB levels that can be used for ethylene/alpha-olefin interpolymers of the present invention.In another embodiment, the PRR of said ethylene/alpha-olefin interpolymers is more than or equal to 4.

In another kind of embodiment, the PRR of said ethylene/alpha-olefin interpolymers is preferably greater than more than or equal to 4 or equals 8, and MWD (MWD) is 1.1～5 preferred 1.5～4.5 more preferably 1.8～3.8 and most preferably 2.0～3.4.Comprise here and disclose 1.1～5 all independent value and sub-range.In a kind of further embodiment, the density of said ethylene/alpha-olefin interpolymers is less than or equal to 0.93g/cc, preferably is less than or equal to 0.92g/cc, is more preferably less than or equals 0.91g/cc.In another kind of embodiment, the density of said ethylene/alpha-olefin interpolymers is more than or equal to 0.86g/cc, be preferably greater than or equal 0.87g/cc, more preferably greater than or equal 0.88g/cc.In another kind of embodiment, the density of said ethylene/alpha-olefin interpolymers is 0.86～0.93g/cc, and comprises and disclose all independent value and the sub-range of 0.86～0.93g/cc here.

In another kind of embodiment; The PRR of said ethylene/alpha-olefin interpolymers is preferably greater than more than or equal to 4 or equals 8; And melt index I2 restrains/10 minutes more than or equal to 0.1, is preferably greater than or equals 0.5 gram perhaps to restrain/10 minutes more than or equal to 1.0 in/10 minutes.In another kind of embodiment, the melt index I2 of said ethylene/alpha-olefin interpolymers is less than or equal to 30 grams/10 minutes, preferably is less than or equal to 25 grams/10 minutes, is more preferably less than or equals 20 to restrain/10 minutes.In another kind of embodiment, the melt index I2 of said ethylene/alpha-olefin interpolymers be 0.1 the gram/10 minutes to 30 the gram/10 minutes, preferred 0.1 the gram/10 minutes to 20 the gram/10 minutes, more preferably 0.1 the gram/10 minutes to 15 the gram/10 minutes.Comprise here and disclose 0.1 and restrain/10 minutes to 30 grams/10 minutes all independent value and sub-range.

Be applicable to that ethylene/alpha-olefin interpolymers of the present invention can pass through the method preparation described in the USP 6680361 (also referring to WO 00/26268).The representative instance of suitable interpretation is single-row in following table 1A.EAO-1, EAO-2-1, EAO-8 and EAO-9 utilize the mixed catalyst system described in the USP 6369176 through the preparation of the method described in the WO 00/26268, and these patents are incorporated this paper into fully through reference.EAO-7-1 prepares in double-reactor through the method described in the WO 00/26268.Preparation described in EAO-E-A such as USP 5272236 and 5278272.USP 5272236,5278272,6680361 and 6369176 is incorporated this paper into through reference separately fully.

Table 1A: ethylene/alpha-olefin interpolymers

EAO	Mooney viscosity	MLRA/MV	PRR	Comonomer	Wt% ethene	Density g/cc
							T-branching (low-level)
EAO-A	26.2	0.3	-2.9	Butylene
							EAO-B	48.6	1.2	-5.5	Butylene
T-branching (low-level) to business level
							EAO-C	21.5	0.8	0.6	Octene
EAO-D	34.4	1.2	-0.8	Octene
							EAO-E	34.1	1.2	-0.5	Octene
EAO-E-A	32		0	Octene	58	0.86
							EAO-F	18.3	0.6	-0.5	Butylene

							T-branching (high level)
EAO-1	40.1	3.8	29	Butylene	87	0.90
							EAO-2	27	2.8	22	Butylene
EAO-2-1	26		19	Butylene	87	0.90
							EAO-3	36.8	2.4	15	Butylene
EAO-4	17.8	2.3	12	Butylene
							EAO-5	15.7	2.0	10	Butylene
EAO-6	37.1	7.6	70	Propylene
							EAO-7	17.4	3.4	26	69.5wt% ethene/30wt% propylene/0.5%ENB	69.5
EAO-7-1	20		21	Propylene/diene	69.5	0.87
							EAO-8	26		45	Propylene	70	0.87
EAO-9	30		17	Octene	70	0.88

H-branching
							EAO-G	24.5	10.9		76.8wt% ethene/22.3wt% propylene/0.9%ENB
EAO-H	27	7.1	72	72wt% ethene/22wt% propylene/6% hexadiene
							EAO-I	50.4	7.1		71wt% ethene/23wt% propylene/6% hexadiene
EAO-J	62.6	8.1	55	71wt% ethene/23wt% propylene/6% hexadiene

Mooney viscosity: the ML in the time of 125 ℃ ₁₊₄

The combination that can have two kinds or more kinds of suitable embodiments as herein described based on the polymkeric substance of ethene.

Ethylene/alpha-olefin interpolymers can have the combination of two kinds or more kinds of suitable embodiments as herein described.

The polymkeric substance that ii) is used for functionalized polymkeric substance based on alkene based on propylene

The suitable interpretation based on propylene comprises alfon, propylene interpretation and polyacrylic copolymer reactor (RCPP), the alpha-olefin comonomer that it can comprise the ethene of about 1～20wt% or contain 4～20 carbon atoms.Said propylene interpretation can be random or segmented copolymer, perhaps based on the terpolymer of propylene.

Be suitable for comprising ethene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecylene, 1-dodecylene and 4-methyl-1-pentene, 4-methyl isophthalic acid-hexene, 5-methyl isophthalic acid-hexene, vinyl cyclohexane and vinylbenzene with the comonomer of propylene polymerization.Preferred comonomer comprises ethene, 1-butylene, 1-hexene and 1-octene, more preferably ethene.

Optional is, said polymkeric substance based on propylene comprises the monomer with at least two two keys, and said monomer is preferably diene or triolefin.Suitable diene and triolefin comonomer comprise: 7-methyl isophthalic acid, 6-octadiene, 3,7-dimethyl--1,6-octadiene, 5,7-dimethyl--1,6-octadiene; 3,7,11-trimethylammonium-1,6,10-sarohornene, 6-methyl isophthalic acid, 5-heptadiene, 1; The 3-divinyl, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene; 1,9-decadiene, 1,10-11 carbon diene, norbornylene, tetracyclododecane, or their mixture; And preferred divinyl, hexadiene, and octadiene; And most preferably 1,4-hexadiene, 1,9-decadiene, 4-methyl isophthalic acid, 4-hexadiene, 5-methyl isophthalic acid, 4-hexadiene, NSC 7352, and 5-ethylidene-2-norbornylene (ENB).

Other unsaturated comonomer comprises: 1,3-pentadiene, norbornadiene and NSC 7352; C _8-40Vinyl aromatic compounds, it comprises vinylbenzene, adjacent-,-and p-methylstyrene, Vinylstyrene, vinyl biphenyl, vinyl naphthalene; And halo C _8-40Vinyl aromatic compounds, for example chlorostyrene and fluorostyrene.

The propylene interpretation that cherishes a special interest comprises the propylene/ethylene interpretation, propylene/1-butene interpretation, propylene/1-hexene interpretation; Propylene/4-methyl-1-pentene interpretation, propylene/1-octene interpretation, propylene/ethylene/1-butylene interpretation; Propylene/ethylene/ENB interpretation, propylene/ethylene/1-hexene interpretation, propylene/ethylene/1-octene interpretation; Propylene/styrene interpretation, and propylene/ethylene/styrene interpolymers.

The method of grasping by one of skill in the art (for example, using single-site catalysts (metallocenes or how much defined catalysts) or Ziegler Natta catalyzer) forms suitable Vestolen PP 7052.(for example people such as Galli is at Angew.Macromol.Chem. to make the condition that propylene and optional comonomers (for example ethene or 'alpha '-olefin monomers) grasp those skilled in the art; Vol.120; 73 (1984) or people such as E.P.Moore at Polypropylene Handbook; Hanser Publishers, New York, disclosed condition in the 1996 concrete 11-98 pages or leaves) polymerization down.Polyacrylic polymer comprises KF 6100 HPP homopolymer polypropylenes of Shell; KS 4005 polypropylene copolymers of Solvay; KS 300 polypropylene terpolymer of Solvay; And all can be from the INSPIRE of The Dow Chemical Company acquisition ^TMPolymkeric substance and VERSIFY ^TMPolymkeric substance.

Preferably; The melt flow (MFR) of said polymkeric substance based on propylene is measured as 0.01～2000 gram/10 minutes according to ASTM D 1238 under 230 ℃/2.16kg condition; More preferably 0.1～1000 gram is/10 minutes; More preferably 0.5～500 gram is/10 minutes, even more preferably 1～100 restrains/10 minutes.

In another kind of embodiment; The melt flow of said propylene/alpha-olefins interpretation (MFR) is measured as 0.01～300 gram/10 minutes according to ASTM D 1238 under 230 ℃/2.16kg condition; More preferably 0.1～200 gram is/10 minutes, and also more preferably 0.5～100 gram perhaps more preferably 1～50 restrained/10 minutes in/10 minutes.Comprise here and disclose 0.01～300 and restrain/10 minutes all independent value and sub-range.

Be used for the polymkeric substance based on propylene of the present invention and can have MWD (MWD) arbitrarily.The method that polymkeric substance based on propylene wide or narrow MWD is grasped by one of skill in the art forms.Can be through viscosity breaking or through utilizing single-site catalysts to make reactor drum grade (non-viscosity breaking) perhaps advantageously provides narrow MWD through these two kinds of methods polymkeric substance based on propylene.

Said polymkeric substance based on propylene can be the reactor drum grade, viscosity breaking, branching or link coupled (coupled), thereby the nucleation and the crystallization rate of increase are provided.Term used herein " link coupled " is meant that the polymkeric substance based on propylene is modification on the rheology, the change of (for example, in the forcing machine just before annular die head) molten polymer resistance to flow during they are presented at and extrude thus." yet viscosity breaking " is the chain rupture direction, and " link coupled " is crosslinked or the direction of knotting.As crosslinked a kind of instance, linking agent (for example, triazo-compound) is added in the polyacrylic polymer of higher melt flow velocity, make to obtain the melt flow more much lower than initial melt flow velocity at the polypropylene polymer composition of extruding the back gained.For coupling or branched p 0 lypropylene, preferred MFR afterwards is less than or equal to 0.7: 1 to the ratio of initial MFR, is more preferably less than or equals 0.2: 1.

The polymkeric substance based on propylene that is applicable to branching of the present invention is commercially available, for example with trade(brand)name Profax PF-611 and PF-814 available from Montell North America.Perhaps; The method preparation that suitable branching or link coupled can be grasped based on the polymkeric substance of propylene by one of skill in the art; For example through superoxide or electron beam treatment, like people such as DeNicola disclosed method (in the atmosphere of oxygen reduction, using high energy (ionization) radiation) in USP 5414027; The EP 0 190 889 of Himont (electron beam irradiation of isotactic polyprophlene at a lower temperature); USP 5464907 (Akzo Nobel NV); The EP 0 754 7 11 (peroxide treatment) of Solvay; And the U.S. Patent application 09/133576 (trinitride coupling agent) of submission on August 13rd, 1998.These patent/applications are all incorporated this paper into through reference separately.

Other suitable polymkeric substance based on propylene also comprises VERSIFY ^TMPolymkeric substance (The DowChemical Company) and VISTAMAXX ^TMPolymkeric substance (ExxonMobil Chemical Co.), LICOCENE ^TMPolymkeric substance (Clariant), EASTOFLEX ^TMPolymkeric substance (Eastman ChemicalCo.), REXTAC ^TMPolymkeric substance (Hunstman), and VESTOPLAST ^TMPolymkeric substance (Degussa).Other suitable polymers comprises propylene/alpha-olefins segmented copolymer and interpretation, and other segmented copolymer and interpretation based on propylene as known in the art.

In one embodiment, the functionalized polymkeric substance based on propylene is to be formed by the polymkeric substance and the preferred trinitride link coupled alfon of link coupled based on propylene.In a kind of further embodiment; The melt flow (MFR) of said trinitride link coupled alfon is measured as 1～100 gram/10 minutes according to ASTM D 1238 under 230 ℃/2.26kg condition; Be preferably 10～50 grams/10 minutes, more preferably 20～40 grams are/10 minutes.In another kind of embodiment; The said functionalized polymkeric substance based on propylene is functionalized alfon; Its melt flow (MFR) is measured as 50～500 grams/10 minutes according to ASTM D 1238 under 230 ℃/2.26kg condition, be preferably 80～450 grams/10 minutes.

In a kind of preferred embodiment of the present invention, will be used as the stock polymer in the graft reaction based on the interpretation of propylene.In a kind of further embodiment, said interpretation based on propylene is the propylene/alpha-olefins interpretation that comprises at least a terminal olefin.In another kind of embodiment, said interpretation also comprises at least a diene.In another kind of embodiment, said interpretation based on propylene is the propylene/ethylene interpretation.

Preferred comonomer includes but not limited to ethene, iso-butylene, 1-butylene, 1-amylene, 1-hexene; The 3-Methyl-1-pentene, 4-methyl-1-pentene, 1-octene, unconjugated diene, polyenoid; Divinyl, isoprene, pentadiene, hexadiene (for example 1,4-hexadiene); Octadiene, vinylbenzene, halogenated styrenes, the substituted vinylbenzene of alkyl, tetrafluoroethylene; Vinyl benzo cyclobutene, naphthenics, cyclenes (for example cyclopentenes, tetrahydrobenzene, cyclooctene), and their mixture.Said comonomer is generally and is preferably ethene or C ₄-C ₂₀Terminal olefin.Preferred comonomer comprises ethene, 1-butylene, 1-amylene, 1-hexene, 1-heptene and 1-octene, more preferably comprises ethene, 1-butylene, 1-hexene and 1-octene.

In another kind of embodiment, said polymkeric substance based on propylene is the propylene/alpha-olefins interpretation, and its MWD is less than or equal to 5, and preferably is less than or equal to 4, is more preferably less than or equals 3.The MWD of more preferably said propylene/alpha-olefins interpretation is 1.1～5, more preferably 1.5～4.5, again more preferably 2～4.In another kind of embodiment, said MWD preferably less than 3.0, is more preferably less than 2.8 less than 3.5, is more preferably less than 2.5, and most preferably less than 2.3.Comprise here and disclose about 1～5 all independent value and sub-range.

In another kind of embodiment; The melt flow of said propylene/alpha-olefins interpretation (MFR) is measured under 230 ℃/2.16kg condition according to ASTM D 1238 and is less than or equal to 2000 grams/10 minutes; Preferably be less than or equal to 1000 grams/10 minutes; Be more preferably less than or equal 500 the gram/10 minutes, even be more preferably less than or equal 100 the gram/10 minutes.In another kind of embodiment; The melt flow of propylene/alpha-olefins interpretation (MFR) is measured under 230 ℃/2.16kg condition more than or equal to 0.01 according to ASTM D 1238 and is restrained/10 minutes; Be preferably greater than or equal 0.1 and restrain/10 minutes; More preferably greater than or equal 0.5 the gram/10 minutes, even more preferably greater than or equal 1 the gram/10 minutes.

In another kind of embodiment; The melt flow of said propylene/alpha-olefins interpretation (MFR) is measured as 0.01～2000 gram/10 minutes according to ASTM D 1238 under 230 ℃/2.16kg condition; More preferably 0.1～1000 gram is/10 minutes; More preferably 0.5～500 gram is/10 minutes, perhaps more preferably 1～100 restrains/10 minutes.Comprise here and disclose 0.01～2000 and restrain/10 minutes all independent value and sub-range.

In another kind of embodiment, the crystallinity percentage of said propylene/alpha-olefins interpretation is less than or equal to 50% through dsc measurement, preferably is less than or equal to 40%, is more preferably less than or equals 35%.Preferably, these crystallinity of polymer percentage ratios are 2%～50%, comprise 2%～50% all independent value and sub-range.Above-mentioned independent value and sub-range disclosed herein.

In another kind of embodiment, the density of said propylene/alpha-olefins interpretation is less than or equal to 0.90g/cc, preferably is less than or equal to 0.89g/cc, is more preferably less than or equals 0.88g/cc.In another kind of embodiment, the density of said propylene/alpha-olefins interpretation is more than or equal to 0.83g/cc, be preferably greater than or equal 0.84g/cc, more preferably greater than or equal 0.85g/cc.

In another kind of embodiment, the density of said propylene/alpha-olefins interpretation is 0.83～0.90g/cm ³, preferred 0.84～0.89g/cm ³, more preferably 0.85～0.88g/cm ³Comprise here and disclose 0.83～0.90g/cm ³All independent value and sub-range.

In another kind of embodiment, said polymkeric substance based on propylene is the propylene/ethylene interpretation, and its MWD is less than or equal to 5, preferably is less than or equal to 4, is more preferably less than or equals 3.The MWD of more preferably said propylene/ethylene interpretation is 1.1～5, more preferably 1.5～4.5, more preferably 2～4.In another kind of embodiment, said MWD preferably less than 3.0, is more preferably less than 2.8 less than about 3.5, is more preferably less than 2.5, and most preferably less than 2.3.Comprise here and disclose about 1～5 all independent value and sub-range.

In another kind of embodiment; The melt flow of said propylene/ethylene interpretation (MFR) is measured under 230 ℃/2.16kg condition according to ASTM D 1238 and is less than or equal to 2000 grams/10 minutes; Preferably be less than or equal to 1000 grams/10 minutes; Be more preferably less than or equal 500 the gram/10 minutes, even be more preferably less than or equal 100 the gram/10 minutes.In another kind of embodiment; The melt flow of propylene/alpha-olefins interpretation (MFR) is measured under 230 ℃/2.16kg condition more than or equal to 0.01 according to ASTM D 1238 and is restrained/10 minutes; Be preferably greater than or equal 0.1 and restrain/10 minutes; More preferably greater than or equal 0.5 the gram/10 minutes, perhaps more than or equal to 1 the gram/10 minutes.

In another kind of embodiment; The melt flow of said propylene/ethylene interpretation (MFR) is measured as 0.01～2000 gram/10 minutes according to ASTM D 1238 under 230 ℃/2.16kg condition; More preferably 0.1～1000 gram is/10 minutes; Also more preferably 0.5～500 restrain/10 minutes, even more preferably 1～100 restrain/10 minutes.Comprise here and disclose 0.01～2000 and restrain/10 minutes all independent value and sub-range.

In another kind of embodiment; The melt flow of said propylene/ethylene interpretation (MFR) is measured as 0.01～300 gram/10 minutes according to ASTM D 1238 under 230 ℃/2.16kg condition; More preferably 0.1～200 gram is/10 minutes; Also more preferably 0.5～100 restrain/10 minutes, perhaps 1～50 gram is/10 minutes.Comprise here and disclose 0.01～300 and restrain/10 minutes all independent value and sub-range.

In another kind of embodiment, the crystallinity percentage of said propylene/ethylene interpretation is less than or equal to 50% through dsc measurement, preferably is less than or equal to 40%, is more preferably less than or equals 35%.Preferably, these crystallinity of polymer percentage ratios are 2%～50%, comprise 2%～50% all independent value and sub-range.Above-mentioned independent value and sub-range disclosed herein.

In another kind of embodiment, the density of said propylene/ethylene interpretation is less than or equal to 0.90g/cc, preferably is less than or equal to 0.89g/cc, is more preferably less than or equals 0.88g/cc.In another kind of embodiment, the density of said propylene/alpha-olefins interpretation is more than or equal to 0.83g/cc, be preferably greater than or equal 0.84g/cc, more preferably greater than or equal 0.85g/cc.

In another kind of embodiment, the density of said propylene/ethylene interpretation is 0.83～0.90g/cm ³, be preferably 0.84～0.89g/cm ³, 0.85～0.88g/cm more preferably ³Comprise here and disclose 0.83～0.90g/cm ³All independent value and sub-range.

In one embodiment, be at least about 60wt% based on the content (based on the gross weight of polymerisable monomer) of the unit that comes from propylene that polymkeric substance comprised in interpretation of propylene, preferably at least about 80wt%, more preferably at least about 85wt%.The typical content of unit in propylene/ethylene copolymer that comes from ethene is at least about 0.1wt%; Preferably at least about 1wt%; More preferably at least about 5wt%; And the maximum level (based on the gross weight of polymerisable monomer) of the unit that comes from ethene that exists in these multipolymers in multipolymer is no more than about 35wt% usually, preferably is no more than about 30wt%, more preferably no more than about 20wt%.If exist, the content (based on the gross weight of polymerisable monomer) of unit in interpretation that comes from other unsaturated comonomer is generally at least about 0.01wt%, preferably at least about 1wt%, more preferably at least about 5wt%; And the maximum level (based on the gross weight of polymerisable monomer) of unit in interpretation that comes from said unsaturated comonomer is no more than about 35wt% usually, preferably is no more than about 30wt%, more preferably no more than about 20wt%.The total content (based on the gross weight of polymerisable monomer) of unit in interpretation that comes from ethene and any unsaturated comonomer is no more than about 40wt% usually, preferably is no more than about 30wt%, more preferably no more than about 20wt%.

In another kind of embodiment; Said polymkeric substance based on propylene comprises propylene and is different from the unsaturated comonomer of ethene with one or more; And the content (based on the gross weight of polymerisable monomer) of its unit that comes from propylene that comprises in interpretation is generally at least about 60wt%; Preferably at least about 70wt%, more preferably at least about 80wt%.The content (based on the gross weight of polymerisable monomer) of said one or more unsaturated comonomers of interpretation in interpretation is at least about 0.1wt%; Preferably at least about 1wt%; More preferably at least about 3wt%; And the maximum level (based on the gross weight of polymerisable monomer) of unsaturated comonomer in interpretation is no more than about 40wt% usually, preferably is no more than about 30wt%.

In one embodiment, said interpretation based on propylene be utilize metal center, heteroaryl ligand catalyst and one or more acvators combined preparation of aikyiaiurnirsoxan beta for example.In certain embodiments, said metal is one or more hafniums and zirconium.More particularly, in some embodiment of catalyzer, found that for heteroaryl ligand catalyst the use with zirconium compared with metal hafnium metal is preferred.In certain embodiments, catalyzer is the compsn that comprises part and metal precursor and randomly also can comprise acvator, acvator combination or acvator bag.

Be used to prepare catalyzer based on the polymkeric substance of propylene and also comprise the catalyzer that contains assistant ligand-hafnium complex, assistant ligand-zirconium complex and optional acvator, this catalyst polymerization and copolymerization (concrete and alkene, diolefine or other unsaturated compound monomer).Can use zirconium complex and hafnium complex.Metal-ligand complex can be to be in neutrality or electriferous state.Metal also can change with the ratio of part, and definite ratio depends on the person's character of part and metal-ligand complex.Metal-ligand complex can take a different form, for example, they can be monomeric, dimerization, or even more high-grade.The appropriate catalyst structure is described in USP 6919407 the 16th hurdle the 6th with relevant part and walks to the 41st hurdle the 23rd row, and it incorporates this paper into through reference.In a kind of further embodiment; Said polymkeric substance based on propylene comprises the propylene of 50wt% (based on the gross weight of polymerisable monomer) and the ethene of 5wt% (based on the gross weight of polymerisable monomer) at least at least, and has and be in about 14.6ppm and 15.7ppm ¹³C NMR peak, said peak is corresponding to zone errors and intensity (for example, walk to the 15th hurdle the 51st row referring to USP 6919407 the 12nd hurdle the 64th, its through with reference to incorporating this paper into) about equally.

Said interpretation based on propylene can be through any preparation of method easily.In one embodiment, the single reaction container of the reagent of this method (just (i) propylene, (ii) ethene and/or one or more unsaturated comonomers, (iii) catalyzer and (iv) optional solvent and/or molecular weight regulator hydrogen for example) being delivered to any appropriate designs is for example in stirring tank, endless tube or the fluidized-bed.The reagent of said method is contacted down to form desired polymkeric substance in conditions suitable (for example solution, slurry, gas phase, suspension, high pressure), then the recovery of reactor drum output is used for post-reaction treatment.Come all outputs of autoreactor disposablely to reclaim (when the situation of one way or batch reactor); Perhaps it can the discharging current form reclaim; It forms only a part of common a fraction of reaction mass (when the situation of continuous processing reactor; Wherein from reactor drum, discharge output stream, thereby make polymerization keep being in steady state conditions) to add the identical speed of speed with reactant." reaction mass " be meant between common polymerization period or polymerization after reactor drum in content.Reaction mass comprises reactant, solvent (if any), catalyzer and product and by product.Recovered solvent and unreacted monomer can be recycled in the reaction vessel.Suitable polymerizing condition is described in USP 6919407 the 41st hurdle the 23rd and walks to the 45th hurdle the 43rd row, and it incorporates this paper into through reference.

The combination that can have two kinds or more kinds of suitable embodiments as herein described based on the polymkeric substance of propylene.

The propylene/alpha-olefins interpretation can have the combination of two kinds or more kinds of suitable embodiments as herein described.

The propylene/ethylene interpretation can have the combination of two kinds or more kinds of suitable embodiments as herein described.

The many block interpolymers of alkene that iii) are used for functionalized polymkeric substance based on alkene

Many block interpolymers of alkene as described herein and preferred copolymer can be used as the stock polymer of functionalised polyolefin equally.

Vi) be used for functionalized polymkeric substance based on alkene based on the olefin polymer blend

In one embodiment of the present invention; The blend of two or more functionalized polymkeric substance based on alkene can be used as the component of functionalized polymkeric substance based on alkene; For example, functionalized polymkeric substance and the blend of functionalized polymkeric substance based on propylene as herein described based on ethene as herein described.

In another kind of embodiment, can use one or more functionalized blends for example as herein described based on the polymkeric substance of alkene and one or more functionalized many block interpolymers of alkene for example as herein described.

In one embodiment, functionalized polymkeric substance based on ethene as herein described can with functionalized many block interpolymers of alkene blend as herein described.

In another kind of embodiment, functionalized polymkeric substance based on propylene as herein described can with functionalized many block interpolymers of alkene blend as herein described.In another kind of embodiment, functionalized polymkeric substance and functionalized polymkeric substance based on propylene as herein described based on ethene as herein described can with functionalized many block interpolymers of alkene blend as herein described.

3. the grafting agent and the initiator that are used for functionalized polymkeric substance based on alkene

The disclosed olefin polymer of this paper can carry out modification through conventional grafting, hydrogenation, nitrene insertion (nitreneinsertion) reaction or other functionalization well known to those skilled in the art.Preferred modification is the graft reaction that adopts free radical mechanism,

Various free redical grafted materials can link to each other with polymkeric substance individually or as short grafting.These materials comprise each self-contained at least one heteroatomic unsaturated molecule.These materials include but not limited to maleic anhydride, dibutyl maleinate, dicyclohexyl maleate, diisobutyl maleate, the two octadecyl esters of toxilic acid, N-phenylmaleimide, citraconic anhydride, tetrahydronaphthalic anhydride, bromination maleic anhydride, chlorination maleic anhydride, NA acid anhydrides (nadic anhydride), methyl N A acid anhydrides, alkenyl succinic anhydride, toxilic acid, FUMARIC ACID TECH GRADE, diethyl fumarate, methylene-succinic acid, citraconic acid, Ba Dousuan, and the ester separately of these compounds, imide, salt and Diels-Alder adducts.These materials also comprise silane compound.

Free redical grafted material in the silicane material can link to each other with polymkeric substance individually or as short grafting.These materials include but not limited to vinyl alkoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyltriacetoxy silane, vinyl trichloro silane etc.In general, this type of material hydrolysable group of including but not limited to link to each other for example alkoxyl group, acyloxy or halogen group with silicon.This type of material also comprises the not hydrolysising group that links to each other with silicon for example alkyl and siloxy-.

Other free redical grafted material can link to each other with polymkeric substance individually or as short grafting.These materials include but not limited to methylacrylic acid; Vinylformic acid; Acrylic acid Diels-Alder adducts; Methacrylic ester (comprising TEB 3K, Jia Jibingxisuanyizhi, NSC 20956, Propenoic acid, 2-methyl, isobutyl ester, ethylhexyl methacrylate, lauryl methacrylate(LMA), stearyl methacrylate, methylacrylic acid hydroxyl ethyl ester, dimethylaminoethyl methacrylate); Propenoate (comprising methyl acrylate, ethyl propenoate, Bing Xisuandingzhi, NSC 20949, EHA, lauryl acrylate, octadecyl acrylate, Hydroxyethyl Acrylate); SY-Monomer G; The trialkoxy silane methacrylic ester, 3-(methacryloxypropyl) propyl trimethoxy silicane and3-(methacryloxypropyl) propyl group-triethoxyl silane for example, methacryloxypropyl methyltrimethoxy silane, methacryloxypropyl Union carbide A-162; Vinyl cyanide; 2-sec.-propyl-2-oxazoline; Vinylbenzene; Alpha-methyl styrene; Vinyl toluene; Dichlorostyrene; The N-vinyl pyrrolidone, vinyl-acetic ester, methacryloxypropyl trialkoxy silane, methacryloxypropyl methyl trialkoxysilane and vinylchlorid.

Can use the free redical grafted substance mixture that comprises at least a above-mentioned substance, illustrative example has phenylethylene/maleic anhydride and styrene/acrylonitrile.

Hot joining branch method is a kind of reaction method, yet, can use such as other light-initiated grafting method, comprise the generation of multi-form radiation, electron beam or redox radical.

When terminal unsaturation group (for example vinyl group) or inner unsaturated group are present in polymkeric substance, also can on this type group, take place functionalized.This type of functionalized hydrogenation, halogenation (for example chlorination), ozonize, hydroxylation, sulfonation, carboxylation, epoxidation and graft reaction of including but not limited to.Can through known chemistry with any functional group for example halogen, amine, acid amides, ester, carboxylic acid, ether, silane, siloxanes etc. or unsaturated functionality compound for example maleic anhydride add to end or inner unsaturated place.Other functionalization methods include the following U.S. Patent 5,849,828 entitled "Metalation? And? Functionalization? OfPolymers? And? Copolymers", U.S. Patent 5,814,708 entitled "Process? For? OxidativeFunctionalization? Of? Polymers? Containing? Alkylstyrene" and U.S. Patent No. 5,717,039 Title the "Functionalization? of? Polymers? Based? on? Koch? Chemistry? and? DerivativesThereof" those methods described.These patents are incorporated this paper through reference into its integral body separately.

Exist several kinds can comprise compound, percarboxylic acids and the percarboxylate, alkylation hydroperoxy-and dialkyl peroxide and the diacyl peroxide etc. that contain azo through being decomposed to form the compound that radical comes the initiation grafting reaction.Many these compounds are described (referring to J.Branderup, E.Immergut, editor's such as E.Grulke " Polymer Handbook " the 4th edition, Wiley, NewYork, 1999, joint II, 1-76 page or leaf) with its character is existing.The material that decomposition through initiator forms is preferably the radical based on oxygen.More preferably initiator is selected from percarboxylate, peroxy ketal, dialkyl peroxide and diacyl peroxide.Some preferred initiators of the modification that is usually used in polymer architecture have been listed below.Also show separately chemical structure and theoretical radical productive rate below.Theoretical radical productive rate is the theoretical value of the radical that produces of every mole of initiator.

Theoretical free

Initiator title initiator structure base productive rate

Lucidol

2

Lauroyl peroxide

2

Dicumyl peroxide

2

Tert-butyl peroxide α-cumyl

2

Ditertiary butyl peroxide

2

Two t-amyl peroxy things

2

T-butylperoxyl benzoate

2

Peroxybenzoic acid tert-pentyl ester

2

Theoretical free

Initiator title initiator structure base productive rate

1; 1-bis(t-butylperoxy)-3; 3,5-trimethyl-cyclohexane

4

α; α '-bis(t-butylperoxy)-1,3-diisopropyl benzene

4

α; α '-bis(t-butylperoxy)-1,4-diisopropyl benzene

4

2; 5-bis(t-butylperoxy)-2,5-dimethylhexane

4

2; 5-bis(t-butylperoxy)-2,5-dimethyl--3-hexin

4

In one embodiment, the present invention provides the olefin polymer with maleic anhydride graft.The olefin interconversion polymers of maleic anhydride graft can comprise also can not comprise a spot of hydrolysate and/or other verivate.In one embodiment, the MWD of the olefin interconversion polymers of maleic anhydride graft is about 1～7, and is preferred 1.5～6, and more preferably 2～5.Comprise here and disclose about 1 to 7 all independent value and sub-range.

In another kind of embodiment, the density of the olefin polymer of said maleic anhydride graft is 0.855～0.955g/cc, preferred 0.86～0.90g/cc, and more preferably 0.865～0.895g/cc.Comprise and disclose all independent value and the sub-range of 0.84g/cc to 0.955g/cc here.

In another kind of embodiment, the amount that is used for the maleic anhydride of graft reaction is less than or equal to 10phr (100 parts umber is by the weight of olefin interconversion polymers), preferably less than 5phr, and more preferably 0.5～10phr, even more preferably 0.5～5phr.Comprise and disclose all independent value and the sub-range of 0.05phr to 10phr here.

In another kind of embodiment; The amount that is used for the initiator of graft reaction is less than or equal to 10 mmole radicals/100 gram olefin interconversion polymers; Preferably be less than or equal to 6 mmole radicals/100 gram olefin interconversion polymers, be more preferably less than or equal 3 mmole radicals/100 gram olefin interconversion polymers.Comprise and disclose all independent value and the sub-range of 0.01～10 mmole/100 gram olefin interconversion polymers here.

In another kind of embodiment, the amount of grafted maleic anhydride composition is measured greater than 0.05wt% (by the weight of olefin interconversion polymers) through titrimetry, FTIR analysis or any other appropriate method on polyolefin chain.In a kind of further embodiment, this is measured greater than 0.25wt%, and in another further embodiment, this is measured greater than 0.5wt%.In an embodiment preferred, grafting the maleic anhydride of 0.5wt%～2.0wt%.Be considered in protection scope of the present invention and be disclosed in this greater than all independent values of 0.05wt% and sub-range.

Can in the presence of radical initiator such as superoxide and azo cpd etc. or through ionizing rays, maleic anhydride and many other undersaturated heteroatoms materials that contains be grafted on the polymkeric substance usually through any ordinary method.Organic initiators is preferred; For example any peroxide initiator; Like dicumyl peroxide, ditertiary butyl peroxide, t-butylperoxyl benzoate, Lucidol, cumene hydroperoxide, the sad tert-butyl ester of mistake, methyl-ethyl-ketone peroxide, 2,5-2,2; 5-dimethyl--2,5-two (t-butylperoxy)-3-hexin, lauryl peroxide and t-butyl peroxy-acetate.Suitable azo cpd is 2,2 '-azo diisobutyl nitrile.Said organic initiators has different reactivities when differing temps, and can produce dissimilar radicals and be used for grafting.Those skilled in the art can be selected from suitable organic initiators according to the grafting condition.

The amount of the amount of the initiator that in graft process, adopts and type, maleic anhydride and reaction conditions can influence (comprising temperature, time, shearing, environment, additive, thinner etc.) final texture of maleation polymkeric substance.For example, maleic anhydride/succinyl oxide, its oligopolymer and verivate (comprising hydrolysate) grafted degree on graftomer thereof are influenced by aforementioned Consideration can.In addition, the degree of branching and type and crosslinked amount also can receive the influence of reaction conditions and concentration.Generally speaking, preferably make crosslinked minimum during maleation technology.The composition of raw material olefin interpretation also can work in the final structure of maleation polymkeric substance.Resulting structures and then influence the character and the purposes of final product.Usually, the consumption of initiator and maleic anhydride is no more than the amount that the maleation level that provides desired and desired fluidity of molten (each free functionalized polymeric and subsequent use thereof require) are determined.

Graft reaction should make grafting degree on the main polymer chain maximum with side reaction (the for example homopolymerization of grafting agent, its not with the grafting of olefin interconversion polymers) carry out under the condition of degree minimum.The some parts of maleic anhydride (and/or its verivate) does not graft on the olefin interconversion polymers much, and expectation minimizes unreacted grafting agent usually.Graft reaction can carry out in melt, solution, solid-state, solvent swelling state etc.Maleation can be carried out in various device, such as but not limited to twin screw extruder, single screw extrusion machine, Brabender mixing tank and batch reactor etc.

The polymkeric substance of preferred maleic anhydride graft comprises can be from the Amplify of The Dow Chemical Company acquisition ^TMPolymkeric substance.Other instance comprises FUSABOND (can obtain from DuPont), EXXELOR (can obtain from ExxonMobil) and POLYBOND (can obtain from Chemtura).

In one embodiment, the polymkeric substance of said maleic anhydride graft comprises the grafted maleic anhydride of 0.3wt% to 1.5wt%, by the gross weight of graftomer.In a kind of further embodiment, the polymkeric substance of said maleic anhydride graft is the polymkeric substance based on ethene of maleic anhydride graft.In a kind of further embodiment, the polymkeric substance of said maleic anhydride graft is the ethylene/alpha-olefin interpolymers of maleic anhydride graft.

Other embodiment of the present invention also provides with other carbonyl containing compound grafted olefin interconversion polymers.In one embodiment, it is described that the MWD of these grafted olefin interconversion polymers and/or density can be same as or be similar to the olefin interconversion polymers that regards to maleic anhydride graft.In another kind of embodiment, the amount of employed graft compound and initiator is same as or is similar to as stated the employed amount of olefin interconversion polymers for maleic anhydride graft in the preparation of these grafted olefin interconversion polymers.In another kind of embodiment, the level of the graft compound that these grafted olefin interconversion polymers comprise is same as or is similar to the level that the olefin interconversion polymers of maleic anhydride graft as stated comprises.

Other carbonyl containing compound includes but not limited to dibutyl maleinate, dicyclohexyl maleate, diisobutyl maleate, the two octadecyl esters of toxilic acid, N-phenylmaleimide, citraconic anhydride, tetrahydronaphthalic anhydride, bromination maleic anhydride, chlorination maleic anhydride, NA acid anhydrides, methyl N A acid anhydrides, alkenyl succinic anhydride, toxilic acid, FUMARIC ACID TECH GRADE, diethyl fumarate, methylene-succinic acid, citraconic acid, Ba Dousuan, and their ester, their imide, their salt and their Diels-Alder adducts.

In one embodiment, the present invention provides with at least a silane compound grafted olefin interconversion polymers.Silane grafted olefin interconversion polymers can comprise also can not comprise a spot of hydrolysate and/or other verivate.

In another kind of embodiment, the MWD of said silane grafted olefin interconversion polymers is about 1～7, and is preferred 1.5～6, and more preferably 2～5.Comprise here and disclose about 1 to 7 all independent value and sub-range.

In another kind of embodiment, the density of said silane grafted olefin interconversion polymers is 0.855～0.955g/cc, preferred 0.86～0.90g/cc, and more preferably 0.865～0.895g/cc.Comprise and disclose all independent value and the sub-range of 0.84g/cc to 0.955g/cc here.

In another kind of embodiment, the amount of silane that is used for graft reaction is more than or equal to 0.05phr (by the weight of olefin interconversion polymers), more preferably 0.5～6phr, even more preferably 0.5～4phr.Comprise and disclose all independent value and the sub-range of 0.05phr to 6phr here.

In another kind of embodiment; The amount that is used for the initiator of graft reaction is less than or equal to 4 mmole radicals/100 gram olefin interconversion polymers; Preferably be less than or equal to 2 mmole radicals/100 gram olefin interconversion polymers, be more preferably less than or equal 1 mmole radical/100 gram olefin interconversion polymers.Comprise and disclose all independent value and the sub-range of 0.01～4 mmole/100 gram olefin interconversion polymers here.

In another kind of embodiment, the amount of grafted silane component is measured more than or equal to 0.05wt% (by the weight of olefin interconversion polymers) through FTIR analysis or other appropriate method on polyolefin chain.In a kind of further embodiment, this is measured more than or equal to 0.5wt%, and in another further embodiment, this is measured more than or equal to 1.2wt%.In an embodiment preferred, the grafting amount of silane component on the olefin interconversion polymers is 0.5wt% to 4.0wt%.Be considered in protection scope of the present invention and be disclosed in this greater than all independent values of 0.05wt% and sub-range.

Suitable silane includes but not limited to those silane of general formula (I):

CH ₂＝CR-(COO) _x(C _nH _2n) _ySiR′ ₃ (I)。

In this formula, R is Wasserstoffatoms or methyl; X and y are 0 or 1, and condition is that y is 1 when x is 1; N is 1～12 the integer that comprises two ends, preferred 1～4; Each R ' is an organic group independently, includes but not limited to contain the alkoxyl group (for example methoxyl group, oxyethyl group, butoxy) of 1～12 carbon atom, aryloxy (for example phenoxy); Aralkoxy (for example benzyloxy); Aliphatic series or aromatics siloxy-, the aromatics acyloxy contains the aliphatic acyloxy (for example methanoyl, acetoxyl group, propionyloxy) of 1～12 carbon atom; Amino or substituted-amino (alkylamino, arylamino) perhaps contain the low alkyl group of 1～6 carbon atom.

In one embodiment, said silane compound is selected from vinyl trialkyl oxysilane, vinyl three acyloxy silanes or vinyl trichloro silane.In addition, can graft to effectively and/or any silane or the silane mixture of crosslinked olefin interconversion polymers all can be used for enforcement of the present invention.Suitable silane comprises the unsaturated silane that comprises undersaturated alkyl of ethylenic (for example vinyl, allyl group, pseudoallyl, crotonyl, cyclohexenyl or γ-(methyl) acryloxy allyl group) and hydrolysable group (for example-oxyl, alkylacyloxy (hydrocarbyloxy), alkyl amino or halogen).The instance of hydrolysable group comprises methoxyl group, oxyethyl group, methanoyl, acetoxyl group, propionyloxy, chlorine and alkylamino or arylamino.Preferred silane is the unsaturated organoalkoxysilane that can graft on the polymkeric substance.These silane and preparation method thereof have in people's such as Meverden USP 5266627 more comprehensively to be described, and this patent is incorporated this paper through reference into its integral body.Preferred silane comprise vinyltrimethoxy silane, vinyltriethoxysilane, 3-(Trimethoxy silane base) propyl methyl acid esters (γ-(methyl) acryloxy propyl trimethoxy silicane), and composition thereof.

Can in the presence of radical initiator such as superoxide and azo cpd etc. or through ionizing rays, silane be grafted on the polymkeric substance usually through any ordinary method.Organic initiators is preferred; For example any peroxide initiator; Like dicumyl peroxide, ditertiary butyl peroxide, t-butylperoxyl benzoate, Lucidol, cumene hydroperoxide, the sad tert-butyl ester of mistake, methyl-ethyl-ketone peroxide, 2; 5-2, lauryl peroxide and t-butyl peroxy-acetate.Suitable azo cpd is 2,2 '-azo diisobutyl nitrile.

The consumption of initiator and silane will influence the final structure of silane polymers grafted, for example the grafting degree of graftomer and the crosslinking degree of cure polymer.Resulting structures and then influence the physical properties and the mechanical properties of final product.Usually, the consumption of initiator and silane is no more than the crosslinked level that provides desired and the amount that polymer property determined of gained.

Graft reaction should carry out making under the minimum condition of grafting degree maximum and side reaction (the for example homopolymerization of grafting agent, it does not graft on the polymkeric substance) degree on the main polymer chain.Some silane reagents are because the steric hindrance characteristic, low reactivity in the molecular structure and/or other are former thereby minimal homopolymerization takes place or homopolymerization does not take place.

Promote the silylanization grafted to solidify (crosslinked) by crosslinking catalyst, and can use any crosslinked catalyzer that can effectively promote concrete grafted silane.These catalyzer generally include bronsted lowry acids and bases bronsted lowry, and organometallic compound, and said organometallic compound includes the complex compound or the carboxylate salt of organic titanate (salt), organic zirconium acid esters (salt) and lead, cobalt, iron, nickel, zinc and tin.

Can use dibutyl tin laurate, dioctyl tin maleate, dibutyltin diacetate, two sad dibutyl tins, stannous acetate, stannous octoate, lead naphthenate, zinc octoate, cobalt naphthenate etc.The amount of catalyzer will depend on concrete system to be solved.

In certain embodiments of the invention, can adopt double cross contact system effectively, it uses the combination of heat, moisture and cross-linking step.For example, can adopt aptly peroxide cross-linking agent and silane crosslinker coupling, peroxide cross-linking agent and radiation coupling, or contain sulfur crosslinking agent and silane crosslinker coupling.System open and requirement protection in USP 5911940 and 6124370 is got in touch in double cross, and the full content of these two pieces of patents is incorporated this paper into through reference.

4. be used for the original position of functionalized polymkeric substance based on alkene amine-functionalized with the original position hydroxy-functional

In a kind of preferred embodiment of the present invention, functionalized polymkeric substance based on alkene is the polymkeric substance of amine-functionalized polymkeric substance or hydroxy-functional based on alkene based on alkene.Can implement the technology of the amine-functionalized or hydroxy-functional of preparation with the form extruded of step based on the polymkeric substance of alkene; Promptly; Maleic anhydride (grafting agent) can be grafted on the polymkeric substance based on alkene in the first part of forcing machine; Carry out imidization, granulation afterwards in the part of back with primary-secondary diamine or alkanolamine then.

Perhaps, can operate two forcing machines or melt-mixing device by series system, to carry out two chemical steps.

For in melt by the acid anhydride grafted based on the polymer manufacture amino-functional of alkene polymkeric substance based on alkene, and not with the crosslinking reaction competition, need use general formula to be H ₂Primary-secondary diamine of N-R-NH-R, wherein R is at least C ₂Alkyl.Can excessive or this diamines of stoichiometry equivalent use of stoichiometry.

Primary suitable-secondary diamine comprises the compound of following structure (I):

H ₂N——R ₁——NH——R ₂ (I)。

In structure (I), R ₁Be bivalent hydrocarbon radical, be preferably formula-(CH ₂) _n-straight chain hydrocarbon, wherein n is more than or equal to 2, preferred n is 2～10, more preferably 2～8, even more preferably 2～6.R ₂For containing the monovalence alkyl of at least two carbon atoms, and the optional heteroatom group such as OH or SH of can being contained replaces.Preferably, R ₂Be formula-(CH ₂) _n-CH ₃Straight chain hydrocarbon, wherein n is 1～10, preferred n is 1～9, more preferably 1～7, even more preferably 1～5.

Other primary-secondary diamine includes but not limited to N-ethylethylenediamine, N-phenylethylenediamine, N-phenyl-1,2-phenylenediamine, N-phenyl-1,4-phenylenediamine and N-(2-hydroxyethyl)-quadrol.The instance of preferred primary-secondary diamine is as follows:

N-(ethyl) quadrol, N-ethyl-1, the 3-tn,

N-ethyl-1,4-tetramethylenediamine N-(2-hydroxyethyl) quadrol

N-(phenyl) quadrol, and N-(2-hydroxypropyl) quadrol

Alkanolamine is the compound that contains amino and at least one hydroxyl (preferably only a hydroxyl).Said amine can be primary amine or secondary amine, and preferred primary amine.Polyamines is to contain at least two amino compound of (preferably only containing two amino).

Suitable alkanolamine is those of following structure (II):

H ₂N——R ₁——OH(II)。

In structure (II), R ₁Be bivalent hydrocarbon radical, and be preferably formula-(CH ₂) _n-straight chain hydrocarbon, wherein n is more than or equal to 2, preferred n is 2～10, more preferably 2～8, even more preferably 2～6.

Other alkanolamine includes but not limited to, thanomin, 2-amino-1-propyl alcohol, 3-amino-1-propyl alcohol, 2-amino-1-butanols and 2-amino-benzene methyl alcohol.

The instance of preferred alkanolamine is as follows:

2-monoethanolamine 1-amino-2-hydroxy propane

3-aminopropanol 2-(2-amino ethoxy) ethanol

The 4-amino butanol

Other instance of suitable alkanolamine and suitable diamines is as shown in the formula shown in (III):

(III)。

In formula (III), X is O or NR ' (R ' be alkyl); R is H, CH independently of one another ₃Or CH ₂CH ₃And n is 0～50.Open and the preparation of azanol can be referring to USP 3231619,4612335 and 4888446, and its instruction is incorporated this paper into through reference.The instance of preferred alkanolamine comprise the 2-monoethanolamine, 1-amino-2-propyl alcohol, 2-amino-1-propyl alcohol, 3-amino-1-propyl alcohol, 2-(2-amino ethoxy) ethanol, 1-amino-2-butanols, 2-amino-3-butanols and polyoxyalkylenes glycol amine.Preferred alkanolamine is the 2-monoethanolamine.

In one embodiment, come the polymkeric substance of functionalized maleic anhydride with primary-secondary diamine or with alkanolamine based on alkene.

In a kind of further embodiment, the consumption of maleic anhydride is 0.10wt%～5.0wt%, is preferably 0.50wt%～3.0wt%, and 1.0wt%～2.0wt% more preferably, based on the weight of not functionalized graftomer based on alkene.

In a kind of further embodiment, the consumption of superoxide is 0.01wt%～0.5wt%, is preferably 0.05wt%～0.3wt%, and 0.1wt%～0.2wt% more preferably, based on the weight of not functionalized graftomer based on alkene.

In another further embodiment, the consumption of primary-secondary diamine or alkanolamine is 1～10 molar equivalent amine with respect to the grafting acid anhydrides, is preferably 2～8 molar equivalent amine, and 4～6 molar equivalent amine more preferably.

5. the maleinamic acid original position functionalization that is used for functionalized polymkeric substance based on alkene

Hydroxyl-also can prepare with single stage method through the corresponding maleinamic acid or derivatives thereof of superoxide initiation grafting with the ethylene-octene copolymer of amino-functional, this maleinamic acid or derivatives thereof are through the reaction formation of maleic anhydride and alkanolamine or primary-secondary diamine.

Maleinamic acid is shown in following structure (IV):

(IV)。

In structure (IV), R ₁And R ₂Be hydrogen or C independently ₁-C ₂₀The alkyl of straight or branched; R ₃Be hydrogen or C ₁-C ₂₀The alkyl of straight or branched; R ₄Be alkyl two bases of straight or branched; X is OH or NHR ₅, R wherein ₅Alkyl or hydroxyethyl for straight or branched.In an embodiment preferred, R ₁And R ₂Be the C of hydrogen or straight or branched independently ₁-C ₁₀Alkyl, the C of preferred straight or branched ₁-C ₈Alkyl, and the more preferably C of straight or branched ₁-C ₆Alkyl.In an embodiment preferred, R ₃C for hydrogen or straight or branched ₁-C ₁₀Alkyl, the C of preferred straight or branched ₁-C ₈Alkyl, and the more preferably C of straight or branched ₁-C ₆Alkyl.In an embodiment preferred, R ₄C for straight or branched ₁-C ₂₀Alkyl, the C of preferred straight or branched ₁-C ₁₀Alkyl, and the more preferably C of straight or branched ₁-C ₈Alkyl, even the more preferably C of straight or branched ₁-C ₆Alkyl.

In an embodiment preferred, R ₅C for straight or branched ₁-C ₂₀Alkyl, the C of preferred straight or branched ₁-C ₁₀Alkyl, and the more preferably C of straight or branched ₁-C ₈Alkyl, even the more preferably C of straight or branched ₁-C ₆Alkyl.In another embodiment, R ₅Be straight chain-(CH ₂) _n-CH ₃, wherein n is more than or equal to 1, and preferred n is 1～9, more preferably 1～7, even more preferably 1～5.R ₅Other instance include but not limited to following structure :-CH ₃,-CH ₂CH ₃,-CH ₂CH ₂CH ₃,-CH ₂CH ₂CH ₂CH ₃,-CH (CH ₃) CH ₃,-CH (CH ₃) CH ₂CH ₃,-CH ₂CH (CH ₃) CH ₃,-CH (CH ₃) CH ₂CH ₂CH ₃,-CH ₂CH (CH ₃) CH ₂CH ₃With-CH ₂CH ₂CH (CH ₃) CH ₃

Other maleinamic acid structure is as follows.In each structure, R ₃And R ₄As above define.

Preferred maleinamic acid has following structure (V):

(V)。

Maleinamic acid with shown in structure (V) comes functionalised polyolefin.

In one embodiment, the consumption of maleinamic acid is 0.10wt%～5.0wt%, is preferably 0.50wt%～3.0wt%, and 1.0wt%～2.0wt% more preferably, based on the weight of not functionalized graft polyolefin.

In a kind of further embodiment; The consumption of superoxide is 0.01wt%～1wt%, is preferably 0.01wt%～0.5wt%, and 0.05wt%～0.3wt% more preferably; Even 0.1wt%～0.2wt% more preferably, based on the amount of not functionalized graft polyolefin.

6. the diamines inhalation (Imbibe Process) that is used for functionalized polymkeric substance based on alkene

Also can use the diamines inhalation to come functionalized polymkeric substance based on alkene as herein described.Among this paper, at first use the group that reacts with amine functional group to carry out functionalized to polymkeric substance based on alkene.Preferably, with the functionalized polymkeric substance of anhydride group based on alkene.Under the temperature that is lower than based on the fusing point of the polymkeric substance of alkene, preferably in room temperature with at least a diamines and this functionalized mixed with polymers based on alkene.Diamines is absorbed or suck in the polymkeric substance based on alkene, and form succinamic acid with diamine reactant property radical reaction.Through mixture being heat-treated (for example in melt extruding technology), accomplish the reaction that diamines and diamine reactant property functional group form imide ring then.Suitable diamines comprises those diamines previously discussed.Inhalation method help to guarantee diamines with based on the polymkeric substance thorough mixing of alkene so that carry out effective functionalization.

Primary suitable-secondary diamine comprises the compound with following structure (VI):

H ₂N-R ₁-NH-R ₂(VI)。

In structure (VI), R ₁Be bivalent hydrocarbon radical, be preferably formula-(CH ₂) _n-straight chain hydrocarbon, wherein n is more than or equal to 2, preferred n is 2～10, more preferably 2～8, even more preferably 2～6.R ₂Be the monovalence alkyl that contains at least 1 carbon atom, the optional heteroatomic group such as OH or SH of can being contained replaces.Preferably, R ₂Be formula-(CH ₂) _n-CH ₃Straight chain hydrocarbon, wherein n is 0～10, preferred n is 0～9, more preferably 0～7, even more preferably 0～5.

Primary suitable-secondary diamine includes but not limited to; N-methyl-quadrol, N-ethylethylenediamine, N-phenylethylenediamine, N-methyl isophthalic acid; 3-tn, N-methyl ethylenediamine, N-phenyl-1; 2-phenylenediamine, N-phenyl-1,4-phenylenediamine, 1-(2-amino-ethyl)-piperazine, and N-(2-hydroxyethyl)-quadrol.The instance of preferred primary-secondary diamine is as follows:

N-(ethyl) quadrol, N-ethyl-1, the 3-tn,

N-ethyl-1,4-tetramethylenediamine N-(2-hydroxyethyl) quadrol

N-(phenyl) quadrol, N-(2-hydroxypropyl) quadrol

N-(methyl) quadrol, the N-methyl isophthalic acid, the 3-tn,

The N-methyl isophthalic acid, 4-tetramethylenediamine, and 1-(2-amino-ethyl) piperazine.

The many block interpolymers of alkene

U. S. application 11/376873 (Dow64405B) that the many block interpolymers of alkene are described in that International Application PCT/US05/008917, the U.S. of submitting on March 17th, 2005 disclose 2006/0199914, U.S. Provisional Application 60/876287, U.S. Provisional Application were submitted at March 15 in 60/876287,2006 and the U.S. Provisional Application of submitting on March 17th, 2,004 60/553906, they all intactly incorporate this paper into through reference.

In a kind of embodiment preferred, the many block interpolymers of said alkene are the many block interpolymers of ethylene/alpha-olefin.In further embodiment, the many block interpolymers of said ethylene/alpha-olefin comprise the ethene (by the total mole number of polymerisable monomer) greater than 50mol%.

The many block interpolymers of said ethylene/alpha-olefin have one or more in the following characteristic:

(1) average block index is greater than 0 and up to about 1.0, and molecular weight distribution mw/mn is greater than about 1.3; Or

(2) when utilizing TREF to carry out fractionation, have at least a between 40 ℃ and 130 ℃ the molecule cut of wash-out, it is characterized in that said cut has at least 0.5 and about at the most 1 blockiness index; Or

Tm＞-2002.9+4538.5 (d)-2422.2 (d) ²Or

(4) has about 1.7 to about 3.5 M _w/ M _n, it is characterized in that melting heat Δ H, in J/g and in degree centigrade the Δ amount, Δ T is defined as the highest DSC peak and the peak-to-peak temperature difference of the highest CRYSTAF, the numerical value of wherein said Δ T and Δ H has following relation:

As Δ H during greater than 130J/g, Δ T >=48 ℃,

Wherein said CRYSTAF peak utilizes at least 5% cumulative polymer determination, and if have discernible CRYSTAF peak less than 5% polymkeric substance, then the CRYSTAF temperature is 30 ℃; Or

When (5) using the film of the compression molding of ethylene/alpha-olefin interpolymers to measure at 300% strain and 1 round-robin elastic recovery rate in per-cent; Re; And has density d; In gram/cubic centimetre, wherein do not contain the satisfied following relation of numerical value of said Re of crosslinked phase time and d basically when said ethylene/alpha-olefin interpolymers:

Re＞1481-1629 (d); Or

(6) has when using the TREF fractionation molecule cut of wash-out between 40 ℃ and 130 ℃; The comonomer molar content that it is characterized in that said cut compares the comonomer molar content height at least 5% of the cut of suitable random ethylene interpretation wash-out between uniform temp with it; Wherein said suitable with it random ethylene interpretation has identical comonomer, and each character of its melt index, density and comonomer molar content (based on whole polymkeric substance) and said ethylene/alpha-olefin interpolymers differ ± 10% in; Or

(7) have storage modulus G ' (25 ℃) and the storage modulus G ' in the time of 100 ℃ (100 ℃) in the time of 25 ℃, wherein G ' (25 ℃) is about 1: 1 to about 9: 1 with the ratio of G ' (100 ℃).

In one embodiment, the many block interpolymers of said ethylene/alpha-olefin have a kind of in above-mentioned character (1)～(7).In another kind of embodiment, the many block interpolymers of said ethylene/alpha-olefin have above-mentioned character (1) at least.

In another kind of embodiment, the many block interpolymers of said ethylene/alpha-olefin have two kinds or more kinds of combinations in above-mentioned character (1)～(7).In another kind of embodiment, the many block interpolymers of said ethylene/alpha-olefin have above-mentioned character (1) at least, with the form of two kinds or more kinds of above-mentioned other character (2)～(7) combination.

In another kind of embodiment, the many block interpolymers of said ethylene/alpha-olefin are characterised in that in the following characteristic one or more:

(a) have about 1.7 to about 3.5 Mw/Mn, at least one in degree centigrade fusing point Tm and in the density d of gram/cubic centimetre, wherein the numerical value of Tm and d meets following relational expression:

T _m＞-2002.9+4538.5 (d)-2422.2 (d) ²Or

(b) has about 1.7 to about 3.5 M _w/ M _n, it is characterized in that melting heat Δ H, in J/g and in degree centigrade the Δ amount, Δ T is defined as the highest DSC peak and the peak-to-peak temperature difference of the highest CRYSTAF, the numerical value of wherein said Δ T and Δ H has following relation:

As Δ H during greater than 130J/g, Δ T >=48 ℃,

When (c) it is characterized in that using the film of the compression molding of ethylene/alpha-olefin interpolymers to measure at 300% strain and 1 round-robin elastic recovery rate in per-cent; Re; And has density d; In gram/cubic centimetre, wherein do not contain the satisfied following relation of numerical value of said Re of crosslinked phase time and d basically when said ethylene/alpha-olefin interpolymers:

Re＞1481-1629 (d); Or

(d) has when using the TREF fractionation molecule cut of wash-out between 40 ℃ and 130 ℃; The comonomer molar content that it is characterized in that said cut compares the comonomer molar content height at least 5% of the cut of suitable random ethylene interpretation wash-out between uniform temp with it; Wherein said suitable with it random ethylene interpretation has identical comonomer, and each character of its melt index, density and comonomer molar content (based on whole polymkeric substance) and said ethylene/alpha-olefin interpolymers differ ± 10% in; Or

(e) it is characterized in that storage modulus G ' (25 ℃) and the storage modulus G ' in the time of 100 ℃ (100 ℃) in the time of 25 ℃, wherein G ' (25 ℃) is about 1: 1 to about 10: 1 with the ratio of G ' (100 ℃); Or

(f) when utilizing TREF to carry out fractionation, have at least a between 40 ℃ and 130 ℃ the molecule cut of wash-out, it is characterized in that said cut has at least 0.5 and about at the most 1 blockiness index and greater than about 1.3 molecular weight distribution mw/mn; Or

(g) average block index is greater than 0 and up to about 1.0, and molecular weight distribution mw/mn is greater than about 1.3.

In one embodiment, the many block interpolymers of said ethylene/alpha-olefin have a kind of in the above-mentioned character (a)～(g).In another kind of embodiment, the many block interpolymers of said ethylene/alpha-olefin have above-mentioned character (g) at least.

In another kind of embodiment, the many block interpolymers of said ethylene/alpha-olefin have two kinds or more kinds of combinations in the above-mentioned character (a)～(g).In another kind of embodiment, the many block interpolymers of said ethylene/alpha-olefin have above-mentioned character (g) at least, with the form of two kinds or more kinds of above-mentioned other character (a)～(f) combination.

But the many block interpolymers of said ethylene/alpha-olefin comprise the ethene of polymerized form and the alpha-olefin comonomer of one or more copolymerization usually, are characterised in that a plurality of blocks or the segment of polymeric monomeric units different on two or more kind chemistry or the physical properties.That is, said ethylene/alpha-olefin interpolymers is a block interpolymer, preferred many block interpolymers or multipolymer.In this paper term " interpretation (interploymer) " and " multipolymer (copolymer) " interchangeable use.In some embodiments, said segmented copolymer can be represented with following formula:

(AB) _n

Wherein n is at least 1, is preferably greater than 1 integer, for example 2,3,4,5,10,15,20,30,40,50,60,70,80,90,100 or higher; " A " expression hard block or segment; " B " expression soft segment or segment.Preferably, A and B line style basically are connected, and are different from branching or star (radial) basically basically.In other embodiments, A block and B block random distribution in polymer chain.In other words, said segmented copolymer does not have following structure usually.

AAA-AA-BBB-BB

In the other embodiment, said segmented copolymer does not contain usually and comprises monomeric the third type block of different copolymer.In the other embodiment, block A and B block have random basically monomer or the comonomer that is distributed in the block separately.In other words, block A or B block all do not comprise two or more different inferior segments of forming (or inferior block), the terminal segments of for example different basically with the remainder of block compositions.

Said multi-block polymer comprises various amounts usually " firmly " with " soft " segment.The amount that " firmly " segment is meant therein ethylene by the weight of polymkeric substance greater than about 95wt% and be preferably greater than the block of the polymerized unit of about 98wt%.In other words, in said hard segment co-monomer content (the monomeric content outside the ethene) by the weight of polymkeric substance less than about 5wt% and preferably less than about 2wt%.In some embodiments, said hard segment comprises that whole ethene are formed or whole basically ethene.On the other hand, " soft " segment be meant co-monomer content (the monomeric content outside the ethene) wherein by the weight of polymkeric substance greater than about 5wt%, be preferably greater than about 8wt%, greater than about 10wt%, or greater than the block of the polymerized unit of about 15wt%.In some embodiments, co-monomer content can be greater than about 20wt% in said soft chain segment, greater than about 25wt%, and greater than about 30wt%, greater than about 35wt%, greater than about 40wt%, greater than about 45wt%, greater than about 50wt%, or greater than about 60wt%.

It usually is to account for about 1wt% of gross weight of block interpolymer to about 99wt% that said soft chain segment is present in amount in the block interpolymer, preferably accounts for about 5wt% about 95wt% extremely of the gross weight of block interpolymer, and about 10wt% is about 90wt% extremely; About 15wt% is to about 85wt%, and about 20wt% is to about 80wt%, and about 25wt% is to about 75wt%; About 30wt% is to about 70wt%; About 35wt% is to about 65wt%, and about 40wt% is to about 60wt%, and perhaps about 45wt% is to about 55wt%.On the contrary, hard segment can similar scope exist.Can be based on the wt% of the data computation soft chain segment that obtains from DSC or NMR and the wt% of hard segment.These class methods with calculate be disclosed in submitted to simultaneously on March 15th, 2006 with Colin L.P.Shan; People's such as Lonnie Hazlitt name is also assigned to the U.S. Patent application 11/376835 (file number 385063-999558) of Dow Global Technologies Inc.; Title is " an ethylene/alpha-olefin block interpolymer ", and its disclosure is incorporated this paper through reference into its integral body.

Term " crystallization " is meant that measuring polymkeric substance through differential scanning calorimetry (DSC) or suitable method has first step transformation or crystalline melting point (Tm) if you are using.This term can exchange with term " hypocrystalline " and use.Term " amorphous " is meant that measuring polymkeric substance through differential scanning calorimetry (DSC) or suitable method does not have crystalline melting point.

Term " segmented copolymer " or " segmented copolymer " be meant contain two kinds or more kinds of preferably with the line style mode engage in chemically different zones or the polymkeric substance of segment (being called " block "); Promptly; Be contained in chemically different unitary polymkeric substance; Said in chemically different unit for polymerising ethylene functional group, engage with the head and the tail mode, rather than to dangle or the grafted mode engages.In preferred embodiments, said block is different in the following areas: the amount of bonded comonomer or type, density, percent crystallinity, the crystallite dimension that is attributable to have the polymkeric substance of this composition, type or degree, degree of regioregularity or regional irregularity degree, branching amount (comprising long chain branching or ultra-branching), homogeneity or any other chemistry or the physical properties of tacticity (isotaxy or syndiotaxy) in block.Said segmented copolymer is characterised in that the unique distribution that polydispersity index (PDI or Mw/Mn), block length distribution and/or block number distribute, and this is because the peculiar methods of preparation multipolymer.More specifically, when preparing with continuous processing, the PDI of said polymkeric substance is suitably 1.7 to 2.9, and is preferred 1.8 to 2.5, and more preferably 1.8 to 2.2, most preferably 1.8 to 2.1.When with intermittently or Semi-batch Process when preparing, the PDI of polymkeric substance is 1.0 to 2.9, and is preferred 1.3 to 2.5, more preferably 1.4 to 2.0, most preferably 1.4 to 1.8.

The many block interpolymers of ethylene/alpha-olefin that are used for embodiment of the present invention (are also referred to as " interpretation of the present invention " sometimes; " polymkeric substance of the present invention ") but the ethene of polymerized form and the alpha-olefin comonomer of one or more copolymerization comprised; Be characterised in that a plurality of blocks or the segment of polymeric monomeric units (block interpolymer) different on two or more chemistry or the physical properties, preferred segmented copolymer.Said ethylene/alpha-olefin interpolymers is characterised in that the one or more aspects that are described below.

On the one hand, the many block interpolymers of ethylene/alpha-olefin that are used for embodiment of the present invention have about 1.7 to about 3.5 M _w/ M _nWith at least one in degree centigrade fusing point Tm and in the density d of gram/cubic centimetre, wherein the numerical value of these variablees is corresponding to the following relationship formula:

T _m＞-2002.9+4538.5 (d)-2422.2 (d) ², preferred

T _m>=-6288.1+13141 (d)-6720.3 (d) ², more preferably

T _m≥858.91-1825.3(d)+1112.8(d) ²。

These fusing point/density relationship are illustrated among Fig. 1.The conventional random copolymers of the ethylene/alpha-olefin that reduces with the reduction of density with fusing point is different, and the fusing point of interpretation of the present invention (representing with rhombus) is independent of density basically, especially when density is between about 0.87g/cc and about 0.95g/cc.For example, when density when 0.875g/cc is to about 0.945g/cc scope, the fusing point of this base polymer is in about 110～130 ℃ of scopes.In some embodiments, when density when 0.875g/cc is to about 0.945g/cc scope, the fusing point of this base polymer is in about 115～125 ℃ of scopes.

On the other hand; The many block interpolymers of said ethylene/alpha-olefin comprise the ethene and one or more terminal olefins of polymerized form; And it is characterized in that in degree centigrade the temperature that is defined as the highest differential scanning calorimetry (" DSC ") peak deduct the Δ T of the temperature at the highest crystal analysis fractionation (" CRYSTAF ") peak; With satisfy in the melting heat Δ H of J/g and Δ T and Δ H below relational expression:

Δ T＞-0.1299 (Δ H)+62.81, preferred

Δ T >=-0.1299 (Δ H)+64.38, more preferably

ΔT≥-0.1299(ΔH)+65.95，

As Δ H at the most during 130J/g.In addition, when Δ H during greater than 130J/g Δ T be equal to or greater than 48 ℃.The CRYSTAF peak be utilize accumulation at least 5% polymer determination (promptly; The polymkeric substance of accumulation at least 5% must be represented in this peak); And if have discernible CRYSTAF peak less than 5% polymkeric substance; So said CRYSTAF temperature is 30 ℃, and wherein Δ H is the numerical value in the melting heat of J/g.More specifically, the highest CRYSTAF peak comprises the polymkeric substance of accumulation at least 10%.Fig. 2 shows that the figure of alkene multi-block polymer and Comparative Examples paints data.Integration peak area and peak temperature calculate through the computerize cartographic programme of apparatus manufacturer supply.Expression is as the corresponding equation DELTA T=-0.1299 (Δ H)+62.81 of oblique line of random ethylene/octene polymer relatively.

Aspect another; The many block interpolymers of said ethylene/alpha-olefin have when using temperature rise drip washing fractionation (Temperature Rising Elution Fractiontion; " TREF ") when carrying out fractionation between 40 ℃ and 130 ℃ the molecule cut of wash-out; The comonomer molar content that it is characterized in that said cut compares the comonomer molar content height of the cut of suitable random ethylene interpretation wash-out between uniform temp with it; Be preferably height at least 5%; More preferably high by at least 10%, wherein said suitable with it random ethylene interpretation contains identical comonomer, and each character of the melt index that is had, density and comonomer molar content (based on whole polymkeric substance) and said block interpolymer differ ± 10% in.Preferably, the M of suitable with it interpretation _w/ M _nM with said block interpolymer _w/ M _nAlso differ ± 10% in, and/or total co-monomer content of the total co-monomer content that has of suitable with it interpretation and said block interpolymer differ ± 10 weight % in.

Aspect another; The many block interpolymers of said ethylene/alpha-olefin are characterised in that the elastic recovery rate Re that on the compression moulding film at ethylene/alpha-olefin interpolymers under 300% strain and 1 periodic condition, measures in %; And have density d in gram/cubic centimetre, and wherein do not satisfy following relational expression when ethylene/alpha-olefin interpolymers has the numerical value of crosslinked phase time Re and d basically:

Re＞1481-1629 (d); Preferably

Re >=1491-1629 (d); More preferably

Re >=1501-1629 (d); Most preferably

Re≥1511-1629(d)。

Fig. 3 has shown that density is to the influence by the elastic recovery rate of the non-oriented film of some interpretations of the present invention and the preparation of conventional random copolymers.For equal densities, interpretation of the present invention has significantly higher elastic recovery rate.

In some embodiments, with the pinblock velocity of separation of 11 cm per minute, the tensile strength of the many block interpolymers of said ethylene/alpha-olefin is higher than 10MPa; Preferred tensile strength >=11MPa; More preferably tensile strength >=13MPa, and/or elongation at break is at least 600%, more preferably at least 700%; Highly preferably at least 800%, topnotch preferably at least 900%.

In other embodiments, the many block interpolymers of said ethylene/alpha-olefin have: (1) 1～50, the ratio G ' (25 ℃) of preferred 1～20, more preferably 1～10 storage modulus/G ' (100 ℃); And/or (2) less than 80%, preferably less than 70%, specifically less than 60%, less than 50% or less than 40%, be low to moderate 0% compressed residual deformation.

In more another embodiment, 70 ℃ of compression sets of the many block interpolymers of said ethylene/alpha-olefin are less than 80%, less than 70%, less than 60% or less than 50%.Preferably, 70 ℃ of compression sets of interpretation are less than 40%, less than 30%, less than 20%, and can be low to moderate about 0%.

In some embodiments; The melting heat of the many block interpolymers of said ethylene/alpha-olefin is equal to or less than 100 pounds per square foots (4800Pa) less than 85J/g and/or pellet adhesion intensity (pellet blocking strength); Preferably be equal to or less than 50 pounds per square foots (2400Pa); Specifically be equal to or less than 5 pounds per square foots (240Pa), and be low to moderate 0 pounds per square foot (0Pa).

In other embodiments; The many block interpolymers of said ethylene/alpha-olefin comprise the ethene of 50mol% polymerized form at least, and at 70 ℃ of compression sets less than 80%, preferably less than 70% or less than 60%; Most preferably less than 40～50%, and be low to moderate near 0%.

In some embodiments, said segmented copolymer has the PDI that meets the Schultz-Flory distribution and do not meet the Poisson distribution.In addition, the characteristic of said multipolymer also is to have polydisperse block distributed and the distribution of polydisperse block size and the most probable distribution with block length.Said segmented copolymer preferably includes end-blocks and comprises 4 or more a plurality of blocks or those segmented copolymers of segmental interior.More specifically, said multipolymer comprises that end-blocks comprises at least 5,10 or 20 blocks or segment.

Co-monomer content any suitable method capable of using is measured, and wherein is preferably based on the method for nucleus magnetic resonance (" NMR ") spectrum.In addition, for the polymkeric substance with broad TREF curve or the blend of polymkeric substance, preferably polymkeric substance is at first utilized TREF to be fractionated into to have separately the cut of 10 ℃ or littler eluting temperature scope.That is to say that the collection temperature window of each eluting fraction is 10 ℃ or littler.Use this method, said block interpolymer has at least one such cut, and this cut has the comonomer molar content higher than the corresponding cut of suitable interpretation.

On the other hand; Said many block interpolymers are the olefin interconversion polymers; But preferably comprise the ethene of polymerized form and the comonomer of one or more copolymerization; The a plurality of blocks (that is, at least two blocks) or segment (block interpolymer), the most preferably segmented copolymer that it is characterized in that polymeric monomeric units different on two kinds or more kinds of chemistry or the physical properties.Preferred said block interpolymer have 40 ℃ with 130 ℃ between the peak (just molecule cut) of wash-out (but need not to collect and/or separate independent cut); It is characterized in that said peak has the co-monomer content that the unfolded ir spectra is estimated through utilizing whole width/half peak (FWHM) area to calculate; The average comonomer molar content of said segmented copolymer is than under identical eluting temperature and utilize whole width/half peak (FWHM) area to calculate and the average comonomer molar content at the suitable with it random ethylene interpretation peak of unfolded is high; Be preferably up to few 5%; Be more preferably up to few 10%; Wherein said suitable with it random ethylene interpretation comprises same comonomer, and the melt index that is had, density and comonomer molar content (based on whole polymkeric substance) drop on said block interpolymer melt index, density and comonomer molar content ± 10% scope in.Preferably; The Mw/Mn of said suitable interpretation also drop on said block interpolymer Mw/Mn ± 10% scope in, and/or total co-monomer content of said suitable interpretation drop on said block interpolymer total co-monomer content ± 10 weight % scopes in.Said whole width/half peak (FWHM) is calculated and is based on from the methyl of ATREF infrared detector and the ratio [CH of the pairing area of methylene radical ₃/ CH ₂], wherein confirm the climax according to baseline, confirm the FWHM area again.For the distribution that utilizes the ATREF peak to measure, the FWHM area is defined as at T ₁And T ₂Between area under a curve, T wherein ₁And T ₂Be the point of confirming on the left side at ATREF peak and right side through following method: peak height is halved, drawn a straight line with baseline values again, the left side of this straight line and ATREF curve and right side are crossing.The working curve of co-monomer content utilizes the random ethylene/alpha-olefin multipolymer to make, and will map to the FWHM area ratio at TREF peak from the co-monomer content of NMR.In this infrared method, form the working curve of the relevant comonomer of same type.The co-monomer content at the TREF peak of alkene multi-block polymer can be utilized the FWHM methyl at its TREF peak: the methylene radical area is than [CH ₃/ CH ₂] through confirming with reference to this working curve.

Co-monomer content any suitable method capable of using is measured, and wherein is preferably based on the method for nucleus magnetic resonance (" NMR ") spectrum.Utilize this method, said block interpolymer has the comonomer molar content higher than the suitable interpretation of correspondence.

Preferably; Interpretation for ethene and 1-octene; The co-monomer content of said block interpolymer TREF cut of wash-out between 40 and 130 ℃ is more than or equal to quantity (0.2013) T+20.07; More preferably greater than or equal quantity (0.2013) T+21.07, wherein T is for as the numerical value of the peak eluting temperature of TREF cut relatively (in ℃).

Fig. 4 illustrates the embodiment of ethene and 1-octene block interpolymer, and wherein several the suitable ethene/co-monomer content of 1-octene interpretation (random copolymers) is consistent with the line (solid line) of the graph of a relation of TREF eluting temperature with representative (0.2013) T+20.07.With dashed lines describes to represent the line of equation (0.2013) T+21.07.Also described the co-monomer content of the cut of several block ethene of the present invention/1-octene interpretation (many-segmented copolymer).Compare with arbitrary line, all block interpolymer cuts have obviously higher 1-octene content in the eluting temperature that equates.This result is the characteristic of interpretation of the present invention, and be considered to be in the polymer chain exist have simultaneously crystallographic property and amorphous property different block caused.

Fig. 5 illustrates the TREF curve and the co-monomer content of the polymer fraction of embodiment 5 (segmented copolymer) and Comparative Examples F polymkeric substance (utilizing the physical blending thing of two kinds of polymkeric substance that the polymerizations simultaneously of two kinds of catalyzer obtain).Two kinds of polymkeric substance from 40 ℃ to 130 ℃, are preferably from 60 ℃ of peaks to 95 ℃ of wash-outs and are divided into three parts, and each part is gone through the TR wash-out that is less than 10 ℃.Represent the real data of embodiment 5 with trilateral.Those skilled in the art can recognize, can be consistent with the TREF value that derives from the contrast interpretation (being preferably the random copolymers that uses metallocenes or other homogeneous catalysis preparation of compositions) with same monomer to containing the suitable calibration curve of the monomeric interpretation structure of different copolymer and being used as correlated line.Interpretation of the present invention is characterised in that, the comonomer molar content greater than in identical TREF eluting temperature from the value that calibration curve records, be preferably big at least by 5%, more preferably big at least 10%.

The aspect and character above the application is described, can characterize the alkene multi-block polymer through one or more further features.On the one hand; The alkene multi-block polymer is the olefin interconversion polymers; But preferably contain the ethene of polymerized form and the comonomer of one or more copolymerization; It is characterized in that two kinds or a plurality of blocks or the segment (block interpolymer) of more kinds of polymeric monomeric units that chemistry or physical properties are different; Most preferably be many-segmented copolymer; Said block interpolymer has the molecule cut of wash-out between 40 ℃ and 130 ℃ when using TREF increment (TREFincrement) fractionation, it is characterized in that the comonomer molar content of said cut is higher than the comonomer molar content of the suitable random ethylene interpretation cut of wash-out between identical eluting temperature, is preferably height at least 5%; More preferably high by at least 10%, 15%, 20% or 25%; Wherein said suitable random ethylene interpretation comprises identical comonomer, is preferably identical comonomer, and melt index, density and the comonomer molar content (based on whole polymkeric substance) of the melt index that is had, density and comonomer molar content (based on whole polymkeric substance) and block interpolymer differ ± 10% in.Preferably, the M of suitable interpretation _w/ M _nM with block interpolymer _w/ M _nAlso differ ± 10% in, and/or total copolymerization monomer content of total copolymerization monomer content of suitable interpretation and block interpolymer differ ± 10% in.

Preferably, top interpretation is the interpretation of ethene and at least a terminal olefin, and especially block polymer density is about 0.855 to about 0.935g/cm ³Those interpretations; And more particularly; For having the polymkeric substance that surpasses about 1 mole of % comonomer; The co-monomer content of said block interpolymer TREF cut of wash-out between 40 ℃ and 130 ℃ is more than or equal to the amount of (0.1356) T+13.89, more preferably more than or equal to the amount of (0.1356) T+14.93, and most preferably is the amount more than or equal to (0.2013) T+21.07; Wherein T is the numerical value of the peak A TREF eluting temperature of the TREF cut that compares, ℃ being that unit is measured.

Preferably, for the top ethene and the interpretation of at least a terminal olefin, especially block polymer density is about 0.855 to about 0.935g/cm ³Those interpretations; And more particularly for having the polymkeric substance that surpasses about 1 mole of % comonomer; The co-monomer content of said block interpolymer TREF cut of wash-out between 40 ℃ and 130 ℃ is more than or equal to the amount of (0.2013) T+20.07; More preferably more than or equal to the amount of (0.2013) T+21.07, wherein T is the numerical value of the peak value eluting temperature of the TREF cut that compares, ℃ being that unit is measured.

Aspect another; The alkene multi-block polymer is the olefin interconversion polymers; But preferably contain the ethene of polymerized form and the comonomer of one or more copolymerization; It is characterized in that two kinds or a plurality of blocks or the segment (block interpolymer) of more kinds of polymeric monomeric units that chemistry or physical properties are different; Most preferably be many-segmented copolymer, said block interpolymer has the molecule cut of wash-out between 40 ℃ and 130 ℃ when using the fractionation of TREF increment, it is characterized in that every kind of cut that co-monomer content is at least about 6 moles of % has greater than about 100 ℃ fusing point.For co-monomer content is about 3 moles of % those cuts to about 6 moles of %, and every kind of cut has about 110 ℃ or higher DSC fusing point.More preferably, said co-monomer content has the DSC fusing point corresponding to following equation for the polymer fraction of at least 1 mole of %:

T _m>=(5.5926) (molecular fraction of comonomer in the cut)+135.90.

Aspect another; Said alkene multi-block polymer is the olefin interconversion polymers; But preferably contain the ethene of polymerized form and the comonomer of one or more copolymerization; It is characterized in that two kinds or a plurality of blocks or the segment (block interpolymer) of more kinds of polymeric monomeric units that chemistry or physical properties are different; Most preferably be segmented copolymer, said block interpolymer has the molecule cut of wash-out between 40 ℃ and 130 ℃ when using the fractionation of TREF increment, it is characterized in that the ATREF eluting temperature more than or equal to every kind of about 76 ℃ cut have corresponding to following equation like fusion enthalpy (melting heat) through dsc measurement:

Melting heat (J/gm)≤(3.1718) (degree centigrade to be the ATREF eluting temperature of unit)-136.58.

Block interpolymer of the present invention has the molecule cut of wash-out between 40 ℃ and 130 ℃ when using the fractionation of TREF increment, it is characterized in that the ATREF eluting temperature 40 ℃ and be less than every kind of cut between about 76 ℃ have corresponding to following equation like fusion enthalpy (melting heat) through dsc measurement:

Melting heat (J/gm)≤(1.1312) (degree centigrade to be the ATREF eluting temperature of unit)+22.97.

Measuring ATREF peak comonomer through infrared detector forms

The comonomer at TREF peak form can use can derive from Spain Valencia Polymer Char ( Http:// www.polymerchar.com/) the IR4 infrared detector measure.

" compositional model " of detector is furnished with measurement inductor block (CH ₂) and form inductor block (CH ₃), said measurement inductor block (CH ₂) and form inductor block (CH ₃) be 2800-3000cm ^-1The fixed arrowband infrared-filtered device in zone.Measure inductor block and detect the methylene radical (CH on the polymkeric substance ₂) carbon (it directly relates to the polymer concentration in the solution), and form the methyl (CH that inductor block detects polymkeric substance ₃).Form signal (CH ₃) divided by measurement signal (CH ₂) the mathematics ratio responsive to the co-monomer content of the measurement polymkeric substance in the solution, and its response is proofreaied and correct with known ethylene standard substance.

When using with the ATREF instrument, detector provides the concentration (CH of wash-out polymkeric substance in the TREF process ₂) and form (CH ₃) signal response.Polymkeric substance specific correction (specific calibration) can be through to having the polymer measurement CH of known co-monomer content (preferably use NMR measure) ₃With CH ₂Area ratio set up.The co-monomer content at polymer A TREF peak can be through using each CH ₃And CH ₂(that is area ratio CH, is proofreaied and correct in the reference of response area ratio ₃/ CH ₂To co-monomer content) estimate.

Can be after using suitable baseline, use whole width/half peak (FWHM) to calculate peak area is calculated, with will be from each signal response integration of TREF color atlas.Whole width/half maximum value calculation is based on the ratio [CH of the methyl response area that derives from the ATREF infrared detector to methylene radical response area ₃/ CH ₂], wherein confirm the climax according to baseline, measure the FWHM area then.For the distribution that utilizes the ATREF peak to measure, the FWHM area is defined as at T ₁And T ₂Between area under a curve, T wherein ₁And T ₂Be the point of confirming on the left side at ATREF peak and right side through following method: peak height is halved, drawn a straight line with baseline values again, the left side of this straight line and ATREF curve and right side are crossing.

The co-monomer content that in this ATREF-infrared method, infrared spectroscopy is used to measure polymkeric substance with as below with reference to described in GPC/FTIR system similar substantially: Markovich, Ronald P.; Hazlitt, Lonnie G.; Smith, Linley; " Development of gel-permeationchromatography-Fourier transform infrared spectroscopy for characterization ofethylene-based polyolefin copolymers "; Polymeric Materials Science andEngineering (1991); 65,98-100; And Deslauriers, PJ.; Rohlfing, D.C.; Shieh, E.T.; " Quantifying short chain branching microstructures in ethylene-1-olefincopolymers using size exclusion chromatography and Fourier transform infraredspectroscopy (SEC-FTIR) "; Polymer (2002); 43; 59-170., incorporate the full content mode by reference of the two into this paper.

In other embodiments, said many blocks ethylene/alpha-olefin interpolymers is characterised in that greater than 0 and about at the most 1.0 average block index ABI with greater than about 1.3 MWD M _w/ M _nAverage block index ABI is the weighted average of the blockiness index (" BI ") of every kind of polymer fraction in preparation TREF, obtaining with 5 ℃ increment from 20 ℃ to 110 ℃:

ABI＝∑(w _iBI _i)，

BI wherein _iBe the blockiness index of the i cut of the ethylene/alpha-olefin interpolymers of the present invention that obtains among the TREF in preparation, and W _iIt is the weight percentage of i cut.

For each polymer fraction, BI defines with one of following two equations (the two all obtains identical BI value):

BI = \frac{1 / T_{X} - 1 / T_{XO}}{1 / T_{A} - 1 / T_{AB}}

Or

BI = - \frac{Ln P_{X} - Ln P_{XO}}{Ln P_{A} - Ln P_{AB}}

T wherein _xBe the preparation ATREF eluting temperature (preferably using K (Kelvin) expression) of i cut, P _XBe the ethene x of i cut, it can be measured through aforesaid NMR or IR.P _ABBe the ethene x of whole ethylene/alpha-olefin interpolymers (before fractionation), it also can be measured through NMR or IR.T _AAnd P _ABe the ATREF eluting temperature and the ethene x of pure " hard segment " (it is meant the crystallization segment of interpretation).If the actual value of " hard segment " can not obtain, then as first approximation, with T _AAnd P _AValue is set at the value of high density polyethylene(HDPE) homopolymer.For the calculating of carrying out among the application, T _ABe 372 ° of K, P _ABe 1.

T _ABBe to have same composition and have P _ABThe ATREF temperature of random copolymers of ethene x.T _ABCan be from following Equation for Calculating:

LnP _AB＝α/T _AB+β

Wherein α and β are two constants, and it can be proofreaied and correct through the known random ethylene multipolymer that uses some amount and confirm.It should be noted that α and β can change with instrument.And people possibly need to form and themselves calibration curve of establishment in the similar molecular weight ranges of cut therewith with interested polymkeric substance.There is slight molecular weight effect.If calibration curve gets the molecular weight ranges of self similarity, this effect can be ignored basically.In some embodiments, relation below the random ethylene multipolymer satisfies:

Ln?P＝-237.83/T _ATREF+0.639

T _XOBe to have same composition and have P _XThe ATREF temperature of random copolymers of ethene x.T _XOCan be from LnP _X=α/T _XO+ β calculates.On the contrary, P _XOBe to have same composition and have T _XThe ethene x of random copolymers of ATREF temperature, it can be from Ln P _XO=α/T _X+ β calculates.

In case obtain the blockiness index (BI) of each preparation TREF cut, weighted average blockiness index ABI that can the computing whole polymkeric substance.In some embodiments, ABI is greater than 0 but less than about 0.3, or from about 0.1 to about 0.3.In other embodiments, ABI is greater than about 0.3 and about at the most 1.0.Preferably, ABI should be about 0.4 to about 0.7, about 0.5 to about 0.7, or about 0.6 to about 0.9 scope.In some embodiments, ABI is about 0.3 to about 0.9, about 0.3 to about 0.8, or about 0.3 to about 0.7, about 0.3 to about 0.6, about 0.3 to about 0.5, or about 0.3 to about 0.4 scope.In other embodiments, ABI is about 0.4 to about 1.0, about 0.5 to about 1.0, or about 0.6 to about 1.0, about 0.7 to about 1.0, about 0.8 to about 1.0, or about 0.9 to about 1.0 scope.

Another feature of said many blocks ethylene/alpha-olefin interpolymers be said many blocks ethylene/alpha-olefin interpolymers comprise at least a can be through the polymer fraction that obtains of preparation TREF; Wherein said cut has greater than about 0.1 and the highest about 1.0 blockiness index, and greater than about 1.3 MWD (Mw/Mn).In some embodiments, the blockiness index that said polymer fraction has is greater than about 0.6 and the highest about 1.0, greater than about 0.7 and the highest about 1.0, and greater than about 0.8 and the highest about 1.0, or greater than about 0.9 and the highest by about 1.0.In other embodiments, the blockiness index that said polymer fraction has is greater than about 0.1 and the highest about 1.0, greater than about 0.2 and the highest about 1.0, and greater than about 0.3 and the highest about 1.0, greater than about 0.4 and the highest about 1.0, or greater than about 0.4 and the highest by about 1.0.In other other embodiment, the blockiness index that said polymer fraction has is greater than about 0.1 and the highest about 0.5, greater than about 0.2 and the highest about 0.5, and greater than about 0.3 and the highest about 0.5, or greater than about 0.4 and the highest by about 0.5.In other other embodiment, the blockiness index that said polymer fraction has is greater than about 0.2 and the highest about 0.9, greater than about 0.3 and the highest about 0.8, and greater than about 0.4 and the highest about 0.7, or greater than about 0.5 and the highest by about 0.6.

For the multipolymer of ethene and terminal olefin, multi-block polymer preferably has (1) at least 1.3, and more preferably at least 1.5; At least 1.7; Or at least 2.0, and most preferably be at least 2.6, the highest 5.0 peak; The highest 3.5 peak more preferably, and especially the highest 2.7 peaked PDI; (2) 80J/g or littler melting heat; The ethylene content of (3) at least 50 weight %; (4) be lower than-25 ℃, more preferably be lower than-30 ℃ glass transition temperature Tg; And/or (5) one and T only _m

In addition, these many block interpolymers can be separately or with the application in any other properties of combination ground of disclosing have storage modulus G ', make log (G ') 100 ℃ temperature for more than or equal to 400kPa, be preferably more than or equal 1.0MPa.And these many block interpolymers have the storage modulus (as shown in Figure 6) of relatively flat function as temperature in 0 to 100 ℃ of scope, and this is the characteristic of segmented copolymer, and for olefin copolymer, especially ethene and one or more C _3-8The multipolymer of aliphatic alpha-olefin is unknown up to now.(term in this context " flat relatively " is meant between 50 and 100 ℃, preferably between 0 and 100 ℃ the decline of logG ' (is unit with pascal) less than an one magnitude).

These many block interpolymers can be further through characterizing to the modulus in flexure of 13kpsi (90MPa) at the 1mm thermo-mechanical analysis needle penetration of at least 90 ℃ temperature and 3kpsi (20MPa).Selectively, said many block interpolymers can have 1mm thermo-mechanical analysis needle penetration at least 104 ℃ temperature, and the modulus in flexure of 3kpsi (20MPa) at least.Can said many block interpolymers be characterized by and have less than 90mm ³Wearability (or VOLUME LOSS).Fig. 7 shows the graph of a relation of TMA (1 mm) that these many block interpolymers compare with other known polymer and modulus in flexure.Flexible-thermotolerance the balance of flexible-other polymkeric substance of thermotolerance equilibrium ratio of these many block interpolymers is significantly better.

In addition, the melt index I of said many blocks ethylene/alpha-olefin interpolymers ₂Can be 0.01 to 2000g/10 minute, be preferably 0.01 to 1000g/10 minute, more preferably 0.01 to 500g/10 minute, and especially be 0.01 to 100g/10 minute.In some embodiments, the melt index I of ethylene/alpha-olefin interpolymers ₂Be 0.01 to 10g/10 minute, 0.5 to 50g/10 minute, 1 to 30g/10 minute, 1 to 6g/10 minute or 0.3 to 10g/10 minute.In some embodiments, the melt index of ethylene/alpha-olefin polymer is 1g/10 minute, 3g/10 minute or 5g/10 minute.

The molecular weight M of these many block interpolymers _wCan be 1000g/mol to 5000000g/mol, be preferably 1000g/mol to 1000000g/mol, 10000g/mol to 500000g/mol more preferably, and especially be 10000g/mol to 300000g/mol.The density of said alkene multi-block polymer can be for 0.80 to 0.99g/cm ³, and be preferably 0.85g/cm for the polymkeric substance that contains ethene ³To 0.97g/cm ³In some embodiments, the density of ethylene/alpha-olefin polymer is 0.860 to 0.925g/cm ³Or 0.867 to 0.910g/cm ³

The preparation method of these many block interpolymers has been disclosed in following patented claim: the U.S. Provisional Application 60/553906 that on March 17th, 2004 submitted to; The U.S. Provisional Application 60/662937 that on March 17th, 2005 submitted to; The U.S. Provisional Application 60/662939 that on March 17th, 2005 submitted to; The U.S. Provisional Application 60/662938 that on March 17th, 2005 submitted to; The PCT application PCT/US2005/008916 that submitted on March 17th, 2005; The PCT application PCT/US2005/008915 that submitted on March 17th, 2005; PCT application PCT/US2005/008917 with submitting on March 17th, 2005 incorporates the full content mode by reference of all these patented claims into this paper.For example, but a kind of such method comprises ethene is contacted with catalyst composition under the addition polymerization condition with one or more optional nonvinylic addition polymerization monomers that said catalyst composition comprises:

Mixture or reaction product that following material mixing is obtained:

(A) have first olefin polymerization catalysis of high comonomer association index,

(B) second olefin polymerization catalysis, its comonomer incorporation index is preferably less than 50% less than catalyzer (A) comonomer incorporation exponential 90%, most preferably be less than 5% and

(C) chain shuttling agent (chain shuttling agent).

Representational catalyzer and chain shuttling agent are following.

Catalyzer (Al) is that [N-(2; 6-two (1-methylethyl) phenyl) amido (amido)) (2-isopropyl phenyl) (α-naphthalene-2-two bases (6-pyridine-2-two bases) methane)] the dimethyl-hafnium; Instruction preparation according to WO 03/40195,2003US0204017, USSN 10/429,024 (submission on May 2nd, 2003) and WO 04/24740.

Catalyzer (A2) is that [N-(2; 6-two (1-methylethyl) phenyl) (2-aminomethyl phenyl) (1 amido); 2-phenylene-(6-pyridine-2-two bases) methane)] dimethyl-hafnium; According to WO 03/40195,2003US0204017, USSN10/429, the instruction of 024 (submission on May 2nd, 2003) and WO 04/24740 preparation.

Catalyzer (A3) is two [N, N ' " (2,4,6-three (aminomethyl phenyl) amido) quadrol] dibenzyl hafnium (bis [N, N ' " (2,4,6-tri (methylphenyl) amido) ethylenediamine] hafnium dibenzyl).

Catalyzer (A4) is two ((2-oxygen base (oxoyl)-3-(dibenzo-1H-pyrroles-1-yl)-5-(methyl) phenyl)-2-phenoxymethyl) hexanaphthenes-1,2-two basic dibenzyl zirconiums (IV), and the instruction according to US-A-2004/0010103 prepares basically.

Catalyzer (B1) is 1,2-pair-(3,5-two-tertiary butyl phenylene) (1-(N-(1-methylethyl) imido grpup) methyl) (2-oxygen base) dibenzyl zirconium

Catalyzer (B2) is 1,2-pair-(3,5-two-tertiary butyl phenylene) (1-(N-(2-methylcyclohexyl)-imido grpup) methyl) (2-oxygen base) dibenzyl zirconium

Catalyzer (C1) is (tertiary butyl amido) dimethyl-(3-N-pyrryl-1,2,3,3a, 7a-η-indenes-1-yl) silane dimethyl-titanium, and the instruction according to USP 6268444 prepares basically:

Catalyzer (C2) is (tertiary butyl amido) two (4-aminomethyl phenyl) (2-methyl isophthalic acid, 2,3,3a, a 7a-η-indenes-1-yl) silane dimethyl-titanium, and the instruction according to US-A-2003/004286 prepares basically:

Catalyzer (C3) is (tertiary butyl amido) two (4-aminomethyl phenyl) (2-methyl isophthalic acid, 2,3,3a, 8a-η-symmetry-indacene (s-indacen)-1-yl) silane dimethyl-titanium, and the instruction according to US-A-2003/004286 prepares basically:

Catalyzer (D1) is two (dimethyl-sily oxide) (indenes-1-yl) zirconium dichlorides, can derive from Sigma-Aldrich:

The employed shuttling agent of shuttling agent comprises zinc ethyl, two (isobutyl-) zinc, two (n-hexyl) zinc, triethyl aluminum, trioctylaluminum, triethyl-gallium, aluminium isobutyl two (dimethyl-(tertiary butyl) siloxanes), two (two (trimethyl silyl) aminate) (i-butylaluminumbis (di (trimethylsilyl) amide)) of aluminium isobutyl, octyl aluminum two (pyridine-2-methoxide) (n-octylaluminumdi (pyridine-2-methoxide)), two (Octadecane base) aluminium isobutyl, two (two (n-pentyl) aminate) (i-butylaluminum bis (di (n-pentyl) amide)) of aluminium isobutyl, octyl aluminum two (2; 6-two-tert.-butylbenzene oxide compound) (n-octylaluminum bis (2; 6-di-t-butylphenoxide)), octyl aluminum two (ethyl (1-naphthyl) aminate) (n-octylaluminum di (ethyl (1-naphthyl) amide)), two (tertiary butyl dimethyl Si thing) (ethylaluminum bis (t-butyldimethylsiloxide)) of aluminium triethyl, aluminium triethyl two (two (trimethyl silyl) aminate) (ethylaluminum di (bis (trimethylsilyl) amide)), aluminium triethyl two (2; 3; 6; 7-dibenzo-1-azepan aminate) (ethylaluminumbis (2; 3; 6; 7-dibenzo-1-azacycloheptaneamide)), octyl aluminum two (2,3,6; 7-dibenzo-1-azepan aminate) (n-octylaluminum bis (2; 3,6,7-dibenzo-1-azacycloheptaneamide)), two (dimethyl-(tertiary butyl) Si oxide (n-octylaluminumbis (dimethyl (t-butyl) siloxide), zinc ethyls (2 of octyl aluminum; 6-diphenyl benzene oxide compound) (ethylzinc (2,6-diphenylphenoxide)) and zinc ethyl (uncle's fourth oxide compound) (ethylzinc (t-butoxide)).

Preferably, preceding method uses the multiple catalyzer that can not transform each other, takes the form of successive soln method to form two kinds or more kinds of monomer (more particularly ethene and C _3-20Alkene or cycloolefin, and the most especially ethene and C _4-20Terminal olefin) segmented copolymer, especially segmented copolymer, preferred line style segmented copolymer.That is, said catalyzer is chemically different.Under the continuous solution polymerization condition, said method is ideally suited for the high monomer transformation efficiency the monomer mixture polymerization.Under these polymerizing conditions, compare with chain growth, move from the shuttle of chain shuttling agent to catalyzer and become favourable, and segmented copolymer (particularly line style segmented copolymer) forms with high-level efficiency.

Many block interpolymers can be with different through the physical blending thing and the segmented copolymer of the random copolymers of the routine of sequential monomer adding, rheology catalyzer, negatively charged ion or the preparation of cation activity polymerization technique, polymkeric substance.Particularly; Compare with the random copolymers with identical monomer and monomer content that percent crystallinity or modulus equate, interpretation of the present invention has preferably that (higher) thermotolerance (measuring through fusing point), higher TMA pin are gone into temperature, higher high temperature tensile strength and/or higher high temperature reverses storage modulus (through dynamic mechanical analysis mensuration).Compare with the random copolymers that contains identical monomer and monomer content, interpretation of the present invention has lower compression set (especially at high temperature), lower stress relaxation, higher creep resistance, higher tear strength, higher resistance to blocking, condense faster (setup) that higher crystallization (curing) temperature causes, higher recovery (especially at high temperature), wear resistance, higher retraction force and oil and filler acceptability preferably preferably.

These many block interpolymers also demonstrate unique crystallization and branching distribution relation.Promptly; Interpretation of the present invention has relatively large difference using between the climax temperature as the function of melting heat of CRYSTAF and dsc measurement; The physical blending thing of the polymkeric substance that especially equates with random copolymers that contains same monomer and single level or total body density (for example, high density polymer and blend than low density copolymer) is all the more so when comparing.The character of this uniqueness of interpretation of the present invention be considered to comonomer in polymer backbone in the block unique distribution caused.Particularly, interpretation of the present invention can comprise that alternative has the block of different copolymer monomer content (comprising homopolymer block).Interpretation of the present invention can also comprise the distribution of the quantity and/or the block size of the polymer blocks with different densities or co-monomer content, and it is that the Schultz-Flory type distributes.In addition, interpretation of the present invention also has unique peak value fusing point and Tc curve, and said curve and density polymer, modulus and form are irrelevant basically.In preferred embodiment; The crystallite preface of polymkeric substance (microcrystalline order) has been illustrated the characteristic spherocrystal and the platelet that can differentiate with random copolymers or segmented copolymer; Even be less than 1.7 in the PDI value, or even less than 1.5, minimum to be less than at 1.3 o'clock also be like this.

And these many block interpolymers can use the degree that influences block or the technology of level to prepare.That is ratio that, each polymer blocks or segmental amount of comonomers and length can be through control catalyst and shuttling agents and type and polymerization temperature change with other polymerization variables.The unexpected benefit of this phenomenon is to find that when block degree (degree of blockness) increased, the optical property of resulting polymers, tear strength and high-temperature reply character improved.Particularly, when the average block number of polymkeric substance increased, mist degree reduced, and transparency, tear strength and high-temperature reply character improve.Have the shuttling agent of required chain transfer ability (high shuttle moves speed under the situation of low chain termination level) and the combination of catalyzer through selection, the polymkeric substance that has suppressed other form effectively stops.Therefore; Few (if any) observed β-hydrogenate and eliminated in according to the polymerization of the ethylene/alpha-olefin copolymerized monomer mixture of embodiment of the present invention; And the crystalline blocks of gained is the line style of height (or complete basically), has few or does not have long chain branching.

Having highly crystalline terminated polymkeric substance can optionally prepare according to embodiment of the present invention.In elastomerics is used, reduce with the end capped polymkeric substance relative quantity of amorphous blocks and can the intermolecular diluting effect to crystal region be reduced.This result can obtain through chain shuttling agent and the catalyzer of selecting hydrogen or other chain terminator to be had suitable response.Particularly; Hang down the crystalline polymer segment (for example through higher comonomer incorporation if produce the catalyzer of the polymkeric substance of highly crystalline than producing; Zone-mistake; Perhaps form nonstereospecific polymer) catalyzer more responsive to chain termination (for example through use hydrogen), the polymer segment of highly crystalline will preferentially occupy the terminal portions of polymkeric substance so.Not only the capping group of gained is a crystal, and after stopping, the catalyst site that forms the highly crystalline polymkeric substance can be used for again the initiated polymerization thing once more and form.Therefore, the initial polymkeric substance that forms is another highly crystalline polymer segment.Therefore, the two ends of the segmented copolymer of gained are preferential highly crystallines.

The ethylene ' alpha '-olefin interpretation that is used for embodiment of the present invention is preferably ethene and at least a C ₃-C ₂₀The interpretation of terminal olefin.Ethene and C ₃-C ₂₀The multipolymer of terminal olefin is preferred especially.Said interpretation may further include C ₄-C ₁₈Diolefine and/or alkenyl benzene.Be used for carrying out the suitable unsaturated comonomer of polymeric and comprise with ethene, for example, ethylenically unsaturated monomers, conjugation or unconjugated diene, polyenoid, alkenyl benzene etc.The example of this comonomer comprises C ₃-C ₂₀Terminal olefin, for example propylene, iso-butylene, 1-butylene, 1-hexene, 1-amylene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene and 1-decene etc.1-butylene and 1-octene are preferred especially.Other monomer that is fit to comprises vinylbenzene, halogenated styrenes or alkyl-substituted vinylbenzene, vinyl benzo tetramethylene, 1,4-hexadiene, 1,7-octadiene and cycloolefin (for example, cyclopentenes, tetrahydrobenzene and cyclooctene).

Although the many block interpolymers of ethylene/alpha-olefin are preferred polymkeric substance, also can use other ethylene/olefin polymkeric substance.The employed alkene of the application is meant the compounds of group based on unsaturated hydrocarbons with at least one carbon-to-carbon double bond.Depend on selection of catalysts, can any alkene be used for embodiment of the present invention.Preferably, the alkene that is fit to is the C that contains vinyl degree of unsaturation (vinylic unsaturation) ₃-C ₂₀Aliphatic series and aromatic substance, and ring compound, for example, cyclobutene, cyclopentenes, Dicyclopentadiene (DCPD) and norbornylene are including, but not limited to being substituted with C at 5 and 6 ₁-C ₂₀The norbornylene of alkyl or cyclic hydrocarbon radical.The mixture and this type of alkene and the C that also comprise this type of alkene ₄-C ₄₀The mixture of diolefin compound.

The example of olefinic monomer includes but not limited to propylene, iso-butylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene; And 1-laurylene, 1-tetradecylene, 1-hexadecylene, 1-octadecylene, 1-icosa alkene, 3-methyl-1-butene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 4,6-dimethyl--1-heptene, 4 vinyl cyclohexene, vinyl cyclohexane, norbornadiene, ethylidene norbornene, cyclopentenes, tetrahydrobenzene, Dicyclopentadiene (DCPD), cyclooctene, C ₄-C ₄₀Diene includes but not limited to 1,3-butadiene, 1,3-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, other C ₄-C ₄₀Terminal olefin etc.In some embodiments, terminal olefin is propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene or their combination.Although any hydrocarbon that contains vinyl all can be used in the embodiment of the present invention potentially; But actual problem (for example, monomer availability, cost and the ability of from the polymkeric substance of gained, removing unreacted monomer easily) monomeric molecule quantitative change too Gao Shihui become more serious.

The described polymerization method of the application is highly suitable for producing the olefin polymer that comprises monovinylidene aromatic monomer, and said monovinylidene aromatic monomer comprises vinylbenzene, neighbour-vinyl toluene, p-methylstyrene and t-butyl styrene etc.Particularly, containing ethene and cinnamic interpretation can prepare through the instruction of following the application.Randomly, can prepare the interpretation with improved character, it comprises ethene, vinylbenzene and C ₃-C ₂₀Terminal olefin randomly comprises C ₄-C ₂₀Diene.

The non-conjugated diene monomers that is fit to can be straight chain, side chain or the cyclic hydrocarbon diene with 6 to 15 carbon atoms.The example of the non-conjugated diene that is fit to is including, but not limited to straight chain non-annularity diene, for example, 1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadiene; Side chain non-annularity diene, for example, 5-methyl isophthalic acid, 4-hexadiene, 3,7-dimethyl--1,6-octadiene, 3,7-dimethyl--1, the mixed isomers of 7-octadiene and dihydromyrcene (dihydromyricene) and dihydro ocimene (dihydroocinene); The alicyclic diene of monocycle, for example, 1,1,1,5-cyclooctadiene and 1,5-encircle 12 carbon diene; And encircle alicyclic condensing and the bridged ring diene more, and for example, tetrahydroindene, methyl tetrahydroindene, Dicyclopentadiene (DCPD), two ring-(2,2,1)-heptan-2,5-diene; The norbornylene of thiazolinyl, alkylidene group, cycloalkenyl group and cycloalkylidene; For example, 5-methylene-2-norbornene (MNB), 5-propenyl-2-norbornylene, 5-isopropylidene-2-norbornylene, 5-(4-cyclopentenyl)-2-norbornylene, 5-cyclohexylidene-2-norbornylene, 5-vinyl-2-norbornylene and norbornadiene.Be generally used for preparing in the diene of EPDM, preferred especially diene is 1,4-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2-norbornylene (VNB), 5-methylene-2-norbornene (MNB) and Dicyclopentadiene (DCPD) (DCPD).Preferred especially diene is 5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).

Can be ethene, C according to one type of ideal polymkeric substance of embodiment of the present invention preparation ₃-C ₂₀The elastocopolymer of terminal olefin (especially propylene) and optional one or more diene monomers.Use formula CH ₂=CHR ^*Expression is used for the preferred terminal olefin of embodiment of the present invention, wherein R ^*Be to have the line style of 1 to 12 carbon atom or the alkyl of branching.The example of the terminal olefin that is fit to includes but not limited to propylene, iso-butylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene and 1-octene.Preferred especially terminal olefin is a propylene.Polymkeric substance based on propylene is commonly referred to as EP or EPDM polymkeric substance in the art.The suitable diene that is used to prepare these polymkeric substance (particularly many blocks EPDM type polymkeric substance) comprises the conjugation that contains 4 to 20 carbon atoms or unconjugated, straight or branched, ring-type or polycyclic diene.Preferred diene comprises 1,4-pentadiene, 1,4-hexadiene, 5-ethylidene-2-norbornene, Dicyclopentadiene (DCPD), cyclohexadiene and 5-butylidene-2-norbornylene.Preferred especially diene is a 5-ethylidene-2-norbornene.

Comprise alternative and contain a large amount of or the diene (comprise and not containing) in a small amount and the segment or the block of terminal olefin (comprise and not containing) because contain the polymkeric substance of diene, so can be in the total amount reduction of not losing under the situation of polymer property subsequently with diene and terminal olefin.That is, because diene and 'alpha '-olefin monomers preferentially are combined in one type the polymer blocks, and non-homogeneous or spread all over whole polymkeric substance randomly, therefore, can be utilized more efficiently, and the cross-linking density of controlling polymers better thereafter.This crosslinkable elastomeric and cured product have favorable properties, comprise higher draw tensile strength and elastic recovery preferably.

In some embodiments, in conjunction with the interpretation of the present invention of two kinds of Preparation of Catalyst of usefulness of comonomer of different amounts have 95: 5 to 5: 95 the block wt ratio that forms thus.It is desirable to, based on the gross weight of polymkeric substance, elastomer polymer has 20 to 90% ethylene content, 0.1 to 10% diene content and 10 to 80% terminal olefin content.More preferably, based on the gross weight of polymkeric substance, many-block elastomer polymkeric substance has 60 to 90% ethylene content, 0.1 to 10% diene content and 10 to 40% terminal olefin content.Preferred polymkeric substance is a high-molecular weight polymer, and it has 10000 to about 2500000, is preferably 20000 to 500000, more preferably 20000 to 350000 weight-average molecular weight (M _w) and be less than 3.5, more preferably be less than 3.0 polymolecularity and 1 to 250 mooney viscosity (125 ℃ of ML (1+4)).More preferably, this polymkeric substance has 65 to 75% ethylene content, 0 to 6% diene content and 20 to 35% terminal olefin content.

Catalyzer

If use, term " spends the night " and is meant about 16-18 hour time, and term " room temperature " is meant 20-25 ℃ temperature, and term " mixed alkanes " be meant can be from ExxonMobil ChemicalCompany with trade(brand)name

The C that is commercially available _6-9The aliphatic hydrocrbon mixture.If the compound title among the application and its structural representation are not inconsistent, then should be as the criterion with structural representation.The preparations synthetic and all screening experiments of all metal complexs all are to use the loft drier technology in dry nitrogen atmosphere, to carry out.All used solvents be the HPLC level and before using, carry out drying.

MMAO is meant the MAO of modification, the MAO of the triisobutyl aluminium modification that can be commercially available from Akzo-Nobel Corporation.

The preparation of catalyzer (B1) is carried out as follows.

A) Preparation (1-methylethyl) (2-hydroxyl-3,5-two (tertiary butyl) phenyl) methylene imine

Add 3 to the 10mL isopropylamine, 5-two-tertiary butyl salicylic aldehyde (3.00g).Solution becomes glassy yellow fast.After envrionment temperature stirred 3 hours, removing volatiles under vacuum obtained jonquilleous crystalline solid (productive rate 97%).

B) Preparation 1,2-pair-(3,5-two-tertiary butyl phenylene) (1-(N-(1-methylethyl) imido grpup) methyl) (2- The oxygen base) dibenzyl zirconium

The solution of (1-methylethyl) (2-hydroxyl-3,5-two (tertiary butyl) phenyl) imines (605mg, 2.2 mmoles) in 5mL toluene is slowly added to Zr (CH ₂Ph) ₄(500mg, 1.1 mmoles) solution in 50mL toluene.The deep yellow solution of gained was stirred 30 minutes.Decompression removes down and desolvates, and obtains title product, is the solid of reddish-brown.

The preparation of catalyzer (B2) is carried out as follows.

A) preparation (1-(2-methylcyclohexyl) ethyl) (2-oxygen base-3,5-two (tertiary butyl) phenyl) imines

2-methylcyclohexyl amine (8.44mL, 64.0 mmoles) is dissolved in the methyl alcohol (90mL), and adds two-tertiary butyl salicylic aldehyde (10.00g, 42.67 mmoles).Reaction mixture was stirred 3 hours, be cooled to-25 ℃ then and reach 12 hours.The yellow solid deposition of gained is collected through filtering, and with cold methanol (2 * 15mL) washing, drying under reduced pressure then.Obtain the 11.17g yellow solid. ¹H NMR is consistent with title product (isomer mixture).

B) Preparation two-(1-(2-methylcyclohexyl) ethyl) (2-oxygen base-3,5-two (tertiary butyl) phenyl) imido grpup) The dibenzyl zirconium

The solution of (1-(2-methylcyclohexyl) ethyl) (2-oxygen base-3,5-two (tertiary butyl) phenyl) imines (7.63g, 23.2 mmoles) in 200mL toluene slowly is added into Zr (CH ₂Ph) ₄In (5.28g, 11.6 mmoles) solution in 600mL toluene.The deep yellow solution of gained was stirred 1 hour at 25 ℃.Further dilute this solution with 680mL toluene, obtain the solution that concentration is 0.00783M.

Promotor 1 methyl two (C _14-18Alkyl) mixture of four of ammonium salt (pentafluorophenyl group) boride (after this being called aliphatic long-chain ammonium boride (armeenium borate)), it is basically like USP 5,919, and 2 disclosures of 9883 embodiment are through long-chain trialkylamine (Armeen ^TMM2HT can derive from Akzo-Nobel, Inc.), HCl and Li [B (C ₆F ₅) _4]Reaction and prepare.

Promotor 2 mixed C _14-18Two (three (pentafluorophenyl group)-aluminium alkane)-2-undecyl imidazole things (imidazolide) of alkyl dimethyl ammonium salt, according to USP 6,395,671 embodiment 16 preparations.

The employed shuttling agent of shuttling agent comprises zinc ethyl (DEZ; SA1), two (isobutyl-) zinc (SA2), two (n-hexyl) zinc (SA3), triethyl aluminum (TEA; SA4), trioctylaluminum (SA5), triethyl-gallium (SA6), aluminium isobutyl two (dimethyl-(tertiary butyl) siloxanes) (SA7), aluminium isobutyl two (two (trimethyl silyl) aminate) (SA8), octyl aluminum two (pyridine-2-methoxide) (SA9), two (Octadecane base) aluminium isobutyl (SA10), aluminium isobutyl two (two (n-pentyl) aminate) (SA11), octyl aluminum two (2; 6-two-tert.-butylbenzene oxide compound) (SA12), octyl aluminum two (ethyl (1-naphthyl) aminate) (SA13), aluminium triethyl two (the tertiary butyl dimethyl Si things) (two (t-butyldimehtylsiloxide of ethylaluminum; SA14), aluminium triethyl two (two (trimethyl silyl) aminate) (SA15), aluminium triethyl two (2; 3; 6; 7-dibenzo-1-azepan aminate) (SA16), octyl aluminum two (2,3,6; 7-dibenzo-1-azepan aminate) (SA17), octyl aluminum two (dimethyl-(tertiary butyl) Si oxide (SA18), zinc ethyl (2,6-diphenyl benzene oxide compound) (SA19) and zinc ethyl (uncle's fourth oxide compound) (SA20).

Embodiment 1-4, comparative example A-C

General high yield parallel polymerization condition

Use can derive from Symyx technologies, and the high yield parallel polymerization reactor drum (PPR) of Inc. carries out polymerization, and operates according to USP 6248540,6030917,6362309,6306658 and 6316663 basically.Use in used total catalyst 1.2 normal promotors 1 (being 1.1 equivalents when MMAO exists) at 130 ℃ and 200psi (1.4MPa) (existing under the situation of needed ethene) and to carry out the ethylene copolymerization reaction.In the parallel pressure reactor drum (PPR) of 48 the separate reactors unit (being furnished with preweighted Glass tubing) that contain 6 * 8 arrangements, carry out a series of polymerizations.Working volume in each reactor unit is 6000 μ L.Provide under the condition of stirring at independent stirring rake, each unit is carried out temperature and pressure control.Monomer gas and cancellation gas are directly sent in (plumbed) PPR unit, and through self-acting valve control.In each reactor unit, add liquid reagent automatically through syringe, and the deposit solvent is a mixed alkanes.Interpolation is mixed alkanes solvent (4ml), ethene, 1-octene copolymer monomer (1ml), promotor 1 or promotor 1/MMAO mixture, shuttling agent and catalyzer or catalyst mixture in proper order.When the mixture that uses promotor 1 and MMAO or two kinds of mixture of catalysts,, add in the reactor drum immediately then these reagent premix in bottle.When in experiment, having omitted reagent, keep above-mentioned other interpolation order.Polymerization was carried out about 1-2 minute, until reaching predetermined ethene consumption.After with the CO quencher, cooling reactor also unloads Glass tubing.These pipes are transferred in centrifugal/vacuum-drying unit, and 60 ℃ of dryings 12 hours.The pipe that will contain dry polymer is weighed, and the difference between this weight and the tare weight has provided the clean yield of polymkeric substance.The result lists in the table 1.In other place of table 1 and the application, control compounds usually with asterisk ( ^*) illustrate.

Embodiment 1-4 illustrates through the present invention and has synthesized line-type block polymer (many block interpolymers), and this is confirmed by following: when having DEZ, forming very narrow MWD, is Monomodal copolymer basically; When not having DEZ, form the product (mixture of polymers of processing respectively) of bimodal wide molecular weight distribution.Because known catalysts (A1) combines more octene than catalyzer (B1), so the different blocks of the multipolymer of the present invention of gained or segment can be distinguished according to the degree of branching or density.

Table 1

Embodiment	Catalyzer (A1) (μm ol)	Catalyzer (B1) (μm ol)	Promotor (μ mol)	MMAO (μmol)	Shuttling agent (μmol)	Output (g)	M _n	M _w/M _n	Hexyl ¹
										A ^*	0.06	-	0.066	0.3	-	0.1363	300502	3.32	-
B ^*	-	0.1	0.110	0.5	-	0.1581	36957	1.22	2.5
										C ^*	0.06	0.1	0.176	0.8	-	0.2038	45526	5.302	5.5
1	0.06	0.1	0.192	-	DEZ(8.0)	0.1974	28715	1.19	4.8
										2	0.06	0.1	0.192	-	DEZ(80.0)	0.1468	2161	1.12	14.4
3	0.06	0.1	0.192	-	TEA(8.0)	0.208	22675	1.71	4.6
										4	0.06	0.1	0.192	-	TEA(80.0)	0.1879	3338	1.54	9.4

¹The C of per 1000 carbon ₆Perhaps more senior chain content

²Bimodal molecular weight distribution

Can find out that and at the polymer phase ratio that does not have to prepare under the shuttling agent condition, multi-block polymer prepared in accordance with the present invention has narrow relatively polymolecularity (M _w/ M _n) and bigger block-multipolymer content (tripolymer, the tetramer or bigger).

Through measured the further characterization data of table 1 polymkeric substance with reference to the figure among the WO/2005/090427 (it incorporates this paper into through reference) of figure 1-7 and submission on March 17th, 2005.More specifically, DSC and ATREF result show below:

Fusing point (the T that the DSC curve display of the polymkeric substance of embodiment 1 is 115.7 ℃ _m), and have the melting heat of 158.1J/g.Corresponding C RYSTAF curve shows the climax at 34.5 ℃, and has 52.9% peak area.DSC T _mAnd T _CrystafBetween difference be 81.2 ℃.

The DSC curve display of the polymkeric substance of embodiment 2 has 109.7 ℃ of fusing point (T _m) the peak, and have the melting heat of 2 14.0J/g.Corresponding C RYSTAF curve shows the climax at 46.2 ℃, and has 57.0% peak area.DSC T _mAnd T _CrystafBetween difference be 63.5 ℃.

The DSC curve display of the polymkeric substance of embodiment 3 has 120.7 ℃ of fusing point (T _m) the peak, and have the melting heat of 160.1J/g.Corresponding C RYSTAF curve shows the climax at 66.1 ℃, and has 71.8% peak area.DSC T _mAnd T _CrystafBetween difference be 54.6 ℃.

The DSC curve display of the polymkeric substance of embodiment 4 has 104.5 ℃ of fusing point (T _m) the peak, and have the melting heat of 170.7J/g.Corresponding C RYSTAF curve shows the climax at 30 ℃, and has 18.2% peak area.DSC T _mAnd T _CrystafBetween difference be 74.5 ℃.

Fusing point (the T that comparative example A's DSC curve display is 90.0 ℃ _m), and have the melting heat of 86.7J/g.Corresponding C RYSTAF curve shows the climax at 48.5 ℃, and has 29.4% peak area.These values are all consistent with low-density resin.DSC T _mAnd T _CrystafBetween difference be 41.8 ℃.

Fusing point (the T that the DSC curve display of Comparative Examples B is 129.8 ℃ _m), and have the melting heat of 237.0J/g.Corresponding C RYSTAF curve shows the climax at 82.4 ℃, and has 83.7% peak area.These values are all consistent with highdensity resin.DSC T _mAnd T _CrystafBetween difference be 47.4 ℃.

Fusing point (the T that the DSC curve display of Comparative Examples C is 125.3 ℃ _m), and have the melting heat of 143.0J/g.Corresponding C RYSTAF curve shows the climax at 81.8 ℃, and has 34.7% peak area, and 52.4 ℃ of peak crystallization that demonstration is lower.Two peak-to-peak separation are consistent with the existence of high crystallization and low-crystalline polymer.DSC T _mAnd T _CrystafBetween difference be 43.5 ℃.

Embodiment 5-19, Comparative Examples D-F, continuous solution polymerization, catalyst A 1/B2+DEZ

In being furnished with the computer-controlled autoclave reactor of internal stirrers, carry out continuous solution polymerization.Be furnished with the chuck that is used for controlled temperature and the 3.8L reactor drum of internal heat galvanic couple, adding, the mixed alkanes solvent of purifying (can derive from the Isopar of ExxonMobil Chemical Company ^TMThe ethene of E), 2.70 Pounds Per Hours (1.22 kilograms/hour), 1-octene and hydrogen (if use).Measure the solvent feed that gets into reactor drum through mass flow controller.The control of speed change surge pump gets into the solvent flow rate and the pressure of reactor drum.When pump discharges, get the flushing flow that effluent is provided for catalyzer and promotor 1 injection pipeline and reactor agitator.These flow through the Micro-Motion mass flow meter measurement, and control through valve or through the manual adjustment of needle-valve.Remaining solvent and 1-octene, ethene and hydrogen (if use) are merged, and be conducted in the reactor drum.The functional quality flow director carries hydrogen to reactor drum on demand.Before getting into reactor drum, use the temperature of heat exchanger control solvent/monomer solution.This flows into the bottom of reactor drum.Use pump and mass flowmeter metered catalyst component solution, and itself and catalyzer rinse solvent are merged, and introduce the bottom of reactor drum.Under intense agitation, reactor drum is moved at the full liquid (liquid-full) of 500psig (3.45MPa).Vent line through reactor head removes product.All vent lines of reactor drum are all with steam heating and adiabatic.Less water is added in the vent line with any stablizer or other additive and makes this mixture through static mixer, stop polymerization thus.Product flow was heated through heat exchanger before devolatilization.Use vented extruder and water-cooled tablets press to extrude, thereby reclaim polymeric articles.Process detail and result are shown in Table 2.The character of the polymkeric substance of selecting is listed in table 3.

Like preceding embodiment, with the polymkeric substance of DSC and ATREF test gained.The result is following:

The DSC curve display of the polymkeric substance of embodiment 5 has 119.6 ℃ of fusing point (T _m) the peak, and have the melting heat of 60.0J/g.Corresponding CRYSTAF curve shows the climax at 47.6 ℃, and has 59.5% peak area.DSC T _mAnd T _CrystafBetween difference be 72.0 ℃.

The DSC curve display of the polymkeric substance of embodiment 6 has 115.2 ℃ of fusing point (T _m) the peak, and have the melting heat of 60.4J/g.Corresponding CRYSTAF curve shows the climax at 44.2 ℃, and has 62.7% peak area.DSC T _mAnd T _CrystafBetween difference be 71.0 ℃.

The DSC curve display of the polymkeric substance of embodiment 7 has 121.3 ℃ of fusing point (T _m) the peak, and have the melting heat of 69.1J/g.Corresponding CRYSTAF curve shows the climax at 49.2 ℃, and has 29.4% peak area.DSC T _mAnd T _CrystafBetween difference be 72.1 ℃.

The DSC curve display of the polymkeric substance of embodiment 8 has 123.5 ℃ of fusing point (T _m) the peak, and have the melting heat of 67.9J/g.Corresponding CRYSTAF curve shows the climax at 80.1 ℃, and has 12.7% peak area.DSC T _mAnd T _CrystafBetween difference be 43.4 ℃.

There are 124.6 ℃ of fusing point (T in the DSC curve display county of the polymkeric substance of embodiment 9 _m) the peak, and have the melting heat of 73.5J/g.Corresponding CRYSTAF curve shows the climax at 80.8 ℃, and has 16.0% peak area.DSC T _mAnd T _CrystafDifference be 43.8 ℃.

The DSC curve display of the polymkeric substance of embodiment 10 has 115.6 ℃ of fusing point (T _m) the peak, and have the melting heat of 60.7J/g.Corresponding CRYSTAF curve shows the climax at 40.9 ℃, and has 52.4% peak area.DSC T _mAnd T _CrystafBetween difference be 74.7 ℃.

The DSC curve display of the polymkeric substance of embodiment 11 has 113.6 ℃ of fusing point (T _m) the peak, and have the melting heat of 70.4J/g.Corresponding CRYSTAF curve shows the climax at 39.6 ℃, and has 25.2% peak area.DSC T _mAnd T _CrystafBetween difference be 74.1 ℃.

The DSC curve display of the polymkeric substance of embodiment 12 has 113.2 ℃ of fusing point (T _m) the peak, and have the melting heat of 48.9J/g.Corresponding CRYSTAF curve display does not have and is equal to or higher than 30 ℃ peak.(be further to calculate, with T _CrystafBe set at 30 ℃).DSC T _mAnd T _CrystafDifference be 83.2 ℃.

The DSC curve display of the polymkeric substance of embodiment 13 has 114.4 ℃ of fusing point (T _m) the peak, and have the melting heat of 49.4J/g.Corresponding CRYSTAF curve shows the climax at 33.8 ℃, and has 7.7% peak area.DSC T _mAnd T _CrystafBetween difference be 84.4 ℃.

The DSC curve display of the polymkeric substance of embodiment 14 has 120.8 ℃ of fusing point (T _m) the peak, and have the melting heat of 127.9J/g.Corresponding CRYSTAF curve shows the climax at 72.9 ℃, and has 92.2% peak area.DSC T _mAnd T _CrystafDifference be 47.9 ℃.

The DSC curve display of the polymkeric substance of embodiment 15 has 114.3 ℃ of fusing point (T _m) the peak, and have the melting heat of 36.2J/g.Corresponding CRYSTAF curve shows the climax at 32.3 ℃, and has 9.8% peak area.DSC T _mAnd T _CrystafBetween difference be 82.0 ℃.

The DSC curve display of the polymkeric substance of embodiment 16 has 116.6 ℃ of fusing point (T _m) the peak, and have the melting heat of 44.9J/g.Corresponding CRYSTAF curve shows the climax at 48.0 ℃, and has 65.0% peak area.DSC T _mAnd T _CrystafBetween difference be 68.6 ℃.

The DSC curve display of the polymkeric substance of embodiment 17 has 116.0 ℃ of fusing point (T _m) the peak, and have the melting heat of 47.0J/g.Corresponding CRYSTAF curve shows the climax at 43.1 ℃, and has 56.8% peak area.DSC T _mAnd T _CrystafBetween difference be 72.9 ℃.

The DSC curve display of the polymkeric substance of embodiment 18 has 120.5 ℃ of fusing point (T _m) the peak, and have the melting heat of 141.8J/g.Corresponding CRYSTAF curve shows the climax at 70.0 ℃, and has 94.0% peak area.DSC T _mAnd T _CrystafDifference be 50.5 ℃.

The DSC curve display of the polymkeric substance of embodiment 19 has 124.8 ℃ of fusing point (T _m) the peak, and have the melting heat of 174.8J/g.Corresponding CRYSTAF curve shows the climax at 79.9 ℃, and has 87.9% peak area.DSC T _mAnd T _CrystafBetween difference be 45.0 ℃.

The DSC curve display of the polymkeric substance of Comparative Examples D has 37.3 ℃ of fusing point (T _m) the peak, and have the melting heat of 31.6J/g.Corresponding CRYSTAF curve display does not have and is equal to or higher than 30 ℃ peak.These numerical value are all consistent with low-density resin.DSC T _mAnd T _CrystafBetween difference be 7.3 ℃.

The DSC curve display of the polymkeric substance of Comparative Examples E has 124.0 ℃ of fusing point (T _m) the peak, and have the melting heat of 179.3J/g.Corresponding CRYSTAF curve shows the climax at 79.3 ℃, and has 94.6% peak area.These numerical value are all consistent with highdensity resin.DSC T _mWith T _CrystafBetween difference be 44.6 ℃.

The DSC curve display of the polymkeric substance of Comparative Examples F goes out to have 124.8 ℃ fusing point (T _m) the peak, and have the melting heat of 90.4J/g.Corresponding CRYSTAF curve shows the climax at 77.6 ℃, and has 19.5% peak area.This two peak-to-peak separation is consistent with the existence of high crystallization and low-crystalline polymer.DSC T _mWith T _CrystafBetween difference be 47.2 ℃.

The physical properties test

The physical properties of assessment polymer samples, for example high temperature resistant character (confirming), pellet adhesion intensity, high-temperature reply property, high temperature compressed set and storage modulus ratio (G ' (25 ℃)/G ' (100 ℃)) with the TMA temperature test.In test, comprise the polymkeric substance that several are available commercially: Comparative Examples G* and be substantial linear ethene/1-octene copolymer (

Can derive from The Dow ChemicalCompany), Comparative Examples H* be elastic substantial linear ethene/1-octene copolymer (

EG8100 can derive from The Dow Chemical Company), Comparative Examples I be substantial linear ethene/1-octene copolymer (

PL1840 can derive from The Dow Chemical Company), Comparative Examples J is the triblock copolymer (KRATON of hydrogenant styrene/butadiene/styrene ^TMG1652 can derive from KRATON polymkeric substance s), Comparative Examples K is TPV (TPV contains the polyolefin blends of dispersion cross-linked elastomer within it).The result lists in table 4.

Table 4: high-temperature machinery character

Embodiment	The TMA-1mm pin go into (℃)	Pellet adhesion intensity lb/ft ²(kPa)	G′(25℃)/ G′(100℃)	300% strain response rate (80 ℃) (%)	Compression set (70 ℃) (%)
						D ^*	51	-	9	Failure	-
E ^*	130	-	18	-	-
						F ^*	70	141(6.8)	9	Failure	100
5	104	0(0)	6	81	49
						6	110	-	5	-	52
7	113	-	4	84	43
						8	111	-	4	Failure	41
9	97	-	4	-	66
						10	108	-	5	81	55
11	100	-	8	-	68
						12	88	-	8	-	79
13	95	-	6	84	71
						14	125	-	7	-	-
15	96	-	5	-	58
						16	113	-	4	-	42
17	108	0(0)	4	82	47
						18	125	-	10	-	-
19	133	-	9	-	-
						G ^*	75	463(22.2)	89	Failure	100
H ^*	70	213(10.2)	29	Failure	100
						I ^*	111	-	11	-	-
J ^*	107	-	5	Failure	100
						K ^*	152	-	3	-	40

In table 4, it is about 70 ℃ that the 1mm pin of Comparative Examples F (it is the physical blending thing that uses two kinds of polymkeric substance that catalyst A 1 and B 1 polymerization obtain simultaneously) is gone into temperature, and the 1mm pin of embodiment 5-9 to go into temperature be 100 ℃ or higher.In addition, the 1mm pin of embodiment 10-19 is gone into temperature and all is higher than 85 ℃, wherein most 1mm TMA temperature be higher than 90 ℃ or even be higher than 100 ℃.This shows that comparing multi-block polymer with the physical blending thing has dimensional stability preferably in higher temperature.Comparative Examples J (commercial SEBS) has about 107 ℃ good 1mm TMA temperature, but it has about 100% extreme difference (70 ℃ of high temperature) compression set, and also replys (breakage) between 300% strain rest period at high temperature (80 ℃).Therefore, this exemplary polymer has unique properties of combination, even these unique properties of combination also can not obtain in the high-performance thermoplastic elastomerics that some can be buied.

Similarly; Table 4 is for multi-block polymer demonstration 6 of the present invention or lower low (well) storage modulus ratio G ' (25 ℃)/G ' (100 ℃); And physical blending thing (Comparative Examples F) has 9 storage modulus ratio, and the random ethylene/octene copolymer of similar density (Comparative Examples G) has the storage modulus ratio (89) of a high order of magnitude.It is desirable to, the storage modulus ratio of polymkeric substance is as far as possible near 1.These polymer phases are to temperature influence more not, and can in wide temperature range, use effectively from the goods of these polymers.This low storage modulus ratio and not the characteristic of temperature influence in elastomerics is used, for example particularly useful in the pressure-sensitive adhesive agent formulation.

Data in the table 4 are also illustrated polymkeric substance of the present invention and are had improved pellet adhesion intensity.Particularly, the pellet adhesion intensity of embodiment 5 is 0MPa, and it is free-pouring to this meaning under test condition, and as comparing, Comparative Examples F and G show suitable adhesion effect.Adhesion intensity is important, and this is because the large quantities of transportations with polymkeric substance of big adhesion intensity can cause when storage or transportation the product caking or stick together, thereby obtains the operability of difference.

The high temperature of said alkene multi-block polymer (70 ℃) compression set is normally good, this means to be less than approximately 80% usually, is preferably and is less than approximately 70%, and is in particular and is less than about 60%.On the contrary, Comparative Examples F, G, H and J all have 70 ℃ of compression sets (maximum possible value, expression does not have answer) of 100%.Good high-temperature compression set (low numerical value) is special needs for the for example application of pad, window frame and o ring etc.

Table 5 demonstration new polymers and various comparative polymer are in the mechanical properties result of envrionment temperature.Can find out that said multi-block polymer has excellent abrasive resistance according to ISO 4649 tests the time, generally be to show to be less than 90mm ³, be preferably and be less than about 80mm ³, and particularly be less than about 50mm ³VOLUME LOSS.In this test, loss is lower with wear resistance thereby high value is represented higher volumes.

The tear strength of passing through stretching tongue tear ionization meter of said alkene multi-block polymer generally is 1000mJ or higher, and is as shown in table 5.The tear strength of said alkene multi-block polymer can be up to 3000mJ, or even up to 5000mJ.Comparative polymer generally has the tear strength that is not higher than 750mJ.

Table 5 also show said alkene multi-block polymer 150% strained back stress than some comparative sample 150% strained back stress better (the back stress value by higher proves).Comparative Examples F, G and H have 400kPa or back stress value still less when 150% strain, and said alkene multi-block polymer has the back stress value of 500kPa (embodiment 11) to the highest about 1100kPa (embodiment 17) when 150% strain.For flexible application, for example spandex fiber and fabric, particularly non-woven fabric, it is quite useful having the polymkeric substance that is higher than 150% back stress value.Other application comprises the waistband application of diaper, sanitary product and medical clothing, for example, overhangs band (tabs) and flexible tie.

Table 5 shows that also with respect to for example Comparative Examples G, said alkene multi-block polymer also has (lower) stress relaxation (when 50% strain) of improvement.Lower stress relaxation means that this polymkeric substance keeps its power preferably in application, for example diaper and when body temperature long-term other clothing that keeps elastic property of expectation.

Many block interpolymers of alkene and optimal ethylene/alpha-olefin multi-block interpretation can comprise the combination of two kinds or more kinds of suitable embodiments as herein described.

In another embodiment, can use the blend of one or more polymkeric substance (for example as described herein) and the many block interpolymers of one or more alkene (for example as described herein) based on alkene.

In another embodiment, a kind of polymkeric substance (as described herein) based on ethene can with the blend of the many block interpolymers of a kind of alkene (as described herein).

In another embodiment, a kind of polymkeric substance (as described herein) based on propylene can with the blend of the many block interpolymers of a kind of alkene (as described herein).

In another embodiment, a kind of polymkeric substance (as described herein) and a kind of polymkeric substance (as described herein) based on propylene based on ethene can with the blend of the many block interpolymers of a kind of alkene (as described herein).

Thermoplastic polyurethane

In the polyurethane component that can randomly use in the compsn not restriction with regard to its prescription; Except requiring it is thermoplastic in itself; This is meant that it is by dual functional composition basically (for example, organic diisocyanate and to contain on the active hydrogen group be dual functional basically component) preparation.Yet, can use a small amount of functionality to be higher than 2 composition sometimes.Especially true when using such as chain extension agents such as USP Kosher, TriMethylolPropane(TMP)s.Such thermoplastic polyurethane component is commonly referred to as the TPU material.Therefore, all available compsn of the present invention of any TPU material known in the art.Representativeness for preparation TPU material is instructed referring to Polyurethanes:Chemistry and Technology, Part II, and Saunders andFrisch, 1964pp 767～769; Interscience Publishers, New York, N.Y. and Macmillan Publishing Co.; Inc., New York, the Polyurethane Handbook that N.Y edits at the G.Oertel of U.S.'s distribution; 1985, pp 405～417, Hanser Publications.For the concrete instruction of various TPU materials and preparation thereof referring to USP 2929800; 2948691; 3493634; 3620905; 3642964; 3963679; 4131604; 4169196; Re 31671; 4245081; 4371684; 4379904; 4447590; 4523005; 4621113; And 4631329, their disclosure is incorporated this paper by reference into.

Preferred TPU is the polymkeric substance by the mixture preparation that comprises organic diisocyanate, at least a polymer diol and at least a difunctional chain extenders.TPU can be according to the method described in the top reference of incorporating into through prepolymer, quasi-prepolymer or single stage method preparation.

The vulcabond that is applicable to the hard segment of preparation urethane of the present invention comprises aromatics, aliphatic series and alicyclic diisocyanate and two kinds or more kinds of these combination of compounds.Following formula (I) representative derives from the instance of the structural unit of vulcabond (OCN-R-NCO):

Wherein R is alkylidene group, cycloalkylidene or arylidene.The representative example of these vulcabond is found in USP 4385133,4522975 and 5167899.

Preferred vulcabond includes but not limited to 4,4 '-the isocyanato ditan, right-phenylene vulcabond, 1,3-two (isocyanato methyl)-hexanaphthene; 1,4-two isocyanatos-hexanaphthene, hexamethylene diisocyanate, 1; The 5-naphthalene diisocyanate, 3,3 '-dimethyl--4,4 '-diphenyl diisocyanate; 4,4 '-two isocyanatos-dicyclohexyl methyl hydride, and 2,4 toluene diisocyanate.4,4 '-two isocyanatos-dicyclohexyl methyl hydride and 4,4 '-two isocyanatos-ditan more preferably.4,4 '-two isocyanato ditans are preferred.

Vulcabond also comprises aliphatic series and alicyclic isocyanate compound, for example 1,6-hexamethylene diisocyanate; Ethylidene diisocyanate; 1-isocyanato-3,5,5-trimethylammonium-1-3-isocyanato methylcyclohexane; 2,4-and 2,6-hexahydrotoluene vulcabond, and corresponding isomer mixture; 4,4 '-, 2,2 '-and 2,4 '-dicyclohexyl-methane diisocyanate, and corresponding isomer mixture.The present invention also can use 1,3-tetramethylene XDI.Said isocyanic ester can be selected from organic isocyanate, modified isocyanate, and based on the prepolymer of isocyanic ester, and the mixture of two kinds or more kinds of these isocyanic ester.

The organic diisocyanate of any aforementioned TPU of being used for preparation be can use, aromatics, aliphatic series, alicyclic diisocyanate and their mixture comprised.Exemplary isocyanic ester includes but not limited to: methylene radical two (phenyl isocyanate), comprise 4,4 '-isomer, 2,4 '-isomer and composition thereof; Between and to phenylene vulcabond; The chlorine phenylene vulcabond; α, α '-eylylene diisocyanate; Commercially available 2,4-and 2,6-tolylene diisocyanate and this two mixture of isomers of back; The tolidine vulcabond; Hexamethylene diisocyanate; 1, the 5-naphthalene diisocyanate; Isophorone diisocyanate etc.; Alicyclic diisocyanate, methylene radical two (cyclohexyl isocyanate) for example, comprise 4,4 '-isomer, 2,4 '-isomer and composition thereof, and their all geometrical isomers (comprise anti-/ anti-, suitable/anti-, suitable/suitable, and composition thereof); The cyclohexylidene vulcabond (1,2-; 1,3-; Or 1,4-); 1-methyl-2,5-cyclohexylidene vulcabond; 1-methyl-2,4-cyclohexylidene vulcabond; 1-methyl-2,6-cyclohexylidene vulcabond; 4,4 '-isopropylidene two (cyclohexyl isocyanate); 4,4 '-two isocyanato dicyclohexyls, and their all geometrical isomers and mixture etc.

The modified form that also comprises methylene radical two (phenyl isocyanate).The latter is meant that making them through handling is the methylene radical two (phenyl isocyanate) of those forms of stabilising liq when envrionment temperature (about 20 ℃).Such product comprises and those of the aliphatic diol of a small amount of (about at the most 0.2 equivalent is whenever the amount POLYMETHYLENE POLYPHENYLISOCYANATE) or aliphatic diol mixture reaction, the methylene radical two (phenyl isocyanate) of the modification described in the for example following USP: USP 3394164; 3644457; 3883571; 4031026; 4115429; 4118411; With 4299347; They incorporate this paper by reference into.The methylene radical two (phenyl isocyanate) of modification also comprises treated and a fraction of vulcabond is converted into corresponding carbodiimide forms those of urea ketone (uretone)-imine group with other vulcabond effect then, as when for example the product of gained is in envrionment temperature described in the USP 3384653, being stable liquid; This patent is incorporated this paper by reference into.The mixture of any in the POLYMETHYLENE POLYPHENYLISOCYANATE of pointing out above can using on demand.

The organic diisocyanate of suitable type comprises aromatics and alicyclic diisocyanate.In these types preferred material be methylene radical two (phenyl isocyanate) (comprise 4,4 '-isomer, 2,4 '-isomer and composition thereof), and methylene radical two (cyclohexyl isocyanate) (comprising above-mentioned isomer).In a kind of embodiment preferred, said isocyanic ester is 1,3-two (isocyanato methyl) hexanaphthene and 1, the mixture of 4-two (isocyanato methyl) hexanaphthene.In further embodiment, these two kinds of isocyanic ester existed with weight ratio in about 1: 1.

The available polymer diol is included in conventional those that use in the elastomeric field of preparation TPU.Polymer diol is to cause in resulting polymers the reason that forms soft chain segment, and molecular weight (number-average molecular weight) preferably falls into scope 200～10000g/mol, more preferably 400～4000g/mol, also more preferably 500～3000g/mol.Use above a kind of polymer diol and be not uncommon and possibly be favourable sometimes.The instance of said glycol has polyether glycol; Polyester glycol; Hydroxy-end capped polycarbonate, hydroxyl terminated poly-butadiene, hydroxyl terminated poly-butadiene-acrylonitrile copolymer; The hydroxy-end capped multipolymer of dialkylsiloxane and oxirane (for example oxyethane, propylene oxide etc. and composition thereof), any one uses with amino-terminated polyethers and amino-terminated polybutadiene-acrylonitrile copolymer as main ingredient (greater than 50%w/w) in the wherein above-mentioned polyvalent alcohol.Other instance of said glycol comprises the natural oil glycol.

Suitable polyether glycol comprises polyoxyethylene glycol and polyoxypropylene diols (they optional ethylene oxide residue end-blockings of using); Random and the segmented copolymer of oxyethane and propylene oxide; Polytetramethylene glycol; Random and the segmented copolymer of THF and oxyethane and/or propylene oxide; And come from above-mentioned any and bifunctional carboxylic acid or be derived from the product of reaction of the ester of said acid, wherein transesterification reaction takes place in the latter, and esterified group is replaced by the polyether glycol group.Preferred polyether glycol is oxyethane and the random and segmented copolymer of propylene oxide and the polytetramethylene glycol polymkeric substance of functionality about 2.0 of functionality about 2.0.

Suitable polyester polyol comprises those that utilization such as initiator polymerization 6-caprolactones such as terepthaloyl moietie, thanomin prepare; And those of the esterification preparation through poly carboxylic acid such as phthalandione, terephthalic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, nonane diacid etc. and polyvalent alcohol such as terepthaloyl moietie, butyleneglycol, cyclohexanedimethanol etc.

Suitable amine terminated polyether is the aliphatic primary amine that comes from polyoxypropylene diols on the structure.This type of polyether diamine can obtain (can obtain from Basell) with trade(brand)name JEFFAMINE from Jefferson Chemical Company at present.

The polycarbonate of suitable hydroxyl comprises through glycol for example 1; Ammediol, 1; 4-butyleneglycol, 1; 6-pinakon, 1,9-nonanediol, 2-methyl isophthalic acid, 8-ethohexadiol, glycol ether, triglycol, DPG etc. and dialkyl carbonate such as diphenyl carbonate or with those of phosgene reaction preparation.

Suitable silicon-containing polyether comprise oxirane and dialkylsiloxane for example the multipolymer of dimethyl siloxane etc. (referring to, for example USP 4057595 or the USP 4631329 before quoted, and incorporated this paper into).

Suitable hydroxyl terminated poly-butadiene multipolymer comprises can be from the compound of Arco Chemical Company with trade(brand)name Poly BD Liquid Resins acquisition.The hydroxyl terminated poly-butadiene multipolymer also can obtain from Sartomer.Hydroxy-end capped and the instance end capped butadiene/acrylonitrile copolymer of amine have can be respectively with hydroxy-end capped (HT) liquid polymer of trade(brand)name HYCAR and the material of amine end capped (AT) liquid polymer acquisition.Preferred glycol is above-mentioned polyether glycol and polyester glycol.

The dual functional chain extension agent that uses can be any in known those chain extension agents in the TPU field of top disclosure.Usually chain extension agent can be aliphatic straight chain and the side chain divalent alcohol that contains individual carbon atom 2～10 (comprising 2 and 10) in the chain.The instance of such glycol has terepthaloyl moietie, 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-pinakon, NSC 6366 etc.; 1,4 cyclohexane dimethanol; Quinhydrones two (hydroxyethyl) ether; Cyclohexylidene glycol (1,4-, 1,3-and 1,2-isomer), isopropylidene two (hexalin); Glycol ether, DPG, thanomin, N-methyl-diethylolamine etc.; And the mixture of above-mentioned arbitrary substance.As noted before, the difunctional chain extenders of a small amount of (less than about 20 equivalent %) can be replaced by trifunctional chain extenders in some cases, does not damage the thermoplasticity of gained TPU; The instance of such chain extension agent has glycerine, TriMethylolPropane(TMP) etc.

Although can use the top arbitrarily diol chain extender of describing and giving an example separately or with form of mixtures; But it is preferred separately or with form of mixtures (mix each other or mixes) use 1 with the aliphatic diol that points out one or more fronts; 4-butyleneglycol, 1; 6-pinakon,

NSC

6366,1,4 cyclohexane dimethanol, terepthaloyl moietie and glycol ether.Concrete preferred glycol is 1,4-butyleneglycol, 1,6-pinakon and 1,4 cyclohexane dimethanol.

The amount that the amount of introducing the chain extension agent in the urethane is needed by concrete reactant composition, hard soft chain segment and be enough to provide the exponential of good mechanical properties (like modulus and tear strength) to select decision.The polyurethane component that in enforcement of the present invention, uses can contain 2～25wt%, preferred 3～20wt% and the more preferably chain extension agent composition of 4～18wt%.

When needed, optional compound (usually being called " chain terminator ") the control molecular weight that can use a functional compound of a small amount of monohydroxy or an amino-functional.This chain terminator be exemplified as propyl alcohol, butanols, amylalcohol and hexanol.In use, chain terminator accounts for 0.1～2wt% of the entire reaction mixture that produces polyurethane component usually to exist on a small quantity.

The equivalence ratio of polymer diol and said chain extension agent can be according to the desired hardness of TPU product and is changed on a large scale.Generally speaking, this is than dropping on respective range about 1: 1 to about 1: 20, preferred about 1: 2 to about 1: 10.Simultaneously, the equivalent of isocyanic ester and the equivalent that contains active hydrogen substance are always than in scope 0.90: 1 to 1.10: 1 and preferred 0.95: 1 to 1.05: 1.

The composition that forms TPU is reacted in organic solvent, but preferably make the composition that forms TPU under the condition of organic solvent-free about 125 ℃～250 ℃ of temperature, react through melt extruding preferred about 160 ℃～225 ℃ the time.

Usually expectation but be not to comprise catalyzer at the reaction mixture that is used for preparing the present composition.The conventional any catalyzer that is used for the catalysis isocyanic ester and contains the reaction between the compound bearing active hydrogen all can be used for the present invention in this area; Referring to, for example, people's such as Saunders Polyurethaness, Chemistry and Technology, Part I, Interscience, New York, 1963, page or leaf 228-232; Also referring to, people's such as Britain J.Applied Polymer Science, 4,207-211,1960; Incorporate this paper separately by reference into.Such catalyzer comprises the organic and inorganic acid salt and the Organometallic derivatives of following material: bismuth, lead, tin, iron, antimony, uranium, cadmium, cobalt, thorium, aluminium, mercury, zinc, nickel, cerium, molybdenum, vanadium, copper, manganese and zirconium, and phosphine and trimethylamine.Representational organotin catalysts is stannous octoate, stannous oleate, two sad dibutyl tins, dibutyl tin laurate etc.Representational trimethylamine catalyzer is a triethylamine; Triethylenediamine; N, N, N ', N '-tetramethylethylened; N, N, N ', N '-tetraethyl-ethylene diamine, N-methylmorpholine; N-ethylmorpholine; N, N, N ', N '-tetramethyl guanidine; N, N, N ', N '-tetramethyl--1,3-tetramethylenediamine; N, the N-dimethylethanolamine; N, the N-diethylethanolamine; Deng.Catalyst consumption is generally in the scope of about 0.02～2.0wt%, based on the gross weight of reactant.

As discussed above; Can be through in " single stage method ", mixing all the components basically simultaneously; Perhaps can become to assign to prepare urethane through in " prepolymer method ", progressively adding each, wherein these methods can or not added under the optional additive condition and carry out in the presence of optional additive.Urethane forms reaction and can under the condition of adding or not adding the suitable catalyst that promotes isocyanic ester and hydroxyl or other functional group reactions, carry out with substance law or solution method.The instance of typical case's preparation of these urethane has been described in USP 5864001.

As stated, other main ingredient of the hard segment of urethane of the present invention is at least a chain extension agent well known in the art.As known, when chain extension agent was divalent alcohol, the product that obtains was thermoplastic polyurethane (TPU).When chain extension agent was diamines or amino alcohol, the product that obtains was thermoplasticity polyureas (TPUU) on technology.

Operable in the present invention chain extension agent is characterised in that to have two or more, preferably has two functional groups, contains " active hydrogen atom " separately.These functional groups are preferably in hydroxyl, primary amino, secondary amino group or these groups form of two kinds or more kinds of mixture.Term " active hydrogen atom " refer to since its in molecule layout and reveal active Wasserstoffatoms according to the Zerewitinoff test chart, like Kohler at J.Am.ChemicalSoc., 49, described in the 31-81 (1927).

Chain extension agent can be aliphatic, alicyclic or aromatics, and example has divalent alcohol, diamines and amino alcohol.Illustrative difunctional chain extenders has terepthaloyl moietie, glycol ether, Ucar 35, DPG, 1, ammediol, 1,3 butylene glycol, 1,4-butyleneglycol, 1; 5-pentanediol and other pentanediol, 2-ethyl-1,3-pinakon, 2-ethyl-1,6-pinakon, other 2-ethyl-pinakon, 1,6-pinakon and other pinakon, 2; 2,4-trimethylpentane-1,3-glycol, decanediol, dodecanediol, dihydroxyphenyl propane, Hydrogenated Bisphenol A 99,1; 4-cyclohexane diol, 1, two (2-the hydroxyl-oxethyl)-hexanaphthenes, 1 of 4-, 3-cyclohexanedimethanol, 1; 4-cyclohexane diol, 1, two (2-hydroxyl-oxethyl) benzene of 4-, Esterdiol 204 (3-hydroxyl-2,2-dimethyl--propionic acid-3-hydroxyl-2; 2-dimethyl-propyl ester derives from TCI America), N-Mono Methyl Ethanol Amine, N-methyl isopropyl amine, 4-Trans-4-Amino Cyclohexanol, 1,1; 3-diaminopropanes, NSC 446, Toluene-2,4-diisocyanate, 4-diamines and toluene-1,6-diamines.The aliphatic cpd that preferably contain 2～8 carbon atoms.If preparation thermoplasticity or solubility urethane, then chain extension agent will be in fact dual functional.The amine chain extension agent includes but not limited to quadrol, a carbinolamine and tn.

The general linear chain extenders of using is generally divalent alcohol, diamines or amino alcohol compound, it is characterized in that molecular weight is not more than 400g/mol (or dalton).In the application's context, " line style " is meant and do not comprise the branching that comes from tertiary carbon.The instance of suitable chain extension agent is represented by following molecular formula: HO-(CH ₂) _n-OH; H ₂N-(CH ₂) _n-NH ₂And H ₂N-(CH ₂) _n-OH, wherein " n " is generally 1～50 number.

A kind of common chain extension agent is 1, and 4-butyleneglycol (" butyleneglycol " or " BDO ") is expressed from the next: HO-CH ₂CH ₂CH ₂CH ₂-OH.Other suitable chain extension agent comprises terepthaloyl moietie; Glycol ether; 1, ammediol; 1, the 6-pinakon; 1, the 5-heptanediol; Tri Ethyleneglycol; 1,2-Rutgers 612 (EHD glycol); And two kinds or more kinds of combinations in these chain extension agents.In one embodiment, said chain extension agent is 1,2-Rutgers 612 (EHD glycol).

Same suitable is Cyclic chain extenders, is generally divalent alcohol, diamines or amino alcohol compound, it is characterized in that molecular weight is not more than 400g/mol.In the application's context, " ring-type " means and is ring texture, and typical ring texture includes but not limited to have the structure of 5～8 yuan of rings of hydroxyl-alkyl branches.The instance of Cyclic chain extenders is represented by following molecular formula: HO-R-(ring)-R '-OH and HO-R-O-(ring)-O-R '-OH, and wherein R and R ' they are the alkyl chain of 1～5 carbon, each ring has 5～8 ring memberses, all is carbon preferably.In these instances, one or two end-OH can be by-NH ₂Substitute.Suitable Cyclic chain extenders comprises cyclohexanedimethanol (" CHDM ") and quinhydrones two-2-hydroxyethyl (hydrxyethyl) ether (HQEE).The structural unit of preferred Cyclic chain extenders CHDM is expressed from the next: HO-CH ₂-(cyclohexane ring)-CH ₂-OH.

As well known to those skilled in the art, the ratio of isocyanic ester and whole functional groups has determined the Mn of polymkeric substance.In some cases, excessive a little isocyanic ester is used in expectation.

For line style, high Mn polymkeric substance, the raw material that every chain has two functional groups is desirable.Yet, can make raw material have the functionality of certain limit.For example, can use the polydiene with an end functional groups to come the two ends of blocked polyurethane, the middle portion of this urethane partly is made up of multiple isocyanic ester chain extension agent.The polydiene that has more than two functional groups will form branched polymer.If functionality is too high, crosslinked and gelling possibly become problem, but this can control through processing condition usually.These branched polymers will be presented at some rheological property of some situation desired, like high fondant-strength.

As stated, in preparation, can randomly use the catalyzer that promotes or help forming carbamate groups.Illustrative useful catalysts is stannous octoate, dibutyl tin laurate, stannous oleate, metatitanic acid tetrabutyl tin, tributyltin chloride, cobalt naphthenate, dibutyl tin oxide, potassium oxide, tin chloride, N; N; N, N '-tetramethyl--1,3-tetramethylenediamine, two [2-(N; The N-dimethylamino) ethyl] ether, 1,4-diazabicylo [2.2.2] octane, zirconium sequestrant, aluminum chelating agent and Bismuth carbonate.When using catalyzer, normally used catalytic amount can for from 0.001wt% with down to more than the 2wt%, based on the total amount of the composition that forms urethane.

Can use additive to change the character of urethane used in the present invention implements.Can prior art and document in known convention amount comprise these additives.Usually use additive the character of certain desired, the for example various inhibitors of this additive, ultraviolet inhibitor, wax, thickening material and filler to be provided as urethane.When using filler, they can be organic or inorganic, but are generally inorganic, for example clay, talcum, lime carbonate, silica etc.In addition, also can add fibering additive such as spun glass or thomel, thereby give specific character.

The urethane that is used for the present invention's enforcement preferably reacts with optional chain extension agent through functionality polyester and isocyanic ester and prepares.In " prepolymer " method, make one or more functionality polydiene and one or more isocyanate reactions usually to form prepolymer.This prepolymer further reacts with one or more chain extension agents.Perhaps, said urethane also can prepare through the single step reaction of all reactants.The number-average molecular weight of typical urethane is 5000～1000000g/mol, and more preferably 20000～100000g/mol.

In a kind of embodiment preferred of the present invention, said urethane is formed by polyester, isocyanic ester and chain extension agent (aliphatic chain extension agent).In a kind of embodiment preferred, these polyester have at least one and more preferably at least two ester groups in molecule, and Mn is 500～10000g/mol usually, more preferably 1000～5000g/mol, even more preferably 1500～3000g/mol.

In another kind of embodiment, said urethane is by the vulcabond that comprises 10～40wt% (vulcabond of preferred 15～35wt%); The polyester of 50～85wt% (polyester of preferred 55～80wt%, the more preferably polyester of 60～80wt%); And the compsn of the chain extension agent of 2～15wt% (chain extension agent of preferred 2～10wt%) forms, and each wt% is all based on the gross weight of reactant.In further embodiment, said vulcabond is aliphatic series or aromatic diisocyanate, and more preferably 4,4 '-diphenylmethanediisocyanate.more further in the embodiment, said chain extension agent is an aliphatic diol.In another kind of embodiment, the Mn of said polydiene glycol is 500～10000g/mol, more preferably 1000～5000g/mol, even more preferably 1500～3000g/mol.

In one embodiment, the density of said urethane is more than or equal to 0.90g/cc, be preferably greater than or equal 0.95g/cc, more preferably greater than or equal 1.00g/cc.In another kind of embodiment, the density of said urethane is less than or equal to 1.30g/cc, preferably is less than or equal to 1.25g/cc, is more preferably less than or equals 1.20g/cc.In another kind of embodiment, the density of said urethane is 0.90～1.30g/cc, preferred 0.95～1.25g/cc, more preferably 1.00～1.20g/cc.Comprise and described all independent values and the sub-range of 0.90～1.30g/cc here.

In another kind of embodiment, the melt index of said urethane more than or equal to 0.1 the gram/10 minutes, be preferably greater than or equal 0.5 the gram/10 minutes, more preferably greater than or equal 1 the gram/10 minutes (ASTMD-1238-04,190 ℃, 8.7kg).In another kind of embodiment, the melt index of said urethane is less than or equal to 100 grams/10 minutes, preferably is less than or equal to 50 grams/10 minutes; Be more preferably less than or equal 20 and restrain/10 minutes; Even be more preferably less than or equal 10 the gram/10 minutes (ASTM D-1238-04,230 ℃, 8.7kg).In another kind of embodiment, the melt index of said urethane is 0.1～100 gram/10 minutes, preferred 0.5～50 gram/10 minutes, and more preferably 1～20 gram is/10 minutes, even more preferably 1～10 restrains/10 minutes.In a kind of embodiment preferred, the melt index of said urethane is 6～10 grams/10 minutes, preferred 7～9 grams/10 minutes.Comprise here and described 0.1～100 and restrain/10 minutes all independent values and sub-range.

Preferred urethane comprises can be from the Pellethane of Dow Chemical Company acquisition ^TMTPUE.

Be applicable to that other urethane of the present invention includes but not limited to: the ESTANE thermoplastic polyurethane; The TECOFLEX thermoplastic polyurethane; The CARBOTHANE thermoplastic polyurethane; The TECOPHILIC thermoplastic polyurethane, TECOPLAST thermoplastic polyurethane and TECOTHANE thermoplastic polyurethane all can obtain from Noveon; Can be from the ELASTOLLAN thermoplastic polyurethane and other thermoplastic polyurethane of BASF acquisition; And can be from the commercial thermoplastic urethane of Bayer, Huntsman and Merquinsa acquisition.

Polyurethane component can comprise one or both combination of aforesaid suitable embodiments.

If need, can be when any suitable stage of preparation, in urethane, add usually and polyurethane elastomer unite use such as additives such as pigment, filler, lubricant, stablizer, inhibitor, tinting material, fire retardants.

Filler

Compsn of the present invention can comprise one or more fillers.This type of filler includes but not limited to silicate, aluminate, aluminosilicate, aluminum oxide, talcum, mica, lime carbonate, titanium oxide and Marinco H.Filler also comprises the filler of surface-treated, includes but not limited to the silica of surface-treated and the silicate of surface-treated (preferably talc).

In one embodiment, said filler is a silicate, and it is by the silicol surface-treated.In another kind of embodiment, said filler is a talcum, and it is by the silicol surface-treated.

In another kind of embodiment, said filler is a silicate, and it is by amine silane surface modified.In another kind of embodiment, said filler is a talcum, and it is by amine silane surface modified.

In another kind of embodiment, said aminosilane is selected from following structure:

(I)，

(II)，

(III)。

For structure I, R ₁, R ₂And R ₃Be alkyl (preferable methyl or ethyl), hydrogen or chlorine independently of one another.

For structure I I, R ₁, R ₂, R ₃, R ₄And R ₅Be alkyl (preferable methyl or ethyl), hydrogen or chlorine independently of one another.

For structure III, R ₁, R ₂, R ₃, R ₄, R ₅, R ₆And R ₇Be alkyl (preferable methyl or ethyl), hydrogen or chlorine independently of one another; N is 0～50, and is preferred 0～20, and more preferably 0～10.

In another kind of embodiment, compsn of the present invention comprises 0～60wt% by the gross weight of compsn, preferred 5～50wt%, and the more preferably at least a filler of 10～40wt%.In a kind of further embodiment, said filler is a silicate.In another kind of embodiment, said filler is a talcum.In another kind of embodiment, said filler is a silicate, and it is by amine silane surface modified.In another kind of embodiment, said filler talcum, it is by amine silane surface modified.

Compsn of the present invention

Compsn of the present invention comprises usually: a) the many block interpolymers of at least a alkene; B) at least a functionalized polymkeric substance based on alkene; And optional c) at least a thermoplastic polyurethane.

1. the compsn that comprises two kinds or more kinds of components

For comprising the many block interpolymers of (a) at least a alkene; And b) compsn of at least a functionalized polymkeric substance based on alkene, the many block interpolymers of preferred said alkene are the many block interpolymers of ethylene/alpha-olefin.

In one embodiment; The amount of said functionalized polymkeric substance based on alkene is less than or equal to 20wt%, is more preferably less than or equals 15wt%, is more preferably less than or equals 10wt%; Even be more preferably less than or equal 5wt%, by the gross weight of compsn.

In another kind of embodiment, the amount of said functionalized polymkeric substance based on alkene is more than or equal to 50wt%, more preferably greater than or equal 60wt%, even more preferably greater than or equal 70wt%, by the gross weight of compsn.

In another kind of embodiment, said compsn comprises said many block interpolymers of alkene optimal ethylene/alpha-olefin multi-block interpretation of 75～95wt% and preferred 80～75wt%, by the gross weight of compsn.Said terminal olefin is preferably C ₃-C ₁₀Terminal olefin, and more preferably be selected from propylene, 1-butylene, 1-hexene and 1-octene.

In another kind of embodiment, said compsn comprises the said functionalized polymkeric substance based on alkene of 1～10wt%; And the many block interpolymers of said alkene of 99～90wt%, optimal ethylene/alpha-olefin multi-block interpretation is based on the gross weight of this two component.Said terminal olefin is preferably C ₃-C ₁₀Terminal olefin, and more preferably be selected from down group: propylene, 1-butylene, 1-hexene and 1-octene.

In another kind of embodiment, said compsn comprises the functionalized polymkeric substance based on alkene of 70～100wt%, and the many block interpolymers of the alkene of 0～30wt%; Each weight percent number average is based on the gross weight of this two component.

In another kind of embodiment, said compsn comprises preferred 10～35wt% of 5～40wt% and the more preferably functionalized polymkeric substance based on alkene of 12～30wt%, by the gross weight of compsn.

In another kind of embodiment, said compsn comprises the many block interpolymers of alkene that are preferably greater than or equal 55wt% more than or equal to 50wt%, by the gross weight of compsn.

In another kind of embodiment, compsn of the present invention comprises preferred 5～50wt% of 0～60wt% and the more preferably at least a filler of 10～40wt%, by the gross weight of compsn.In a kind of further embodiment, said filler is a silicate.In another kind of embodiment, said filler is a talcum.In another kind of embodiment, said filler is a silicate, and it is with amine silane surface modified.In another kind of embodiment, said filler is a talcum, and it is with amine silane surface modified.

In another kind of embodiment, said compsn comprises the many block interpolymers of alkene of the preferred 50～55wt% of 45～60wt%; The functionalized polymkeric substance of the preferred 10～15wt% of 5～20wt% based on alkene; And the filler of the preferred 30～40wt% of 25～45wt%; Each weight percent number average is based on the gross weight of this three component.In a kind of further embodiment, said filler is a silicate.In another kind of embodiment, said filler is a talcum.

In another kind of embodiment, said compsn comprises the many block interpolymers of alkene of the preferred 50～55wt% of 45～60wt%; The functionalized polymkeric substance of the preferred 10～15wt% of 5～20wt% based on alkene; And the filler of the surface-treated of the preferred 30～40wt% of 25～45wt%; Each weight percent number average is based on the gross weight of this two component.In a kind of further embodiment, said filler is a silicate, and it is with amine silane surface modified.In another kind of embodiment, said filler is a talcum, and it is with amine silane surface modified.

Compsn of the present invention can randomly comprise one or more additives.Can in compsn of the present invention, add additive, for example process oil, slip(ping)agent, anti, AO, UV, filler.Usually, compsn of the present invention will contain one or more stablizers, for example inhibitor such as Irganox ^TM1010 and Irgafos ^TM168, both supply by Ciba Specialty Chemicals.Usually extrude or other melting treatment before handle polymkeric substance with one or more stablizers.Other polymeric additive includes but not limited to, ultraviolet absorbers, static inhibitor, pigment, dyestuff, nucleator, filler, slip(ping)agent, fire retardant, softening agent, processing aid, lubricant, stablizer, protection from fumes agent, viscosity control agent, anti, releasing agent, fire retardant, resistance to wears and abrades additive (abrasion and scratch maradditives), antiseptic-germicide, static inhibitor and linking agent.

2. the compsn that comprises at least three kinds of components

For comprising the many block interpolymers of (a) at least a alkene; B) at least a functionalized polymkeric substance based on alkene; And c) compsn of at least a thermoplastic polyurethane; The amount of usually preferred said functionalized polymkeric substance based on alkene is less than or equal to 20wt%; Be more preferably less than or equal 15wt%, even be more preferably less than or equal 10wt%, by the gross weight of compsn.

In one embodiment, said compsn comprises the thermoplastic polyurethane of 15～35wt% and preferred 20～30wt%, by the gross weight of compsn.

In another kind of embodiment, said compsn comprises the many block interpolymers of alkene of 55～80wt% and preferred 60～75wt%, by the gross weight of compsn.The many block interpolymers of preferred said alkene are ethylene/alpha-olefin interpolymers.Said terminal olefin is preferably C ₃-C ₁₀Terminal olefin, and more preferably be selected from propylene, 1-butylene, 1-hexene and 1-octene, also more preferably 1-octene.

In one embodiment, said compsn comprises the functionalized polymkeric substance based on alkene of 5～10wt%; The thermoplastic polyurethane of 15～35wt%; And the many block interpolymers of the alkene of 55～80wt%, by the gross weight of compsn.The many block interpolymers of preferred said alkene are ethylene/alpha-olefin interpolymers.Said terminal olefin is preferably C ₃-C ₁₀Terminal olefin, and more preferably be selected from propylene, 1-butylene, 1-hexene and 1-octene, also more preferably 1-octene.

In another kind of embodiment, said compsn comprises the functionalized polymkeric substance based on alkene of 5～10wt%; The thermoplastic polyurethane of 20～30wt%; And the many block interpolymers of the alkene of 60～75wt%, by the gross weight of compsn.The many block interpolymers of preferred said alkene are ethylene/alpha-olefin interpolymers.Said terminal olefin is preferably C ₃-C ₁₀Terminal olefin, and more preferably be selected from propylene, 1-butylene, 1-hexene and 1-octene, also more preferably 1-octene.

3. the additive of compsn of the present invention

The above-mentioned compsn that comprises two kinds or more kinds of component or at least three kinds of components can randomly comprise one or more additives.Can in compsn of the present invention, add additive, for example process oil, slip(ping)agent, anti, AO, UV, filler.Usually, compsn of the present invention will contain one or more stablizers, for example inhibitor such as Irganox ^TM1010 and Irgafos ^TM168, both supply by CibaSpecialty Chemicals.Usually extrude or other melting treatment before handle polymkeric substance with one or more stablizers.Other polymeric additive includes but not limited to, ultraviolet absorbers, static inhibitor, pigment, dyestuff, nucleator, filler, slip(ping)agent, fire retardant, softening agent, processing aid, lubricant, stablizer, protection from fumes agent, viscosity control agent, anti, releasing agent, fire retardant, resistance to wears and abrades additive, antiseptic-germicide, static inhibitor and linking agent.

5. comprise the polymkeric substance and at least a compound and/or at least a present composition that contains the compound of carboxylic acid that contains acid anhydride based on alkene

The preferred present composition comprises following component: a) the many block interpolymers of at least a alkene; B) at least a thermoplastic polyurethane; And c) by polymkeric substance and at least a compound and/or at least a at least a functionalized polymkeric substance that contains the compound formation of carboxylic acid that contains acid anhydride based on alkene based on alkene.

In one embodiment, the amount of functionalized polymkeric substance based on alkene is less than or equal to 20wt% by the gross weight of compsn, preferably is less than or equal to 15wt%, is more preferably less than or equals 10wt%, even be more preferably less than or equal 5wt%.In an embodiment preferred, the amount of functionalized polymkeric substance based on alkene is less than or equal to 10wt% by the gross weight of compsn, and preferably is less than or equal to 5wt%.

In another kind of embodiment, said compsn comprises the thermoplastic polyurethane (preferred as described herein) of 10～90wt% and the many block interpolymers of at least a alkene of 90～10wt%, by the gross weight of this two component.In a kind of further embodiment, said compsn comprises the functionalized polymkeric substance based on alkene of 1～10wt%.

In another kind of embodiment, said compsn comprises 10～50wt%, and preferred 25～40wt%, and the more preferably thermoplastic polyurethane of 25～37wt% (preferred as described herein) are by the gross weight of compsn.

In another kind of embodiment, said compsn comprises 55～80wt%, and preferred 60～75wt%, even the more preferably many block interpolymers of alkene of 63～75wt%, by the gross weight of compsn.

In another kind of embodiment, said compsn comprises 55～80wt%, and preferred 60～75wt%, even the more preferably many block interpolymers of alkene of 63～75wt% (preferred as described herein), by the gross weight of compsn.Preferably, the many block interpolymers of said alkene are the many block interpolymers of ethene, and said terminal olefin is selected from propylene, 1-butylene, 1-hexene and 1-octene, and more preferably 1-octene.

In one embodiment, said compsn comprises the functionalized polymkeric substance based on alkene of 1～10wt%; The thermoplastic polyurethane of 15～50wt% (preferred as described herein), and the many block interpolymers of the alkene of 55～80wt% are by the gross weight of compsn.Preferably, the many block interpolymers of said alkene are the many block interpolymers of ethene, and said terminal olefin is selected from propylene, 1-butylene, 1-hexene and 1-octene, and more preferably 1-octene.

In another kind of embodiment, said compsn comprises the functionalized polymkeric substance based on alkene of 1～10wt% by the gross weight of compsn; The thermoplastic polyurethane of 25～40wt% (preferred as described herein), and the many block interpolymers of the alkene of 60～75wt%.Preferably, the many block interpolymers of said alkene are the many block interpolymers of ethene, and said terminal olefin is selected from propylene, 1-butylene, 1-hexene and 1-octene, and more preferably 1-octene.

In one embodiment, said compsn comprises the functionalized polymkeric substance based on alkene of 1～10wt% by the gross weight of compsn; The thermoplastic polyurethane of 15～50wt% (preferred as described herein), and the many block interpolymers of the ethene of 55～80wt% (preferred as described herein).Said terminal olefin is preferably selected from propylene, 1-butylene, 1-hexene and 1-octene, and more preferably 1-octene.

In another kind of embodiment, said compsn comprises the functionalized polymkeric substance based on alkene of 1～10wt% by the gross weight of compsn; The thermoplastic polyurethane of 25～40wt% (preferred as described herein), and the many block interpolymers of the ethene of 60～75wt% (preferred as described herein).Said terminal olefin is preferably selected from propylene, 1-butylene, 1-hexene and 1-octene, and more preferably 1-octene.

In another kind of embodiment, the amount of the many block interpolymers of said alkene is more than or equal to 50wt%, and the amount of urethane is less than or equal to 50wt%, and wherein wt percentage number average is based on the gross weight of many block interpolymers of alkene and urethane.The thermoplastic polyurethane of the many block interpolymers of the alkene of the preferred 50～90wt% of content and 45～10wt%, and the more preferably many block interpolymers of alkene and the 45～15wt% thermoplastic polyurethane of 55～85wt%.In another kind of embodiment, said compsn comprises the many block interpolymers of alkene of 55～80wt% and the urethane of 45～20wt%.Selecting content to make total value is 100wt%.Comprise and disclose all independent value and sub-ranges of the many block interpolymers of alkene of 50～90wt% here.Comprise and disclose all independent value and sub-ranges of the urethane of 50～10wt% here.Preferably, the many block interpolymers of said alkene are the many block interpolymers of ethene, and said terminal olefin is selected from propylene, 1-butylene, 1-hexene and 1-octene, and more preferably 1-octene.

In another kind of embodiment, compsn of the present invention comprises the above and above many block interpolymers of alkene of preferred 60wt% of 50wt%, and the thermoplastic polyurethane below the following and preferred 40wt% of 50wt%.In one embodiment, said compsn comprises the many block interpolymers of alkene of 50wt%～80wt% and preferred 55wt%～77wt%; And the thermoplastic polyurethane of 20wt%～50wt% and preferred 23wt%～45wt%; Wherein wt percentage number average is based on the gross weight of many block interpolymers of alkene and urethane.Preferably, the many block interpolymers of said alkene are the many block interpolymers of ethene, and said terminal olefin is selected from propylene, 1-butylene, 1-hexene and 1-octene, and more preferably 1-octene.

In another kind of embodiment, the gross weight of many block interpolymers of the alkene that compsn of the present invention comprises and thermoplastic polyurethane greater than 85wt%, is preferably greater than 90wt% by the gross weight of compsn, and more preferably greater than 95wt%.Preferably, the many block interpolymers of said alkene are the many block interpolymers of ethene, and said terminal olefin is selected from propylene, 1-butylene, 1-hexene and 1-octene, and more preferably 1-octene.

If compositions for use comprises component for example filler, the pigment etc. outside the above-mentioned polymeric constituent in enforcement of the present invention; The gross weight of the many block interpolymers of alkene, thermoplastic polyurethane and functionalized polymkeric substance based on alkene is preferably greater than 85wt% by the gross weight of blend so; Be preferably greater than 90wt%, and more preferably greater than 95wt%.

In one embodiment, the melt index (I of compositions for use in enforcement of the present invention ₂) utilize ASTM D-1238 (190 ℃, 2.16kg load) to be determined as 0.01～100g/10min, preferred 0.1～50g/10min, and more preferably 1～40g/10min, even more preferably 5～40g/10min.In another kind of embodiment, the I of said compsn ₂More than or equal to 0.01g/10min, be preferably greater than or equal 1g/10min, and more preferably greater than or equal 5g/10min.In another kind of embodiment, the I of said compsn ₂Be less than or equal to 100g/10min, preferably be less than or equal to 50g/10min, and be more preferably less than or equal 20g/10min.The I of compsn ₂Be promptly not contain meeting remarkably influenced I at pure blend ₂The blend of other component of measurement on record.

In another kind of embodiment, the crystallinity percentage of said compsn is less than or equal to 50% through dsc measurement, preferably is less than or equal to 30%, and is more preferably less than or equals 20%.In one embodiment, these crystallinity of polymer percentage ratios are 2～50%, comprise all independent value and sub-ranges of 2～50%.The percent crystallinity of compsn is promptly not contain at pure blend can remarkably influenced to record on the blend of other component of measurement of percent crystallinity.

In another embodiment, the density of said compsn is more than or equal to 0.855 gram per centimeter ³(g/cm ³Or g/cc), be preferably greater than or equal 0.86g/cm ³, more preferably greater than or equal 0.87g/cm ³In another embodiment, the density of said compsn is for being less than or equal to 1g/cm ³, preferably be less than or equal to 0.97g/cm ³, be more preferably less than or equal 0.96g/cm ³, even be more preferably less than or equal 0.95g/cm ³In one embodiment, said density is 0.855～0.97g/cm ³, preferred 0.86～0.95g/cm ³, and more preferably 0.865～0.93g/cm ³The density of compsn is promptly not contain at pure blend can remarkably influenced to record on the blend of other component of measurement of density.Compsn comprises in those embodiments of one or more fillers such as permanent white, talcum etc. therein, and maximum density can surpass 1g/cm ³, for example, maximum density can near or surpass 1.4g/cm ³, this depends on character and content of filler etc.

In another kind of embodiment, the tensile strength of the compsn of pure form and shaping form (fabricated form) is 5～40 MPas (MPa), preferred 8～30 MPas, even more preferably 9～20 MPas.

In another kind of embodiment, the longitudinal tensile strain rate of the compsn of pure form and shaping form or cross direction elongation are 50～600 when measuring according to ASTM D-638-03, perhaps 50～500.

In another kind of embodiment, the melt strength of the compsn of pure form is 0.5～50 li of ox (cN), more preferably 0.5～20 li of ox, even more preferably 0.5～10 li of ox.

In another kind of embodiment, the surface tension of the compsn of pure form is 10～100 dynes per centimeter (dyn/cm) when room temperature or 23 ℃, more preferably 20～70dyn/cm and even more preferably 30～50dyn/cm.

In another kind of embodiment, the surface tension of the compsn of pure form when room temperature or 23 ℃ more than or equal to 32dyn/cm, more preferably greater than or equal 33dyn/cm, even more preferably greater than or equal 35dyn/cm.

In another kind of embodiment, when when extruding with 80lbs/hr through the hanger-style die of 40 mil thick, 2 feet wide, compsn of the present invention produces the surface energy greater than 35dyn/cm at 200 ℃ of die head temperatures (180～190 ℃ of district's temperature).

In another kind of embodiment, composition molding of the present invention is an extrusion sheet, and this extrusion sheet keeps at least 50% of its original elongation in 120 ℃ of thermal ageings 500 hours (ASTM D-882-02) back, preferably at least 60%.

In another kind of embodiment, the present invention provides such above-mentioned compsn, and the many block interpolymers of wherein said alkene (optimal ethylene/alpha-olefin multi-block interpretation) are to exist continuously or with the common successive form mutually of thermoplastic polyurethane.

In another kind of embodiment, the present invention provides such above-mentioned compsn, and the many block interpolymers of wherein said alkene (optimal ethylene/alpha-olefin multi-block interpretation) exist to be total to successive form mutually with thermoplastic polyurethane.

Compsn of the present invention can prepare through merging the many block interpolymers of one or more alkene (and preferably the many block interpolymers of one or more ethylene/alpha-olefins) and one or more thermoplastic polyurethanes.Usually, compsn of the present invention through reactor drum after (post-reactor) polymer blend component (the many block interpolymers of alkene, urethane and functionalized polymkeric substance) based on alkene prepare.The illustrative examples of blend is for extruding behind the reactor drum, wherein with two kinds or more kinds of solid polymer is sent into forcing machine and physical mixed becomes the compsn of homogeneous basically.Compsn of the present invention can be crosslinked and/or foaming.In a kind of embodiment preferred, compsn of the present invention is through preparing with each component of smelting process blend.In a kind of further embodiment, this smelting process is for melt extruding technology, and preferred " online " compounding technology.

In another kind of embodiment; Said compsn also comprises the polyacrylic polymer component, for example the coring blend of the blend of the multipolymer of the homopolymer of propylene, propylene and ethene or at least a terminal olefin or homopolymer and multipolymer, coring homopolymer, coring multipolymer or homopolymer and multipolymer.Terminal olefin in the propylene copolymer can be 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene or 4-methyl-1-pentene.Ethene is preferred comonomer.Said multipolymer can be the blend of random copolymers or segmented copolymer or random copolymers and segmented copolymer.Said polymkeric substance can also be a branching.Thus, preferably this component is selected from down group: HPP homopolymer polypropylene and propylene/ethylene copolymer, perhaps their mixture.The melt flow rate(MFR) of this component (MFR) (230 ℃ and 2.16kg heavy burden) is 0.1 gram/10 minutes to 150 gram/l0 minutes; Preferred 0.3 the gram/10 minutes to 60 the gram/10 minutes; More preferably 0.8 the gram/10 minutes to 40 the gram/10 minutes, most preferably 0.8 the gram/10 minutes to 25 the gram/10 minutes.Comprise here and disclose 0.1～150 and restrain/10 minutes all independent values and sub-range.The density of this component can be 0.84～0.92g/cc, more preferably 0.85～0.91g/cc, most preferably 0.86～0.90g/cc.Comprise and disclose all independent values and the sub-range of 0.84～0.92g/cc here.This component can have the fusing point greater than 125 ℃.

" coring " used herein is meant the polymkeric substance of modification through adding nucleator (as available from

dibenzyl Sorbitol Powder).Also can use other conventional nucleator.

Can in any present composition as herein described, add additive, for example process oil, slip(ping)agent, anti, AO, UV, filler.Usually, said compsn will contain one or more stablizers, for example inhibitor such as Irganox ^TM10l0 and Irgafos ^TM168, both supply by CibaSpecialty Chemicals.An instance of hindered phenol anti-oxidants is

1076 inhibitors, and it can obtain from Ciba-Geigy Corp.Usually extrude or other melting treatment before handle polymkeric substance with one or more stablizers.Other polymeric additive includes but not limited to, ultraviolet absorbers, static inhibitor, pigment, dyestuff, nucleator, filler, slip(ping)agent, fire retardant, softening agent, processing aid, lubricant, stablizer, protection from fumes agent, viscosity control agent and anti.Other additive comprises but is not limited to, and surface tension modifier, pigment, process oil, wax, whipping agent, anti-hard caking agent (anti-block agent), pore forming material, static inhibitor, releasing agent, whipping agent, pore forming material, static inhibitor, releasing agent, fire retardant, resistance to wears and abrades additive, antiseptic-germicide, static inhibitor and linking agent.

Use

The above-mentioned compsn that comprises two kinds or more kinds of component or at least three kinds of components can be used in the many kinds of different application.For example, the present invention provides a kind of goods that comprise at least one assembly that is formed by the present composition as herein described.Compsn of the present invention specifically is applicable to tack coat between injection-molded item, blow-molded article, lamination injection-molded item, extrusion sheet, tackiness agent, the extrusion sheet, the tack coat between the cast-sheet, intermembranous tack coat, the tack coat between the section bar, fiber and dispersion-s (moisture and not moisture).Other goods comprise the carpet composition; Leatheroid; Artificial turf; Tackiness agent; Fabric; Dispersion-s; The sheath of line; Cable; Vest; Coating; Coated article; Laminate; Foam layer is fit; Footwear component (footwear outer bottom for example; At the bottom of sole middle level and the footwear list (shoe unit-sole)); Common plastics footwear (boots for example; Sandals (sandal); Overshoes (galoshes)); Perhaps synthesize and the natural leather goods; Perhaps automobile product (air bag for example; Head rest; Arm rest; Underlayment; But japanning trolley part etc.) and to the tackiness agent of Kevlar.

In another kind of embodiment, goods are automobile crust (test board shell or door face board shell); Awning; Oilcloth; The roof building goods (for example; The tackiness agent that is used for all rooftop applications to epoxy, carbamate or acrylic substrate, rooftop applications connects (insulation bonding), liquid roof (liquid roofing), facade sealing agent (facade sealant), expansion pipe (expansionjoint), moist room sealing agent (wet-room sealant), goes up bituminous roof, the adherent roof of acrylics, pitch connection and the adherent trimming of PUR-roof (refurbishment) like insulation); Bearing circle; Powder coating; Powder slush moulding thing; Durable consumer goods; Handle; Handle; Computer module; Band; Attach ornaments; Shoe assembly; Travelling belt or Timing Belt; Lubricant and oil formulation; Fiber; Film, the film packing of various size; Fabric; Leatheroid; The injection moulding object, but like the toy of injection moulding and/or japanning; Artificial turf; Leatheroid; Tackiness agent to Kevlar; Film, the film packing of various size; Dispersion-s; Powder coating, powder slush moulding thing or rotational casting thing (common granularity separately is less than 950 microns), durable consumer goods, handle; Handle, computer module (for example keyseat), band, the tackiness agent of fabric/urethane (PU) foam layer fit (for example attaching ornaments and footwear); For example be used for wearing layer is bonded to the tackiness agent (melt of heat or other) on the extruded product, travelling belt or Timing Belt, fabric, carpet; Artificial turf, coating, line and cable, and raincoat and similar vest.

Concrete application comprises the tackiness agent to polyurethane film and foams, to the tackiness agent of polyester; Dyestuff; Paint tackiness agent and paint adhere to activator (paint adhesion enabler); Welding applications; Automotive interior and outside; The expanding material of polymer compsn; And the toughner of polymer compsn.

Particularly; Compsn of the present invention can be used for following application: at the bottom of the footwear outer bottom of the standard polyurethane adhesive system assembling of (a) using at present with shoemaking industry, sole middle level, the footwear list and the footwear stiffener; (b) with of the coating of the present urethane paint that uses of shoemaking industry to footwear outer bottom, sole middle level, and (c) multilayer sole and the polyolefine in sole middle level and the lamination injection moulding of two component polyurethane.In addition, compsn of the present invention can be used for other application like automotive applications and structure applications.Automotive applications includes but not limited to make bumper fascia (bumper fascia), vertical panel, soft TPO shell, interior trim and panel enclosure.Structure applications includes but not limited to make furniture and toy.

Other application comprises bonding (wherein one or more base materials be with functional group such as hydroxyl is compatible or reaction with it) of co-extruded films, and based on layer close (for example, glass coating closes) of polyolefinic film and other polar substrates.Application in addition comprises leatheroid is adhered to polar substrates for example on urethane, SE (PVC) and other base material.Used for artificial leather adheres to be used for seat, inside roof lining (head liner) with urethane in automotive interior.

Compsn of the present invention also is applicable to the health articles for use as wiping away paper, cleaning thin paper, but foams or substantive dyeing fiber.Compsn of the present invention can be used for improving and separates or ventilative elastomeric wetting ability with the new membrane structure.Compsn of the present invention also is suitable for being used as at the metal of automobile or the autoadhesion elastomerics on the textile structural.As stated, compsn of the present invention is very suitable for having blend and the expanding material of enhanced to the effect of polar polymer such as TPU, EVA, PVC, PC, PET, PLA (POLYACTIC ACID), polyesteramide and PBT.Such blend can be used for the novel formulation of footwear, automobile, durable consumer goods, utensil, electronic shell, clothes and travelling belt.

Compsn of the present invention also can be used as the expanding material between natural fiber and other polyolefine, is used for using like bonding wood materials prescription or the bonding prescription of Mierocrystalline cellulose.Compsn of the present invention can be used for the blend with one or more polyether block amides (

polymkeric substance that for example can obtain from Arkema) equally.Compsn of the present invention also can be used as the impact modifier of nylon.The amino protonated or alkylation that in addition, can make the present composition is to form quaternary nitrogen or ionomer, as antiseptic-germicide.

Compsn of the present invention also can be used for strengthening the effect to filler such as silica, carbon black or clay, is used for the preparation of toning agent, tire, coating or other formulation.Compsn of the present invention also can be used for engine oil viscosity modifier, engine oil dispersion agent, clothes and maybe can print fiber, paint tackifier, glass and stick with glue the composition in agent, metal and PVDC opacity resin, dispersion-s and priming paint and the sizing agent with dying.

Therefore the present invention also provides a kind of paint substrates coated, and wherein this base material is formed by the present composition as herein described, and paint comprises following at least a: acrylic polymers; Synolac is based on cellulosic material, melamine resin; Urethane resin, carbamate resins, vibrin; Vinyl acetate resin, polyvalent alcohol and alcohols.In a kind of further embodiment, said paint is based on the paint of water.In another kind of embodiment, said paint is based on the paint of organic solvent.

Embodiment of the present invention works to being coated with agent prescription widely well.The main ingredient of solvent-borne type (solvent-borne) paint and coating is solvent, tackiness agent, pigment and additive.In paint, the combination of tackiness agent and solvent is called and is coated with agent carrier.Pigment and additive are dispersed in this carrier.The amount of every kind of component changes with concrete paint, but solvent accounts for about 60% of whole prescriptions usually.Typical solvent comprises toluene, YLENE, methylethylketone, MIBK and water.The about 30wt% of binder constitutes, pigment accounts for 7～8wt%, and additive accounts for 2～3wt%.Some polymkeric substance that in being coated with agent prescription, use comprise with other additive: acrylic polymers, and Synolac is based on cellulosic material such as cellulose acetate butyrate; Melamine resin, carbamate resins, vibrin; The vinyl acetate resin, urethane resin, polyvalent alcohol; Alcohols, inorganics such as titanium oxide (rutile), sheet mica, red stone, silica, aluminium etc.

The present invention also provides a kind of lamination injection-molded item, and these goods form by polar substrates with by the moulding veneer that the present composition as described herein forms.In another kind of embodiment, the present invention provides a kind of lamination injection-molded item, and these goods are formed by base material that comprises the present composition as described herein and the moulding veneer that comprises polar material.In further embodiment, said goods are the form of handle, handle or band.

In another kind of embodiment; The present invention provides a kind of lamination injection-molded item; It comprises polycarbonate as base sheet; This base sheet has variable thickness and preferably has the face that can adhere to the veining of the present composition at least one its, at 140 ℃ neutral temperature the present composition is adhered to this face through compression-molding process usually.Such goods have excellent adhesivity.The welding technique of routine capable of using perhaps can adhere to second polycarbonate sheet with texturizing surfaces the exposed surface of present composition film as exerting pressure and heating is further closed these goods with polyolefin layer.

The present invention also provides a kind of laminate structures that comprises the first layer and the second layer, and said the first layer is to be formed by the present composition as described herein, and the said second layer is to be formed by the compsn that comprises polar material.In a kind of further embodiment, the one deck in the said layer is the form of foams.In another kind of embodiment, the one deck in the said layer is the form of fabric.In a kind of further embodiment, said laminate structures is the form of awning, oilcloth, automobile crust or bearing circle.

In another kind of embodiment; The present invention provides a kind of laminate structure; It comprises polycarbonate as base sheet; This base sheet has variable thickness and preferably has the texturizing surfaces that can adhere to the present composition at least one its, at 140 ℃ neutral temperature the present composition is adhered to this surface through compression-molding process usually.Such laminate has shown to have excellent adhesivity.For example with the situation of the secondary amine functionalized polyolefin of concentration 1.1wt% the time, has the stripping strength of 1N/mm.The welding technique of routine capable of using is as exerting pressure and heating is further closed these goods with polyolefin layer.In addition, can second polycarbonate sheet with texturizing surfaces be laminated on the compsn of the present invention (having texturizing surfaces on the interface).

Another embodiment of the present invention is the multiple-layer laminated body structure of polycarbonate membrane and polyolefin film, and the insertion of polycarbonate membrane and polyolefin film is used to increase the toughness of final structure.Another embodiment will be the elastomer coatings that is deposited on the present composition on the polycarbonate surface, thereby the assembling coating of anti scuffing is provided, and it can easily carry out thermoforming at for example 160 ℃ hot-forming temperature.

The present invention also provides a kind of moulded parts that comprises first integral part and second integral part, and wherein said first integral part is formed by polar material, and said second integral part is formed by the present composition as described herein.In a kind of further embodiment, said goods are the automobile crust, attach ornaments, the form of footwear, travelling belt, Timing Belt or durable consumer goods.

Term such as " laminate ", " layer closes " is meant the for example rete contact closely each other of two or more layers.Laminate comprises the moulded parts of coating.Although one or more layers constituted blend of laminate, laminate are not blends.

Term such as " polarity ", " polar polymer " is meant that polymer molecule has permanent dipole, and promptly polymer molecule has positive terminal and negative electricity end.In other words, the electronics in polar molecule is not even distribution between the atom of this molecule.On the contrary, terms such as " nonpolar ", " non-polar polymer " refer to that polymer molecule does not have permanent dipole, that is, polymkeric substance does not have positive terminal and negative electricity end.Electronics in non-polar molecule basically even distribution between the atom of this molecule.Most of hydrocarbon liquids and hydrocarbon polymer are nonpolar.

By substituted polymkeric substance such as carboxyl, hydroxyl polar polymer often.Goods by non-polar polymer preparation have lower surface energy, promptly less than about 32 dynes per centimeter (dyn/cm), have higher surface energy by the goods of polar polymer preparation, promptly 32dyn/cm or more than.Non-polar material of the present invention comprises one or more nonpolar thermoplastic olefin polymers usually, is generally elastomerics, does not contain the polar functional group of any significant quantity, for example groups such as hydroxyl, carboxyl, carbonyl, ester, ether, acid amides, mercaptan, halogenide.Polar material of the present invention generally includes one or more polymkeric substance that contains one or more polar functional groups.The typical polymers that comprises one or more polar functional groups includes but not limited to polyester, polyethers, POLYACTIC ACID, polycarbonate, nylon, polysulphide, polysulfones, urethane, Z 150PH, Yodo Sol VC 400, SE, vinyl cyanide, ABS, polyesteramide and ZGK 5.

" polar functional group that can ignore content " waits quantity not sufficient that term is meant the polar functional group that polymkeric substance is contained to give by the goods of its preparation surface energy at least about 32dyn/cm.

" lamination injection moulding " waits term to be meant a kind of resin injected and contain the mould that presets base material, and on this base material this resin of moulding.Usually, through a kind of resin lamination is injected on another polymeric substrate, use the performance and the character of lamination injection moulding raising the finished product.Can use the lamination injection moulding to form jointless integrated component.The instance of the parts of lamination injection moulding is included in the flexible grasps handle on power tool and the kitchen appliance, and it provides extra grasping character and does not have to assemble relevant hygienic issues with machinery usually.Said base material can be any suitable material, like plastics, metal or ceramic component.

" moulding veneer (overlayer) " waits term to be meant the goods that comprise at least two parts that combine (articles injection-moulded and base material).Place on the base material articles injection-moulded, the outside is an injection mold.Can use tackiness agent this articles injection-moulded and base material that bonds.Said base material can be any suitable material, like plastics, metal or ceramic component.

Its base material that can use compsn of the present invention is comprised the polarity or the non-polar material of wide region, such as but not limited to polymkeric substance, metal, timber, concrete, glass, pottery, and the various matrix materials of two kinds or more kinds of above-mentioned materialss.Perhaps, can these materials be administered on the goods that formed by compsn of the present invention.

Application process comprises coating, printing, dyeing, lamination injection moulding etc., also comprises separately multiple variant such as spread-coating, spraying, dip-coating, method such as extrudes.Compsn of the present invention can be before being applied to base material, among or carry out crosslinkedly afterwards, and the mode (for example superoxide, sulphur, moisture, silane, radiation, heating etc.) that they can any routine is carried out crosslinked.In one embodiment, compsn of the present invention is applied to base material, and when it is used and/or its make compsn of the present invention crosslinked after using.For crosslinked, compsn of the present invention comprises degree of unsaturation usually, for example, contains the polyolefine (PO) of diene.

In one embodiment; Compsn of the present invention can be used for forming the tack coat between polar material and the non-polar material; It specifically is the tack coat of (for example, between the rete of nonpolar PO such as Vilaterm or polyacrylic rete and polar polymer such as POLYACTIC ACID (PLA) or polymeric amide or polyester) between polar polymer material and the non-polar polymer material.Compsn of the present invention is suitable for as the tack coat that makes following (a) and (b) bond together admirably: (a) Vilaterm or polypropylene screen, the perhaps Vilaterm of moulded parts or polypropylene surface; (b) film or the molded article surface of the multipolymer of the multipolymer of ethylene/acrylic acid copolymer (EAA) or PLA or polyethylene terephthalate (PET).Any to coextrusion, extrusion laminate, sticky lamination and/or foam casting or extrude the method that makes up and all can be used for forming these laminate structures (comprising that one deck wherein comprises the structure of foams).

Compsn of the present invention also can be used for dispersion-s, for example is used as the dispersion-s based on water of the priming paint of olefines footwear, should promote the adhesion to polyurethane adhesive and leather based on the dispersion-s of water; Textile coating adheres to (to PET, Nylon, PP comprises POE, EPDM or other nonpolar elastomeric high-elastic gonosome TPO, perhaps the adhesion of their combination etc.).

Generally speaking, the present composition can be used for adhesion application, but for example coating and impressionability are used in the lamination injection moulding.Said composition also can be used for dyestuff and uses.Concrete adhesion application is included in the tackiness agent of urethane in automotive applications such as test board shell and the door face board shell, the tackiness agent in the for example all kinds of shoe assemblies of footwear applications, and in the EPDM travelling belt tackiness agent of polyester.The tackiness agent that can be used as bonding polyolefin layer and layer of polyurethane in the footwear by the dispersion-s based on water of present composition preparation.Based on the present composition also can be used as the priming paint of olefines shoe assembly based on the dispersion-s of water, to promote to the adhesion of polyurethane adhesive with to the adhesion of leather.Other application comprises tackiness agent to textile coating (for example, to PET, Nylon, PP comprises POE, EPDM or other nonpolar elastomeric high-elastic gonosome TPO, perhaps the adhesion of their combination etc.).But the present composition also can be used as coating, paint, tackiness agent, glue, film print surface, can dye film and fiber, the assembly of leatheroid, vest, artificial turf, carpet fiber, textiles, medical treatment product (for example blood is with bag, pipe), toy, flexible overlapping injecting products, soft handle, tSportswear etc., perhaps wherein is the assembly of any application of expectation to polyolefinic adhesion.This paper has also described other application.

Other concrete preferred application comprises the tide of motorism shell molds, and the PU foams adhere to (preferably need not to use at present based on the polyolefinic water-based primer of chlorination maleation), and the house coats (wherein needs high humidity transmission rates (100%PELLETHANE ^TM2103-70A meets the demands) and to the good adhesion of Vestolen PP 7052 woven fabric (scrim)); Gluing film (blowing or curtain coating); Co-extruded films (wherein POE/TPU for example, need utilize PU glue to carry out the adherent roof film as thin adhesive bonds layer).In these situations, the present composition usually uses under suitable glycol, isocyanic ester, POE and/or expanding material condition.With regard to regard to the adhesion of polar material, the surface energy that compsn of the present invention can cause increasing (＞37dyn/cm).If TPU is fully aliphatic (no aromaticity, no unsaturated), then the POE/TPU system can play anti-marquis's coating (just opposite with the adhesive bonds layer).

In one embodiment, the present invention is a kind of method of giving high frequency (HF) weldableness and/or impressionability to the goods that comprise low surface energy (being non-polar material).The HF weldableness can make polyolefin sheets or film be used for application examples such as roof film, fixture, leatheroid etc., wherein polyolefine because of cost/performance advantage with recycling property but expectation.The material and the method for HF welding are as known in the art, and are summarized among the US2004/0077791.

Known method comprises: add resin such as MAH grafted resin or EAA, EEA, EMA, EBA or the EMAA multipolymer that zeolite perhaps contains polar functional group to nonpolar olefine kind resin, again this non-polar polymer is carried out HF welding or printing.Yet, utilize the result of analogous material under conditions of similarity of similar quantity with respect to this embodiment of the present invention, these methods generally provide poor weldability and/or impressionability result.

In another kind of embodiment, the present invention is a kind of method of giving at least a following surface properties to the goods that comprise low-surface-energy material: but but paint line, impressionability, dyeability and lamination injection moulding property.

This embodiment of the present invention works to being coated with agent prescription widely well.The main ingredient of solvent-borne type paint and coating is solvent, tackiness agent, pigment and additive.In paint, the combination of tackiness agent and solvent is called and is coated with agent carrier.Pigment and additive are dispersed in this carrier.The amount of every kind of component changes with concrete paint, but solvent accounts for about 60% of whole prescriptions usually.Typical solvent comprises toluene, YLENE, methylethylketone, MIBK and water.The about 30wt% of binder constitutes, pigment accounts for 7～8wt%, and additive accounts for 2～3wt%.Some polymkeric substance that in being coated with agent prescription, use comprise with other additive: acrylic polymers, and Synolac is based on cellulosic material such as cellulose acetate butyrate; Melamine resin, carbamate resins, vibrin; The vinyl acetate resin, urethane resin, polyvalent alcohol; Alcohols, inorganics such as titanium oxide (rutile), sheet mica, red stone, silica, aluminium etc.

As limiting examples, the present composition can be used for promoting bonding between the following material: (i) PU thermosetting foams body and polyolefin elastomer (POE), specifically as the tack coat between extrusion sheet, film or the section bar; (ii) POE/pd-TPU blown film; (iii) pure TPU and POE; (iv) divinyl rubber and TPU or TPV (TPV) for example describe among the EP 0 468 947 those; (v) extrude or moulding technology in nylon or another polar plastic and crosslinked chlorinatedpolyethylene or EPDM; (vi) Vestolen PP 7052 and TPU fiber are for example in carpet, artificial turf etc.; (vii) for example line and cable insulation layer, coating etc. of polarity filler and non-polar material, (and viii) heat fusing tackiness agent and polar substrates, (ix) POE and pd-TPU in moulded parts for example in footwear and automobile; And (x) can be made into the for example aqueous dispersion of film of various goods.

Its base material that can use compsn of the present invention is comprised the polarity or the non-polar material of wide region, such as but not limited to polymkeric substance, metal, timber, concrete, glass, pottery, and the various matrix materials of two kinds or more kinds of above-mentioned materialss.Perhaps, can these materials be administered on the goods that comprise said blend.Application process comprises coating, printing, dyeing, lamination injection moulding etc., also comprises separately multiple variant such as spread-coating, spraying, dip-coating, method such as extrudes.Compsn of the present invention can be before being applied to base material, among or carry out crosslinkedly afterwards, and the mode (for example superoxide, sulphur, moisture, silane, radiation, heating etc.) that they can any routine is carried out crosslinked.In one embodiment, compsn of the present invention is applied to base material, and when it is used and/or its make compsn of the present invention crosslinked after using.For crosslinked, compsn of the present invention comprises degree of unsaturation usually, for example, contains the polyolefine (PO) and/or the unhydrided TPU of diene.

In one embodiment; Compsn of the present invention is as the tack coat that forms between polar material and the non-polar material; It specifically is the tack coat of (for example, between the rete of polyolefine such as Vilaterm or polyacrylic rete and polar polymer such as POLYACTIC ACID (PLA) or polymeric amide or polyester) between polar polymer material and the non-polar polymer material.Pd-TPU of the present invention is suitable for as the film or the molded article surface agglutinating tack coat that make Vilaterm or polyacrylic film or molded article surface and ethylene/acrylic acid copolymer (EAA) or PLA or polyethylene terephthalate (PET) admirably.Any to coextrusion, extrusion laminate, sticky lamination and/or foam casting or extrude the method that makes up and all can be used for forming these laminate structures (comprising the structure that wherein comprises foams).

In another kind of embodiment of the present invention, a kind of film that formed by compsn of the present invention and goods of urethane foam of comprising are provided, wherein said film and said urethane foam surperficial bonding.Such goods can be test boards.In a kind of further embodiment; Bonding between film of the present invention and the said urethane foam is better than bonding between said foams and another film, and said another film is by the preparation of compositions that except functional polyethylene, comprises with film same composition of the present invention.

In one embodiment of the present invention, a kind of film that is formed by compsn of the present invention that comprises is provided.In another kind of embodiment, a kind of film two-layer at least or cord body (ply) that comprises is provided, wherein one deck or cord body are formed by the present composition as herein described at least.In another aspect of this invention, such film closes formation through coextrusion or layer.Such film can comprise one or more morphological specificitys as herein described, and preferably comprises based on the common successive of the polymkeric substance of ethene and urethane mutually.The present invention also provides and has comprised at least one assembly that comprises such film or by the goods of so film formed assembly.This based article includes but not limited to automotive interior spare, panel enclosure, fabric coating, vacuum forming section bar, shoe assembly, laminate film and other goods.This based article can be through corresponding prepared as herein described.

In another kind of embodiment of the present invention, a kind of film that comprises at least three layers or cord body is provided, wherein one deck or cord body are formed by the present composition as herein described at least.In another aspect of this invention, such film closes formation through coextrusion or layer.Such film can comprise one or more morphological specificitys as herein described, and preferably comprises based on the common successive of the polymkeric substance of ethene and urethane mutually.The present invention also provides and has comprised at least one assembly that comprises such film or by the goods of so film formed assembly.This based article includes but not limited to automotive interior spare, panel enclosure, fabric coating, vacuum forming section bar, shoe assembly, laminate film and other goods.This based article can be through corresponding prepared as herein described.

In another kind of embodiment; The invention provides a kind of two-layer at least film that comprises; Wherein one deck is formed by the present composition at least, and wherein at least another layer be to form by comprising the compsn of melt strength more than or equal to the ethylene/alpha-olefin interpolymers of 5cN.The present invention also provides the goods that comprise such film or by so film formed goods.

The present invention also provides the goods that comprise at least one assembly that is formed by the present composition as described herein.This based article can pass through one or more prepared separately, and said technology includes but not limited to extrude, thermoforming, blowing, injection moulding, foaming and calendering.In one embodiment, goods described herein are non-automobile products, and can be used for non-automotive applications.

The present invention also provides the method for preparation compsn as herein described and goods.The present invention also provides various embodiments and two kinds of compsn as herein described, goods and method or the combination of more kinds of embodiments.

Definition

Any numerical range as herein described comprise smaller value and higher value therebetween with all numerical value of an incremented, condition is at the interval that has at least two units arbitrarily between smaller value and the higher value.For example, physical properties or the mechanical properties (for example, molecular weight, viscosity, melt index etc.) like fruit component is 100 to 1000; Then mean and clearly enumerated whole single numerical value in this specification sheets as 100,101,102 etc.; And sub-range such as 100-144,155-170,197-200 etc.For containing, think that aptly a unit is 0.0001,0.001,0.01 or 0.1 less than 1 numerical value or greater than the scope of 1 mark (for example 1.1,1.5 etc.).Scope for containing less than 10 number (for example, 1-5), it has been generally acknowledged that a unit is 0.1.These only are the examples of the content that specifically meant, and the institute of cited Schwellenwert and the numerical value between the mxm. might make up and all is considered to clear record in this application.For melt index, melt flow rate(MFR), MWD, percent crystallinity percentage, density and other character, so the place is discussed that kind and has been stated digital scope in this application

Term used herein " compsn " comprises the multiple mixtures of material that constitutes said composition, and the reaction product and the degradation production that are formed by the multiple material of said composition.

Term used herein " blend " or " blend polymer " refer to the blend of two kinds or more kinds of polymkeric substance.This blend can be molten (on molecular level, not being separated) of mixing or immiscible.This blend can be that be separated or non-being separated.Measure according to known other method of transmission electron microscopy, light scattering method, x-ray scattering method and prior art, this blend can contain or not contain one or more farmland structures (domain configuration).

Term used herein " polymkeric substance " refers to the macromolecular compound for preparing through same type or dissimilar monomeric polymerizations.Therefore general term polymer comprises the term interpolymer of term homopolymer and hereinafter definition, and homopolymer only is commonly used to refer to the polymkeric substance that prepared by one type monomer.Term " ethylene/alpha-olefin polymer " is the interpretation that expression is described below with " propylene/alpha-olefins polymkeric substance ".

Term used herein " interpretation " refers to the polymkeric substance for preparing through at least two kinds of dissimilar monomer polymerizations.Thereby this generic term interpretation comprises multipolymer (being commonly used to refer to the polymkeric substance by two kinds of different monomers preparations), and by the polymkeric substance more than two kinds dissimilar monomers preparations.

Term used herein " based on the polymkeric substance of alkene " refers to comprise polymerization of olefin monomers (for example ethene or propylene) greater than 50mol% (based on the total amount of polymerisable monomer) and the polymkeric substance that randomly can comprise one or more comonomers.

Term used herein " based on the polymkeric substance of ethene " refers to comprise polymerizing ethylene monomer (based on the total amount of polymerisable monomer) greater than 50mol% and the polymkeric substance that randomly can comprise one or more comonomers.This term that uses among this paper is not meant the many block interpolymers of alkene as herein described.

Term used herein " ethylene/alpha-olefin interpolymers " refers to comprise polymerizing ethylene monomer (based on the total amount of polymerisable monomer) and the interpretation of at least a terminal olefin greater than 50mol%.This term that uses among this paper is not meant the many block interpolymers of alkene as herein described.

Term used herein " based on the polymkeric substance of propylene " refers to comprise polypropylene monomer (based on the total amount of polymerisable monomer) greater than 50mol% and the polymkeric substance that randomly can comprise one or more comonomers.This term that uses among this paper is not meant the many block interpolymers of alkene as herein described.

Term used herein " propylene/alpha-olefins interpretation " refers to comprise polypropylene monomer (based on the total amount of polymerisable monomer) and the interpretation of at least a terminal olefin greater than 50mol%.This term that uses among this paper is not meant the many block interpolymers of alkene as herein described.

Term used herein " propylene/ethylene interpretation " refers to comprise the interpretation of polypropylene monomer (based on the total amount of polymerisable monomer) greater than 50mol%, vinyl monomer and optional at least a terminal olefin, and this term that uses among this paper is not meant the many block interpolymers of alkene as herein described.

Term used herein " amine reactive group " refer to can with the chemical group or the chemical part of amino reaction.

Term used herein " hydroxyl-reactive group " or " hydroxyl-reactive group " refer to can with the chemical group or the chemical part of hydroxyl reaction.

Term used herein " compound that contains acid anhydride " refers to comprise the compound of at least one anhydride group.

Term used herein " compound that contains carboxylic acid " refers to comprise the compound of at least one hydroxy-acid group.

Term used herein " amine-containing compound " refers to comprise at least one amino compound.

Refer to term used herein " hydroxy-containing compounds " or " containing hydroxy compound " to comprise at least one-compound of OH group.

Term used herein " functionalized polymkeric substance based on alkene " refers to by based on the polymkeric substance of alkene and the polymkeric substance of one or more compound formation, each self-contained at least one functional group of said one or more compounds (for example acid anhydride, carboxylic acid, amine, hydroxyl or imide).

Term used herein " amine-functionalized polymkeric substance based on alkene " refers to by based on the polymkeric substance of alkene and the polymkeric substance of one or more compound formation, and wherein at least a compound comprises at least one amino.

Term used herein " hydroxy-functional is based on the polymkeric substance of alkene " refers to by based on the polymkeric substance of alkene and the polymkeric substance of one or more compound formation, and wherein at least a compound comprises at least one hydroxyl.

Term used herein " the functionalized polymkeric substance based on alkene of imide " refers to by based on the polymkeric substance of alkene and the polymkeric substance of one or more compound formation, and wherein at least a compound comprises at least one and can form imido imide precursor (referring to following EXPERIMENTAL EXAMPLE).

Testing method

Density is that (method B measures for American Society for Testing andMaterials, ASTM) rules ASTM D792-00 according to American Society for Testing and Materials.

Melt index (I ₂) to be to use ASTM D-1238-04 (version C)/10 minutes be the unit measurement with gram under 190 ℃/2.16kg of condition.Symbol " I ₁₀" be meant use ASTM D-1238-04 under 190 ℃/10.0kg of condition with/10 minutes melt indexs of gram for unit measurement.Symbol " I ₂₁" be meant use ASTM D-1238-04 under 190 ℃/21.6kg of condition with/10 minutes melt indexs of gram for unit measurement.Vilaterm is measured at 190 ℃ usually, and Vestolen PP 7052 is measured in the time of 230 ℃ usually.MFR is meant melt flow rate(MFR) for the polymkeric substance based on propylene, and utilizes 230 ℃/2.16kg of ASTM D-1238 condition to measure.For except PELLETHANE ^TMThe polymkeric substance based on carbamate (blend that comprises this base polymer) beyond the polymkeric substance, melt index is measured according to 190 ℃/2.16kg of ASTM D-1238 condition.For PELLETHANE ^TM(Pellethane ^TM2102-80A and 2103-70A), melt index is measured according to 190 ℃/8.7kg of ASTM D-1238 condition.

Dsc (DSC) is to utilize the TAI model Q1000 DSC of equipment RCS cooling attachment and automatic sampler to carry out.Adopted the nitrogen purging air-flow of 50cc/min.Sample is pressed into film and in about 175 ℃ of fusions in press, then air cooling to room temperature (25 ℃).Then the material with 3～10mg is cut into the 3mm diameter disk, and accurately weighing places light aluminium dish (about 50mg), then crimping sealing (crimped shut).The thermal behavior of temperature distribution study sample below utilizing.Sample is quickly heated up to 180 ℃ and kept isothermal 3 minutes, to remove any previous thermal history.Sample is cooled to-90 ℃ and kept 3 minutes with 10 ℃/min speed of cooling then at-90 ℃.Thereafter the rate of heating with 10 ℃/min is heated to 150 ℃ with sample.The record cooling and second heating curve.Melt temperature (Tm) is confirmed by second heating curve.Tc (Tc) is confirmed by first cooling curve.

Ultimate tensile strength and extension at break are measured according to ASTM D-638-03.At 23 ℃ cross cutting D638 type IV sample is carried out this two kinds of measurements.

Surface tension is measured according to ASTM D2578-04a method B and DIN 53364 (1986).Use ARCOTEC test printing ink, it is the fluid that surface tension is confirmed, and can in the scope of 28～56mN/m, obtain.Test is carried out when room temperature (23 ℃).

Surface energy is that utilization can be from the ARCOTEC of Lotar Enterprises acquisition ^TMTest printing ink and test pencil are measured.As the origin of each verification, should use test printing ink or test pencil with intermediate value such as 38mN/m (dyn/cm).If the line of printing ink on the surface of material, keep at least 2 seconds constant and be not transformed into drop, then the surface energy of this material is equal to or higher than this fluidic surface tension.When this situation, the test printing ink/test pencil that will have next high value such as 40mN/m (dyn/cm) imposes on this surface.Must repeat this verification and reach such point until capillary next high value, this time fluidic line in 2 seconds, be transformed into isolating drop.If fluid line has formed drop when said origin (38mN/m (dyn/cm)), to use so than the test printing ink/test pencil of low value and proceed to verify, this is common situation for metal.As general qualification, 32mN/m (dyn/cm) is usually mentioned.If surface energy level is lower than this value, it will be poor adhering to so; It will be that get well or enough that the words that are higher than this value adhere to.

The sheet material hardness properties is measured according to ASTM D2240-05.Tensile property is measured according to standard test methods ASTM D638-03.

Melt tension is measured selected polymer samples in 190 ℃ of temperature on Goettfert Rheotens melt tester for elongation.This Rheotens tester is made up of the wheel of two reverse rotations, the melting thread mass that its traction is extruded from kapillary die head constant speed.These wheels are furnished with balance, to measure the stress response of melt when wheel quickens.Make these wheels quicken to break until the line material.The power that makes the fracture of line material is used as melt tension, in a li ox (cN).

RR (V0.1/V100) is through utilizing the melt rheology technology at Rheometric Scientific, and Inc.ARES (Advanced Rheometric Expansion System) dynamic mechanical spectrometer (DMS) goes up that sample for reference measures.Use dynamic frequency pattern and parallel plate anchor clamps to come sample for reference at 190 ℃ with the 25mm diameter in 2 millimeters (mm) gaps.Strain rate with 8% and from 0.1 increase to 100 radian per seconds gradually oscillation rate, the frequency of per ten analyses is got 5 data points.180 ℃ in 20, following 1 minute of the pressure of 000psi (137.9 MPas (MPa)) is compression molded into each sample (pellet or bale packing) test plate (panel) of 3 inches of 1/8 inch (0.049cm) thick diameters (7.62 centimetres (cm)).These test plate (panel)s of quenching and 1 minute time of warp are cooled to room temperature.Downcut " 25mm test plate (panel) " from the centre portions of bigger test plate (panel).Then the aliquots containig of these 25mm diameters is inserted among 190 ℃ the ARES, and before beginning test, made its balance 5 minutes.Sample is remained in the nitrogen atmosphere, thereby oxidative degradation is minimized.Use arrangement and the processing of accomplishing data based on the software package of ARES2/A5:RSI Orchestrator Windows 95.RR measures viscosity to the ratio in the shear rate curve.

The mooney viscosity MV of interpretation (at 125 ℃ ML 1+4) measures according to ASTM D1646-04.The processing rheology is calculated by MV and RR according to following formula than PRR: PRR=RR+ [mooney viscosity of 3.82-interpretation (at 125 ℃ ML1+4)] * 0.3.ML is meant the Mooney ectotrochanter.This viscometer is a Monsanto MV2000 instrument.

Tensile strength and elongation are measured according to ASTM D-882-02, and sample is an extrusion sheet.

Tear (Type C) and measure according to ASTM D-882-02, sample is an extrusion sheet.

Glossiness (60 degree) is measured according to ASTM D-2457-03, and sample is an extrusion sheet.

Thermal ageing research: for each analysis, 120 ℃ in the convection oven (Lindberg Blue Oven, Model ESP-400C-5, force air) heat treated sample (extrusion sheet) reach table 9 and 10 pointed periods among the following embodiment.After this thermal treatment, make sample balance to room temperature (16～96 hours) referring to ASTM D573,10.5.Measure tensile strength and elongation according to ASTM D-882-02 then.

Moisture vapor transmission test (ASTM E 96/E 96M-05, Imperial Method)-be used to measure moisture transmission rates (MVT) and penetration degree (permeance) through the siccative method.Temperature that is used to estimate and relative humidity are respectively 72 ° of F and 50%.Contain the opening of the examination dish of siccative with the sealing of non-laminate film, and this subassembly is placed the controlled atmosphere of 72 ° of F and 50% relative humidity.Measure water vapour with the periodicity weighing and see through the movement velocity that sample gets into siccative.With 13.3 of ASTM E 96/E 96M-05 different be through multiply by MVT with the thickness that records and penetration degree is carried out stdn to MVT and penetration degree by film thickness, to obtain standardized MVT and moisture permeable coefficient respectively.It is directly relevant with the thickness of sample and the variable thickness property that in the film ME, causes with MVT that the reason of doing like this is a penetration degree.

Fourier transform infrared spectroscopy (FTIR) is analyzed

Maleic anhydride content

Through maleic anhydride at 1791cm ^-1The peak height at wave number place and polymkeric substance (, be positioned at 2019cm with reference to the peak for Vilaterm ^-1Wave number) ratio is confirmed maleic anhydride concentration.Through being multiply by suitable meter constant, this ratio calculates maleic anhydride content.The equality that is used for the maleation graft polyolefin has following form:

MAH (wt.%)=A*{ [FTIR peak area 1791cm ^-1]/[FTIR peak area 2019cm ^-1]+B* [FTIR peak area 1712cm ^-1]/[FTIR_ peak area 2019cm ^-1] (equality 1)

Use ¹³The CNMR standard substance can be confirmed this meter constant A.According to instrument and polymkeric substance, actual meter constant can be slightly different.At 1712cm ^-1There is toxilic acid in the explanation of the second section at wave number place, and it is negligible for grafted material just.Yet along with the time goes over, in the presence of moisture, maleic anhydride is converted into toxilic acid easily.Depend on surface-area, under envrionment conditions, only just remarkable hydrolysis can take place in several days.The characteristic peak of toxilic acid is at 1712cm ^-1The wave number place.Constant B in the equality 1 is the correction to optical extinction coefficient difference between anhydride group and the acid groups.

The specimen preparation program starts from thermocompressor, between two protective membranes, suppressing sample 1 hour at 150-180 ℃, and thickness is generally 0.05～0.15 millimeter.Mylar and Teflon are suitable protective membranes, and the protection sample is avoided the destruction of platen.Do not use aluminium foil (maleic anhydride and reactive aluminum).Platen should pressurized (～10ton) about 5 minutes.Make sample be cooled to room temperature, place suitable specimen holder, in FTIR, scan then.Before each sample scanning or should carry out background scans when needed.When inherent variability (inherent variability) less than ± 5% the time, measuring accuracy is good.Sample should be deposited to prevent undue hydrolysis with siccative together.Moisture content in the product records up to 0.1wt%.Yet acid anhydrides is a reversible to the transformation of acid at a certain temperature, possibly need the time of cost up to 1 week but transform fully.This conversion is carried out the best in 150 ℃ decompression baking oven, need good vacuum tightness (near 30 inches Hg).If vacuum degree deficiency, sample is oxidation often, causes at about 1740cm ^-1Infrared peak occurs, make aforementioned value too low.Maleic anhydride and acid are respectively by at about 1791cm ^-1And 1712cm ^-1The spectrum peak at place is represented.

The testing method relevant with the sign of the many block interpolymers of alkene

1. the GPC method that is used for sample 1-4 and A-C

The automatic fluid processing machine arm that use is furnished with the hot pin that is set at 160 ℃ with enough with 300ppm Ionol stable 1,2, the 4-trichlorobenzene is added into each exsiccant polymer samples, to obtain the ultimate density of 30 mg/ml.Little glass stirring rod is placed in each pipe, and sample is heated to 160 ℃ and lasting 2 hours on the heating rail mounted shaking table with the 250rpm rotation.Then, use automatic fluid processing machine arm and the hot pin that is set at 160 ℃ to be diluted to 1 mg/ml spissated polymers soln.

The molecular weight data that Symyx Rapid GPC system is used to measure each sample.With the Gilson that is set at 2.0 ml/min flow velocitys 350 pumps be used for that pumping helium purged with 300ppm Ionol stable 1; The 2-dichlorobenzene is as moving phase, place through series connection and be heated to 10 microns (μ m) Mixed B of three Plgel 300mm * 7.5mm post of 160 ℃.Use Polymer Labs ELS 1000 detectors, vaporizer is set at 250 ℃, atomizer is set at 165 ℃, and nitrogen flow rate is set at 1.8 SLM (N ₂Pressure is 60-80psi (400-600kPa)).Polymer samples is heated to 160 ℃, and uses liquid handling machine arm and hot pin that each sample is injected in the 250 μ l loops.Use two conversion loops and overlapping injection to carry out the successive analysis of polymer samples.Symyx Epoch is collected and used to sample data ^TMSoftware is analyzed.With the manual integration in peak, and the molecular weight information of being reported does not contrast the polystyrene standard calibration curve and revises.

2. standard C RYSTAF method

It is to use CRYSTAF 200 Instrument measurings that can be commercially available from the PolymerChar of Spain Valencia through crystal analysis fractionation (CRYSTAF) that branching distributes.With sample be dissolved in 160

℃

1,2,4-trichlorobenzene (0.66 mg/ml) 1 hour, and stablized 45 minutes at 95 ℃.Probe temperature with the rate of cooling of 0.2 ℃/min from 95 ℃ of changes to 30 ℃.Infrared detector is used to measure polymer solution concentration.When temperature decline polymer crystallization, measure accumulation solvend concentration.The short-chain branched distribution of the analysis derivative reflection polymkeric substance of summation curve.

Peak analysis module through being included in the CRYSTAF software (version 2 001.b, the PolymerChar of Spain Valencia) is confirmed CRYSTAF peak temperature and area.CRYSTAF peak peak-seeking procedure identification goes out as the peaked peak temperature in the dW/dT curve, and the area between the maximum positive flex point of the both sides at the peak that in derivative curve, identifies.Be to calculate the CRYSTAF curve, preferred processing parameter be temperature limitation be 70 ℃ with smooth parameter (smoothing parameter) for being higher than temperature limitation 0.1 and being lower than temperature limitation 0.3.

3.DSC standard method (getting rid of sample 1-4 and A-C)

Difference formula scanning calorimetry result is to use the TAI model Q1000 DSC that is furnished with RCS cooling attachment and automatic sampler to confirm.Use the nitrogen flow of purge gas of 50 ml/min.Sample is pressed into film and in about 175 ℃ of fusions in press, then air cooling to room temperature (25 ℃).Then, the material of 3-10 milligram is cut into the disk of 6mm diameter, weighs exactly, place in the light aluminum pot (about 50 milligrams), then, the crimping sealing.Thermal behavior with following temperature distribution study sample.Sample is quickly heated up to 180 ℃ and constant temperature kept 3 minutes, to remove any previous thermal history.Sample is cooled to-40 ℃ and reach 3 minutes with the rate of cooling of 10 ℃/min then-40 ℃ of maintenances.Thereafter the heating rate with 10 ℃/min is heated to 150 ℃ with sample.The record cooling and second heating curve.

Linear baseline with respect between-30 ℃ and fusing stop, drawing melts peak value with DSC and measures according to the peak in the heat flow rate (W/g).Use linear baseline, the area under the melting curve between melting heat is stopped according to-30 ℃ and fusing is measured.

4.GPC method (getting rid of sample 1-4 and A-C)

The gel permeation chromatography system is made up of Polymer Laboratories model PL-210 or PolymerLaboratories model PL-220 instrument.Post and travelling belt compartment are 140 ℃ of operations.Use 3 Polymer Laboratories 10-micron Mixed-B posts.Solvent is 1,2, the 4-trichlorobenzene.With sample with the prepared at concentrations of 0.1 gram polymkeric substance in 50 milliliters of solvents that contain 200ppm Yoshinox BHT (BHT).Through preparing sample in 2 hours 160 ℃ of gentle agitation.Used injection volume is 100 microlitres, and flow velocity is 1.0 ml/min.

Using molecular weight is that 21 narrow molecular weight distributions polystyrene standards of 580 to 8400000 are carried out the correction of GPC column assembly, with the arranged in form of 6 kinds of " cocktail " mixtures, and at least ten times (decade) at interval between each molecular weight wherein.Said standard substance available from Polymer Laboratories (Shropshire, UK).Be equal to or greater than 1000000 in 50 milliliters of solvents, 0.025 restrain being equipped with polystyrene standards for molecular weight, for molecular weight less than 1000000 in 50 milliliters of solvents, 0.05 to restrain and be equipped with polystyrene standards.80 ℃ of mild stirring 30 minutes polystyrene standards is dissolved.At first test narrow standard substance mixture, and the order of successively decreasing by the highest weight component, so that minimize degradation.Equation below utilizing (like Williams and Ward, J.Polym.Sci., Polym.Let., described in 6,621 (1968)) and the accurate peak of PS molecular weight is converted into molecular weight of polyethylene: M _Vilaterm=0.431 (M _PS).

Using Viscotek TriSEC software version 3.0 to carry out the Vilaterm equivalent weight calculates.

5. compression set

Compression set is to measure according to ASTM D 395.Sample prepares through following method: pile up 3.2mm, 2.0mm and the thick 25.4mm diameter disk of 0.25mm, until the total thickness that reaches 12.7mm.Under the following condition with the compression moulding print of 12.7 centimetres of 12.7 cm x of thermocompressor moulding on cutting disc: continue 3 minutes at 190 ℃ with 0 pressure, continue 2 minutes at 190 ℃ with 86MPa then, cool off in that press is inner with cold flow water at 86MPa then.

6. density

Preparation is used for the sample of density measurement according to ASTM D1928.In 1 hour of sample compacting, utilize ASTM D792 method B to measure.

7. modulus in flexure/secant modulus/storage modulus

Use 1928 pairs of samples of ASTM D to carry out compression moulding.Measure modulus in flexure and 2% secant modulus according to ASTM D-790.Measure storage modulus according to ASTM D 5026-01 or equivalent technologies.

8. optical property

Use thermocompressor (the Carver model #4095-4PR1001R) film that compression moulding 0.4mm is thick.Pellet is placed between the teflon plate, heated 3 minutes in 55psi (380kPa), reach 3 minutes in 1.3MPa again, reach 3 minutes in 2.6MPa then at 190 ℃.Then, this film was cooled off in press 1 minute with the cold water that flows at 1.3MPa.Compressive films is used for opticmeasurement, stretch behavior, recovery and stress relaxation.

Use BYK Gardner Haze-gard such as ASTM D 1746 defineds to measure transparency.

Use 45 ° of BYK Gardner Glossmeter Microgloss as 45 ° of glossiness of ASTM D-2457 defined measurement.

Based on ASTM D 1003 process A, use BYK Gardner Haze-gard to measure interior mist degree.MO is applied to the film surface to remove surperficial scratch.

9. mechanical properties: stretch, lag behind and tear

Use ASTM D 1708 little tension specimens to measure the stress-strain behavior in the uniaxial extension.With Instron with 500%min ^-1At 21 ℃ of stretching samples.MV report tensile strength and elongation at break according to 5 samples.

Use Instron ^TMInstrument uses ASTMD 1708 little tension specimens to be loaded on 100% and 300% strain and to measure 100% and 300% hysteresis from cyclicity.21 ℃ with sample with 267% minute ^-1Load and unload 3 circulations.The cyclicity experiment at 300% and 80 ℃ is carried out in environment for use chamber (environmental chamber).In 80 ℃ of experiments, before test, make sample probe temperature balance 45 minutes.In the experiment of 21 ℃ and 300% strained cyclicity, the record first unloading round-robin 150% strained back stress.The answer percentage of all experiments is calculated in strain when first unloading recycles load and is back to baseline.To reply percentage is defined as:

Wherein, ε _fBe the strain that cyclicity loads, and ε _sBe first strain of unloading when cycle period, load was back to baseline.

Use is furnished with the Instron of environmental chamber ^TMInstrument was measured stress relaxation 12 hours 50% strain and 37 ℃.Measuring device (gauge) geometrical shape is 76mm * 25mm * 0.4mm.In environmental chamber 37 ℃ of balances after 45 minutes, with sample with 333% minute ^-1Be stretched to 50% strain.The function of stress as the time write down 12 hours.Stress relaxation percentage after 12 hours uses computes:

Wherein, L ₀Be to be 0 o'clock 50% strained load the time, and L ₁₂Be 50% strained load after 12 hours.

On sample, use Instron with 0.88g/cc or density still less ^TMStretch tongue tear experiment of instrument.Geometrical shape is made up of the metering zone of 76mm * 13mm * 0.4mm, and has the 2mm otch in the incision sample at half place of specimen length.With sample at 21 ℃ with 508mm minute ^-1Be stretched to fracture.Area under the strain when being up to ultimate load with stress-extension curve calculates tearing energy.The MV of at least 3 samples of report.

10.TMA

On the thick compression moulding disk of 30mm diameter * 3.3mm, carry out thermo-mechanical analysis (pin is gone into temperature), said compression moulding disk is to carry out 5 minutes with the 10MPa molding pressure at 180 ℃, and is air quenched then and form.Used instrument is the brand TMA 7 that can derive from Perkin-Elmer.In this test, the probe that will have 1.5mm radius most advanced and sophisticated (P/N N519-0416) is applied to the surface of sample disk with the power of 1N.With 5 ℃/min from 25 ℃ of intensifications.The probe pin is gone into distance to be measured as the function of temperature.When the probe pin is gone in the sample 1mm, finish experiment.

11.DMA

On the compression moulding disk, measure dynamic mechanical analysis (DMA), said compression moulding disk be in thermocompressor in 180 ℃ with 10MPa pressure under carried out 5 minutes, in press, form then with 90 ℃/min water-cooled.Use is furnished with the controlled strain rheometer of ARES (TAInstruments) of two cantilever stationary installations of using of test moment of torsion and tests.

Compacting 1.5mm sheet material also is cut into the strip that is of a size of 32 * 12mm.The sample two ends are clipped between the stationary installation of separating 10mm (spacing jig Δ L), and apply-100 ℃ to 200 ℃ continuous temperature rank (every rank are 5 ℃).When each temperature, measure torsion modulus G ' with the radian frequency of 10rad/s, between strain amplitude remains on 0.1% and 4% to guarantee that moment of torsion is enough and to measure remaining on linear condition.

The initial static(al) (stretch mode automatically) that keeps 10g, lax when preventing thermal expansion in the sample.Therefore, spacing jig Δ L is along with temperature improves, and is all the more so when particularly temperature is on the fusing point of polymer samples or softening temperature.In top temperature or when the spacing between the stationary installation reaches 65mm, stop test.

12. melt index

Melt index or I ₂According to ASTM D 1238 for based on poly polymkeric substance under the 190 ℃/2.16kg condition (for based on polyacrylic polymkeric substance under 230 ℃/2.16kg condition) measure.Melt index or I ₁₀Measure down according to 190 ℃/10kg of ASTM D 1238 conditions

13.ATREF

According to USP 4,798,081 and Wilde, L.; Ryle, T.R.; Knobeloch, D.C.; Peat, I.R.; Determination of Branching Distributions in Polythylene and EthyleneCoplymers; J.Polym.Sci.; 20; Method described in the 441-455 (1982) is analyzed with temperature rise drip washing fractionation (ATREF) and is analyzed, and incorporates their full content mode by reference into this paper.Compsn to be analyzed is dissolved in the trichlorobenzene, and makes its crystallization in the post that comprises inert support (stainless shot) through temperature slowly being reduced to 20 ℃ with 0.1 ℃/minute rate of cooling.This post is furnished with infrared detector.Come wash-out crystalline polymer sample from post through the temperature of eluting solvent (trichlorobenzene) slowly being risen to 120 ℃ from 20 ℃ then, thereby produce the ATREF chromatographic curve with the speed of 1.5 ℃/min.

14. ¹³C NMR analyzes

Add 3 gram tetrachloroethane-d through the 0.4g sample in 10mm NMR pipe ²/ orthodichlorobenzene 50/50 mixture prepares sample.Through being heated to 150 ℃, NMR pipe and content thereof make sample dissolution and homogenizing.Corresponding 100.5MHz's ¹³The C resonant frequency uses JEOL Eclipse ^TM400MHz spectrometer or Varian Unity Plus ^TMThe 400MHz spectrometer is collected data.Use 4000 transitions/data file,, obtain data with 6 pulse per second (PPS) duplicate delays.For quantitative analysis,, a plurality of data files are added to together in order to realize minimum SNR.Spectrum width is 25000Hz, and minimum file size is the 32K data point.At 130 ℃ with 10mm broad band probe analysis sample.Use tlv triple method (Randall, the J.C. of Randall; JMS-Rev.Macromol.Chem.Phys., C29,201-317 (1989)) measure comonomer incorporation, incorporate its full content mode by reference into this paper.

15. polymkeric substance fractionation through TREF

15-20 was restrained polymkeric substance in 4 hours and be dissolved in 2

liter

1,2 through stirring, 4-trichlorobenzene (TCB) and carry out extensive TREF fractionation at 160 ℃.Through 15psig (100kPa) nitrogen polymers soln is placed on 3 inches * 4 feet (12 centimetres of 7.6 cm x) steel columns; Said steel column is filled with 30-40 order (600-425 μ m) globular technical quality glass beads (can derive from Potters Industries; HC 30Box 20.Brownwood, TX, 76801) and stainless 0.028 " (0.7mm) 60: 40 of the steel wire cut pill of diameter (cut wireshot) (can derive from Pellets; Inc.63 Industlrial Drive; North Tonawanda, NY, 14120) (v: v) mixture.This post is dipped in the thermal control oil jacket that is initially set to 160 ℃.At first tubing string ballistic (ballistically) is cooled to 125 ℃, then, slowly cools to 20 ℃ with 0.04 ℃/minute, and kept 1 hour.Fresh TCB is introduced with about 65 ml/min, make temperature simultaneously with 0.167 ℃ of/minute rising.

To be collected in the hot run tank in 16 stations (16station heated fraction collector) from about 2000 milliliters part elutriant of preparation property TREF post.Use Rotary Evaporators that the polymkeric substance in each cut is concentrated, until about 50 to 100ml the polymers soln of residue.With this enriching soln hold over night, add excessive methyl alcohol then, filter and drip washing (methyl alcohol that comprises the last about 300-500ml of drip washing).Filtration step is to utilize 5.0 μ m teflon-coating filter paper (can derive from OsmonicsInc., Cat#Z50WP04750) on 3 position vacuum aided filter stations, carry out.With the cut that filters dried overnight in 60 ℃ vacuum drying oven, and weighing on analytical balance, be used for further test then.

16. melt strength

Melt strength (MS) is to use the capillary rheometer of 20: 1 die heads being furnished with the 2.1mm diameter to measure with about 45 degree of inlet angle.Make sample after 190 ℃ of balances 10 minutes, with the speed operation piston of 1 inch per minute clock (2.54 cm per minute).The standard testing temperature is 190 ℃.With sample with 2.4 mm/second ²The acceleration stresses uniaxial extension quicken folder (accelerating nips) to being positioned at one group of the following 100mm of die head.With the function record of required force-to-stretch as the winding speed of nip rolls.The maximum stretching force that will in test, obtain is defined as melt strength.Demonstrate at polymer melt under the situation of draw resonance, the force-to-stretch before draw resonance is begun is regarded as melt strength.With melt strength with centinewton (" cN ") record.

Embodiment

Below the embodiment example description the present invention, but both indeterminately implicitly do not limit the present invention yet.

Component below in following examples, using.

Pellethane ^TM2102-80A is thermoplastic polyurethane, and density is 1.18g/cc, melt index (I ₂) 190 ℃ with 8.7kg under be measured as 4g/10 minute (deriving from The Dow ChemicalCompany).

Pellethane ^TM2103-70A is thermoplastic polyurethane, and density is 1.06g/cc (ASTM D792), melt index (I ₂) 190 ℃ with 8.7kg under be measured as 11g/10 minute (deriving from The DowChemical Company).

Pellethane ^TM2355-80AE is thermoplastic polyurethane, and density is 1.18g/cc (ASTM D792), melt index (I ₂) 190 ℃ with 8.7kg under be measured as 7g/10 minute (deriving from The DowChemical Company).

Pellethane ^TM2103-80AEF is thermoplastic polyurethane, and density is 1.13g/cc (ASTM D792), melt index (I ₂) 190 ℃ with 8.7kg under be measured as 13g/10 minute (deriving from The DowChemical Company).

Isoplast ^TM2530, engineering thermoplastic polyurethane derives from The Dow chemical Company.

CAPRON for polymeric amide (nylon 6), derives from BASF.

Calibre ^TM200-14 is polycarbonate, derives from The Dow Chemical Company.

Eastman EASTAR EN-001 is polyethylene terephthalate, derives from EastmanChemicals.

GE Plastics 315-1001 is polybutylene terephthalate, derives from GE Plastics.

Engage ^TM8200, be ethylene/octene-1 multipolymer, density is 0.870g/cc, melt index (I ₂) be 5g/10 minute, 190 ℃ with down measurement (deriving from The Dow Chemical Company) of 2.16kg.

Engage ^TM8100, be ethylene/octene-1 multipolymer, density is 0.870g/cc, melt index (I ₂) be 1g/10 minute, 190 ℃ with down measurement (deriving from The Dow Chemical Company) of 2.16kg.

Engage ^TM7086 or ENR 7086.01, be ethene/butene-1 copolymer, density is 0.901g/cc, melt index (I ₂) for＜0.5g/10 minute (deriving from The Dow Chemical Company).

Amplify ^TMGR-216 is ethylene/octene-1 multipolymer with about (roughly) 0.8wt% maleic anhydride graft, and density is 0.875g/cc, melt index (I ₂) be 1.3 (deriving from The Dow ChemicalCompany).

EVA 265 is for containing the ethylene-vinyl acetate copolymer of 28wt% vinyl acetate, and melt flow is 3.0dg/min (deriving from DuPont).

SANTOPRENE TPV 191-55PA is TPV, derives from AdvancedElastomer Systems.

SANTOPRENE TPV 8291-70PA is TPV, derives from AdvancedElastomer Systems.

SANTOPRENE TPV 8271-55B100 is TPV, derives from AdvancedElastomer Systems.

LOTADER 8900 is the terpolymer of ethene, methyl acrylate and SY-Monomer G, derives from Arkema.

POLYBD 2035 is the TPU based on polybutadiene diol, and Tg is-34 ℃, and proportion is 0.995g/cc in the time of 25 ℃, and tensile strength is 1711psi, I ₂Be 1g/10 minute, hard segment content is 35wt%, and softening temperature is 90 ℃, and elongation is 559% (to derive from Sartomer Company, Inc.).

Affinity-g-Amine is also referred to as AffinityGA 1950-g-Amine or AffinityGA-g-Amine, through small-sized REX forcing machine melting mixing Affinity GA 1950 resins (density is that 0.87g/cc, maleic anhydride content the are 0.7wt%) reaction of maleic anhydride graft is prepared again through the ethylethylenediamine that sucks 2 molar equivalents.Affinity GA1950 resin is the resin of very low molecular weight, characterizes with viscosity rather than melt index usually.Before the MAH grafting, the Brooskfield viscosity of this resin in the time of 177 ℃ is 17000 centipoises (pressing ASTM D 1084 measures).

OBC 9007.10 is the olefin block copolymers that can obtain from Dow Chemicals, and melt index is 0.5 and density is 0.866g/cc.

8407-g-Amine is ENGAGE ^TM8407-g-(2-[N-the ethylamino]-ethyl succinimide (density of 0.87g/cc; About 5 melt index; 1.2wt% [N-ethylamino]-ethyl succinimide).This graftomer makes the Engage of maleic anhydride graft through adopting 2 normal diamines/acid anhydrides ^TM8407 (density of 0.87g/cc, the MI of 5g/10min, about 0.8wt%MAH grafting levels) are reacted with ethylethylenediamine and are prepared.Diamines is sucked maleic anhydride graft Engage ^TMIn 8407 the pellet, melt blending should be through the pellet that sucks in small-sized REX forcing machine.

8407-g-MAH is that 0.87g/cc and melt index are that 30 ENGAGE 8407 ethylene-octene copolymers and maleic anhydride react and prepare through density.Final melt index is near 5, and maleic anhydride content is near 0.8wt%.

The ethylethylenediamine of the homo-polypropylene of Polybond3150-g-Amine through grafted maleic anhydride (polymer P olybond3150, MFR (230C/2.16kg) is 50, MAH content is 0.5wt%, can obtain from Chemtura) and 3 molar equivalents reacts and prepares.

8402-g-Amine is by 0.8wt%MAH grafted ENGAGE 8402 (density=0.9, MI is 30 before grafting, MI is 5 after grafting) preparation: the ethylethylenediamine that at first sucks 2 molar equivalents makes through the pellet that sucks through the REX forcing machine again.

AMPLIFY GR216-g-Amine be meant through the ethylethylenediamine that at first sucks 2.0 molar equivalents (DEDA) again in reactive extruder melt blending be converted into the AMPLIFY of imidization amine

GR216 maleic anhydride (MAH) polymers grafted (can obtain from Dow, have 1.25 MI, 0.87 density, the grafting amount of 0.8wt%).

LDPE 662i is a new LDPE (film grade), can obtain from Dow Chemicals, and density is 0.917g/cc, melt index be 0.47 (190 ℃/2.16kg).

VERSIFY 2000-g-DEDA is prepared by 0.9wt%MAH grafted VERSIFY 2000 propylene-ethylene copolymers (ethylene content is 5wt%).The MFR of initial VERSIFY multipolymer be 2 (230 ℃/2.16kg) and density be 0.888g/cc.MAH grafting warp is converted into imidization amine with the ethylethylenediamine reaction of 3 molar equivalents.

OBC 9817.10-g-Amine utilizes the ethylethylenediamine of 3 molar equivalents to be prepared by 1.17%MAH grafted OBC 9817.10 (density=0.877, MI is 3.04) through reactive expressing technique.

OBC 9807.10-g-Amine utilizes the ethylethylenediamine of 3 molar equivalents to be prepared by 1.13wt%MAH grafted OBC 9807.10 (density=0.866, MI is 3.80) through reactive expressing technique.

OBC (32MI)-g-Amine utilizes the ethylethylenediamine of 3 molar equivalents to be prepared by 1.09wt%MAH grafted OBC (density=0.877, MI is 7.08) through reactive expressing technique.

The sample that is called 8407-g-Amine (A) is ENGAGE 8407-g-(2-[N-ethylamino] butyl succinimide (0.87 a density; About 5 melt index, and have following structure).It makes Engage 8407 (0.87 density, 5MI) material (the MAH grafting level of about 0.74wt%) and the preparation of butyl reacting ethylenediamine of maleic anhydride graft through adopting 2 normal diamines/acid anhydrides.Making this diamines suck pellet makes it pass through small-sized REX forcing machine again.

8407-g-Amine (B) is ENGAGE ^TM8407-g-(2-[N-ethylamino] ethyl succinimide (density 0.87g/cc; About 5 melt index; And have the structure shown in the following synoptic diagram A 1.2wt% [N-ethylamino] ethyl succinimide).This graftomer makes the Engage of maleic anhydride graft through adopting 2 normal diamines/acid anhydrides ^TM8407 (density 0.87g/cc, 5g/10 minute MI, about 0.74wt%MAH grafting levels) and ethylethylenediamine prepared in reaction.Make this diamines suck the Engage of maleic anhydride graft ^TM8407 pellets make through sucking pellet melt blending in small-sized REX forcing machine again.

(synoptic diagram A)

8407-g-OH is ENGAGE ^TM-g-(2-hydroxyethyl the succinimide) (density of 0.87g/cc; About 5g/10 minute melt index; The hydroxyethyl succinimide of 1.0wt%), it makes the Engage of maleic anhydride graft through adopting 3.5 normal thanomin/acid anhydrides ^TM8407 (0.87 density, 5 MI, 0.74wt% acid anhydrides) and thanomin react in forcing machine and prepare.This reaction is shown in synoptic diagram B:

Synoptic diagram B

8407-g-DEDA is meant that the MAH of the about 0.8wt% of grafting utilizes the ethylethylenediamine (DEDA) of 3 molar equivalents in reactive extruder, to be converted into the Engage 8407 (MI is 5, and density is 0.87g/cc) of imidization amine again.

AMPLIFY GR216-g-DEDA is meant that the ethylethylenediamine (DEDA) that utilizes 3 molar equivalents is converted into AMPLIFY GR216 maleic anhydride (MAH) polymers grafted of imidization amine in reactive extruder; Can obtain from Dow; MI is 1.25, and density is 0.87, and the grafting amount is 0.8wt%.

OBC 9507 is ethylene/octene-1 segmented copolymers, and density is 0.866g/cc, and melt index (I2) is 5g/10 minute (can obtain from The Dow Chemical Company).

OBC 9000 or OBC 9000.00 are ethylene/octene-1 segmented copolymers, and density is 0.877g/cc, and melt index (I2) is 0.5g/10 minute (can obtain from The Dow Chemical Company).

OBC 9500 is ethylene/octene-1 segmented copolymers, and density is 0.877g/cc, and melt index (I2) is 5g/10 minute (can obtain from The Dow Chemical Company).

Fusabond 493D is the ethylene-octene copolymer of maleic anhydride graft, can obtain from DuPont, and density is 0.87g/cc, melt index (I2) be 1.2 (190 ℃/2.16kg).

Amplify GR216 is the ethylene-octene copolymer of maleic anhydride graft, can obtain from The DowChemical Company, and density is 0.87g/cc, melt index (I2) be 1.25 (190 ℃/2.16kg).

OBC 9807.10 is olefin block copolymers, can obtain from The Dow Chemical Company, and density is 0.877, melt index (I2) be 15 (190 ℃/2.16kg).

Dark grey or ebony look enriched material can obtain from Americhem.The identifier of Dark grey is 53008-H1-101, and ebony identifier is 53169-H1-101.Vector resin is Escorene AN13K.

The embodiment that comprises the present composition of two kinds or more kinds of components

Embodiment in this joint comprises many block interpolymers of (a) at least a alkene and b) at least a functionalized polymkeric substance based on alkene, and title also comprises c for the embodiment of the following joint of " embodiment that comprises the present composition of at least three kinds of components ") at least a thermoplastic polyurethane.

With each base material (Isoplast ^TM2530, Pellethane ^TM2102-80A, CAPRON (nylon 6), polycarbonate Calibre ^TM200-14, PET (Eastman Eastar En-001) and PBT GE plastics315-1001) be injection molded into and be of a size of 3 inches * 3.5 inches * test piece of 0.0625 inch (thickness).Then each test piece is inserted in mould (0.125 " thickness); and 0.5 inch wide scotch tape (scotch tape) bar is disposed across the end (along outward flange; be parallel to said 3 inches limit) of test piece, thereby at base material be used for producing no bonding zone between the compsn of lamination injection molded layers.The said compsn that is used for the lamination injection molded layers is shown in table 6 and 7.Under die temperature near 250 ℃ melt temperature and 18 ℃, each compsn lamination is injection-moulded on above-mentioned each base material, form the lamination injection molded substrate.

With a slit die, 3 inches of being parallel to test piece are wide with every kind of lamination injection molded substrate, strike out 6～8 bars.Each bar is of a size of, and: 5.2mm is wide and 3 inches long.The free end (that end that contains the inner transparent adhesive tape layer) of lamination injection molded substrate is inserted in 23 ℃ and 50%RH (relative humidity) down in the pneumatic clamping on the equilibrated 4201Instron stretching testing machine.The synoptic diagram that has shown this test set at Fig. 8.The base material test piece is tightly peeled off on the base station of test set attached to Instron; And can move with the speed identical with pinblock through the sliding panel (referring to Fig. 8) that ball moves, wherein utilize the pulley of peeling off test set the vertical motion of spider to be converted into the tangential movement of sliding panel.This whole power that causes applying is perpendicular to test piece.This special-purpose setting is called " 90 degree are peeled off test ", with reference to ASTM D6862-04 standard.The constant airspeed that moves is at " 0.3mm/s ", and the Bluehill software through Instron writes down power and each displacement automatically.Divided by the width of bar, obtaining with N/mm is the stripping strength of unit with load (with newton (N) record).The MV and the standard deviation of 10～30 millimeters scope record stripping strengths are " MV ± standard deviation ", shown in following table 6 and 7.Each has tested 6～8 samples in analyzing.

Table 6: stripping strength (n=6-8)

		Isoplast?2530	Polycarbonate Calibre 200-14	Pellethane 2102-80A
						The lamination injection moulding composition	Stripping strength (N/mm)	Stripping strength (N/mm)	Stripping strength (N/mm)
Comparative Examples 1	Lotadar?8900	0.37±0.11	1.32±0.18	0.022±0.005
					Comparative Examples 2	EVA?265	0.26±0.11	3.33±0.09	0.091±0.020
Embodiment 5	5%8407-g-Amine (A) is in ENGAGE 8200	1.02±0.34	0.012±0.002	0.61±0.15
					Embodiment 6	5%8407-g-Amine (A) is in OBC 9507	1.67±0.77	0.11±0.04	0.39±0.08
Embodiment 7	5%8407-g-OH is in ENGAGE 8100	0.017±0.010	0.18±0.06
					Embodiment 8	5%8407-g-OH is in OBC 9000	0.07±0.11
Embodiment 3	5%8407-g-Amine (B) is in ENGAGE 8100	1.86±0.41	0.11±0.03	0.24±0.03
					Embodiment 4	5%8407-g-Amine (B) is in OBC 9000	4.62±0.26	0.35±0.04	3.30±0.06
Embodiment 1	5%Affinity-g-Amine is in ENGAGE 8100	1.61±0.28	0.08±0.01
					Embodiment 2	5%Affinity-g-Amine is in OBC 9000	3.05±0.05		2.30±0.17
Embodiment 6A	8407-g-OH	0.05±0.01	0.55±05
					Comparative Examples 6	AMPLIFY?GR?216	0.90±0.16	0.19±0.04
Embodiment 5A	8407-g-Amine(B)	2.58±0.14	0.16±0.02
					Comparative Examples 7	Engage ^TM7086/Polybd 2035?63∶37	0.25±0.04	0.44±0.07

Table 7: stripping strength (n=6-8)

		PET(Eastar EN-001)	PBT?GE?Plastics 315-1001	Nylon Capron 6
						The lamination injection moulding composition	Stripping strength (N/mm)	Stripping strength (N/mm)	Stripping strength (N/mm)
Comparative Examples 1	Lotadar?8900	0.28±0.07	0.081±0.012	0.038±0.008
					Comparative Examples 2	EVA?265	0.37±0.02	0.043±0.014	0.029±0.009
Embodiment 5	5%8407-g-Amine (A) is in ENGAGE 8200	0.023±0.002		0.019±0.012
					Embodiment 6	5%8407-g-Amine (A) is in OBC 9507			0.064±0.008

		PET(Eastar EN-001)	PBT?GE?Plastics 315-1001	Nylon Capron 6
					Embodiment 7	5%8407-g-OH is in ENGAGE 8100			0.023±0.009
Embodiment 8	5%8407-g-0H is in OBC 9000	0.077±0.011	0.026±0.011	0.027±0.007
					Embodiment 3	5%8407-g-Amine (B) is in ENGAGE 8100	0.054±0.004	0.048±0.007	0.023±0.013
Embodiment 4	5%8407-g-Amine (B) is in OBC 9000	0.15±0.02	0.12±0.02	0.033±0.005
					Embodiment 1	5%Affinity-g-Amine is in ENGAGE 8100	0.19±0.02	0.14±0.02	0.042±0.021
Embodiment 2	5%Affinity-g-Amine is in OBC 9000		0.045±0.012	0.046±0.015
					Comparative Examples 3	Santoprene?TPV 191-55PA			0.24±0.06
Comparative Examples 4	Santoprene?TPV 8291-70PA			0.13±0.02
					Comparative Examples 5	Santoprene?TPV 8271-55B100			0.082±0.028
Embodiment 6A	8407-g-OH	0.02±0.00		0.02±0.01
					Comparative Examples 6	AMPLIFY?GR?216	0.09±0.02	0.02±0.01	0.90±0.43
Embodiment 5A	8407-g-Amine(B)	0.28±0.02		0.39±0.05
					Comparative Examples 7	Engage ^TM?7086/Polybd 2035?63∶37	0.17±0.02	0.37±0.03	0.17±0.02

As stated, table 6 and 7 has been listed the stripping strength and the standard deviation of pure functionalized sample, comparative sample, the blend of low-level functionalized sample in OBC and random EO matrix.

The compsn of the embodiment of the invention has good adhesivity to polar substrates.For ISOPLAST2530 base material and PELLETHANE base material, the lamination injection moulding composition that contains OBC causes very high peel strength value.

The present composition also can be used for moisture and water-free dispersion-s.Aqueous dispersion can prepare like this: compsn and water to compatibilized in forcing machine carry out melt blending, thereby produce the stable and uniform dispersion-s that mean particle size is generally about 300nm.The solids content of this dispersion-s is generally 35～50wt% by the gross weight of dispersion-s.With dispersion agent UNICID for example ^TM350 acid are (by solid 6wt%; It is a kind of synthetic C26 carboxylic acid that is converted into sylvite, and can obtain from Baker Petrolite) add to the dispersion-s.Then dispersion-s is applied on Vestolen PP 7052 (BOPP) film of diaxial orientation as casting films, and the surface measurements ability.

Compsn of the present invention also can be used as the adhesion promotor of urethane,, extrudes so that artificial turf (or artificial grass filaments (grass yarn)) to be provided perhaps with the form of blend with pure form.

For example, compsn of the present invention can be extruded on band extruding production line (tape extrusion line) and stretch 5 times.The sample band can be tied up then, and with 5 strands each other folded bundle, imitates the bundle (bundle) of artificial turf silk after forming carpet clustering.Can these bundles be placed mould, again polycondensation glycol-isocyanic ester blend (for example shown in following table 8) injected this mould to the part of bundle.After about 30 minutes, can estimate the adhesivity of resulting polymers sample 25 ℃ of curing to urethane.

Table 8: glycol prescription

Therefore, compsn of the present invention can be used as the adhesion promotor of urethane in artificial turf and other are used, and its reactable introduces in polyolefine, and the manufacturing that the latter is used for artificial turf is with bunch be entangled with (the tuft lock) of the silk that improves the artificial turf carpet.

Adhesion obtains promoting that said coating is applied on the carpet backing with polyblend through functional group and polyurethane coating reaction.In the carpet backing side, cluster artificial grass filaments/belt surface exposes, and applies said coating on it.With the blend that is applicable to any Vilaterm that artificial grass filaments is used or propylene in, the concentration of adhesion promotor can be 100% of the present composition, also can extend to 10% of the present composition downwards.

Compsn of the present invention also can be used for making hydrophilic artificial grass filaments, and intention produces more " the player close friend's " surface properties.Particularly, thermoplastic polyurethane and the poly blend with compsn increase-volume of the present invention can be used for forming artificial turf.

Normally used paint is available from gondola Kenda Farben S.P.A. in footwear industry.With 5pbw equally available from isocyanic ester (NCO) prepolymer and the blend in advance of this paint of Kendra.With atomizer sample is applied the paint less than 20 micron thick.Heated sample 15 minutes in 110 ℃ oven heat then.Drew lattice paint adhesiveness test 24 hours according to ASTM D 3359-02 after a while.Use cutter to obtain 10 * 10mm ²Grid.TESA Tesafix (04970-00154-00) type adhesive tape is pressed on the sample.After about 60 seconds, fast adhesive tape is vertically torn from sample.When the paint square leaves sample,

repeat

2 or 3 times.The square that calculating peels also is recorded in following table with the % adhesivity.

The brushing adhesivity of footwear paint

Shown in blend " blend in the Hakke twin screw extruder 3/4." urethane (PU) the glue adhesiveness test that the test piece of thickness and carrying out is used in the footwear industry that makes 0.125.Usually, the polymer samples that in footwear industry, uses need be through the stripping strength of 5N/mm.With toluene cleaning polymer surfaces and with the sand papering of class 60.By the paint brush, use the mixture of MEK, Footwear tackiness agent ForestaliPoligrip M328 and Desomdur RFE to be PET backing and polymer surfaces priming.Make them in drying at room temperature, then 100 ℃ of heating 30 seconds.Then, with two parts of mixture paint of tackiness agent and DesomdurRFE and make it in drying at room temperature.Heated polymerizable thing test piece 5 minutes and in 110 ℃ baking oven with PET backing heating 1 minute.The adhesive faec of the adhesive faec of PET backing and polymkeric substance is put together and leniently suppressed with hammer.With this sandwich structure put into thermocompressor and between the thick foam sheet of two 2cm 10bar and room temperature pressed 1 minute.Then the gained sample is peeled off test, and the stripping strength number is recorded in the following table.

Polymkeric substance	Wt％	Wt％	Wt％	Wt％
					Engage ^TM?8200	0	0	0	0
Amplify?GR?216-g-DEDA	0	20	100	0
					8407-g?DEDA	20	0	0	100
OBC?9500	80	80	0	0

Adhesive power [N/mm]

7.5

8.5

4.3

8.9

For all samples in the following table, at first injection moulding test piece is then at these lamination injection moulding lamination injection moulding Isoplast, Pellethane 2102-80A, Pellethane 2355-80AE and Pellethane2103-70A above test piece.Use 90 degree to peel off test and produce the peel strength data shown in the following table in N/mm.

	Isoplast 2530	Pellethane 2102-80A	Pellethane 2355-80AE	Pellethane 2103-70A
					OBC?9500	Too low	Too low	Too low	Too low
5%8407-g-Amine is in OBC 9007.10	4.7	3.7	3.9	2.5
					5%AffinityGA1950-g-Amine is in OBC 9007.10	2.4	2.8	1.9	3.4
5%8407-g-Amine is in OBC 9000	3.1	3.1	2.8	1.9
					5%AffinityGA 1950-g-Amine is in OBC 9000	3.4	2.7	2.6	3.9
5wt%8407-g-MAH is in OBC 9000	0.2	Too low	Too low	0.3
					5wt%Polybond3150-g-Amine is in OBC 9000	1.5	3.9	5.1	4.9
5wt%8402-g-Amine is in OBC 9000	3.1	2.8	3.9	2.5
					5wt%GR216-g-Amine is in OBC 9500	4.2	3.9	4.1	4.8
Neat?8407-g-Amine	3.3	4.4	6.5	10.0
					Neat?8402-g-Amine	3.3	1.1	8.7	6.8
Neat?8407-g-MAH	Too low	Too low	Too low	Too low
					5wt％Engage?8407-g-Amine， 95wt％OBC?9000	5.3	4.8	6.1	2.5
5wt％Engage?8407-g-Amine， 15wt％LDPE?662i， 80wt％OBC?9000	2.3	3.7	7.0	3.5
					5wt％VERSIFY?2000-g-DEDA， 95wt％OBC?9000	2.4
5wt％OBC?9817.10-g-Amine， 95wt％OBC?9000.00	3.2
					5wt％OBC?9807.10-g-Amine， 95wt％OBC?9000.00	2.5	4.9	3.6	5.6
5wt％OBC(32MI)-g-Amine， 95wt％OBC?9000.00	1.9	3.1	3.6	2.1

As above shown in the table, a large amount of functional polyolefin elastomericss that cover certain percent crystallinity and MI scope are the suitable candidate of sneaking into the elastomer blended OBC matrix of functionality.Graft polyolefin such as AffinityGA1950 that the material of very high MI makes have negative impact to adhesivity.Usually, contain the functionality POE of 5～10wt% functionality POE and the blend of OBC and be equivalent to or be better than pure functionality POE aspect the adhesivity stripping strength at least.They are also all good than MAH polymers grafted.And the blend of OBC and functionality polymkeric substance often performance is better than the blend of functionality polymkeric substance and random EO or P/E multipolymer.

Tested the brushing adhesivity of other paint system.The Sherman Williams G55N2096Soft Touch urethane paint that is generally used for the obducent V66VM100 of the containing catalyzer of air bag is the another kind of paint system to these sample tests.Use 3.5: 1 volumetric mixture ratio and use the target of 1.8 mils to use thickness.With the weight ratio of mixture be 100: 14 be that the NB coating 04172R7982K Black Mono urethane paint system that contains the C775 single catalyst that 1.0 mils are used is the another kind of paint system of estimating with target thickness.This automobile external of being everlasting uses.On 5 samples of every batch (lot), draw the test of lattice brushing adhesivity, write down adhesion failure percentage ratio and be recorded in following table with MV.

The brushing adhesivity

	NB coating paint	Sherman Williams paint
			5wt%AffinityGA-g-Amine is in OBC 9000.00	100	100
5wt%AffinityGA-g-Amine is in OBC 9007.10	93.5	98
			8407-g-Amine	92.5	100
5wt%Polybond3150-g-Amine is in OBC 9000	86	100
			5wt%8407-g-Amine is in OBC 9000	82.5	100
5wt%Polybond3150-g-Amine is in ENGAGE 8100	69	100
			5wt%8407-g-Amine is in ENGAGE 8100	37.5	94.3

From last table, can obviously find out, contain the functionality POE of 5～10wt% functionality POE and the blend of POE and be equivalent to or be better than pure functionality material aspect the brushing adhesivity at least.And, be better than the random EO multipolymer of suitable MI and density with the brushing adhesivity of the blend of OBC.High MI material of grafted such as AffinityGA1950 help the brushing adhesivity.

The embodiment that comprises the present composition of at least three kinds of components

The embodiment of this joint comprises usually: (a) the many block interpolymers of at least a alkene; B) at least a functionalized polymkeric substance based on alkene; And c) at least a thermoplastic polyurethane.Each component as stated.

Extrusion sheet can be formed by compsn of the present invention.Extrusion sheet is formed by the compsn shown in the table 9 and 10.All weight percent number averages are based on the gross weight of compsn.

Each component is delivered to respectively or delivered in the hopper of WP-ZSK twin screw extruder with one of dry blends.Addition manner does not influence the character of extrusion sheet.The speed of forcing machine is approximately 500 RPM, and zone temperatures is following: section 1=about 140 ℃ with about 170 ℃ of section 2-8=.When leaving forcing machine,, form the compounding pellet with the line material granulation of extruding.

In the static baking oven of routine under about 80 ℃ with compounding pellet dried overnight, to remove residual moisture.The exsiccant pellet is sent into Killion forcing machine (3 rollers bank up (roll stack)), and be extruded into the sheet material that thickness is the 20-40 mil.Extrude the used sheet material of table 9-10, thickness is the 20-40 mil.The speed of forcing machine is approximately 75-100RPM, and zone temperatures is following: section 1=180 ℃, and section 2-4=190 ℃.Flat hanger-style die through 20-40 mil thick and 2 feet wide is extruded compsn with 80lbs/hr, produces about 96s ^-1(for 40 mil thickness) and 385s ^-1The shearing rate of (for 20 mil thickness).This processing provides the extruded film with higher surface energy.

To each film surface measurements ability, thermostability, elongation, tear strength and glossiness, and be recorded in the table 9 and 10." NM " refers to not measure.In table 9, also write down the Permeability Parameters that moisture sees through test (ASTME 96/E 96M-05, Imperial method).

Table 9:POE/PELLETHABE/ functionalized polyolefin blend

	4	5	6	7	8	9

Engage ^TM?7086	57	69.5	57	69.5	59.5	63.8
							Pellethane?2102-80A	36	25	36	25	36	30
8407-g-OH	5	3.5	0	0	0	0
							8407-g-Amine	0	0	5	3.5	2.5	4.2
The Dark grey enriched material	2	2	2	2	2	2
								100	100	100	100	100	100
The surface energy extrusion sheet	36	36	41	38	43	41
							The surface energy standard is qualified/lost efficacy (＞35 dynes per centimeter, qualified)	Qualified	Qualified	Qualified	Qualified	Qualified	Qualified
Ultimate tensile strength (MPa) MD	14.4	16.7	17.9	23.3	19.9	22.2
							Elongation (%) MD	527.1	582.0	599.1	700.3	628.2	619.8
Mould C tear strength (N/mm)	83.9	94.7	89.8	72.4	85.5	94.4
							60 degree gloss	19.3	5.4	3.4	30.7	26.8	4.3
120 ℃ of thermal ageings	NM	NM		NM		NM
							Incipient extension			27.07		31.56
72hr			25.56		39.56
							7 days			28.53		NM
14 days			26.31		NM
							21 days					NM

							The initial elongation rate			749		551
72hr			706		644
							7 days			694		NM
14 days			746		NM
							21 days					NM

Table 10:POE/PELLETHANE/ functionalized polyolefin blend

	10	11	12	Pure 2103-70A	Correlated 63: 37 Engage ^TM?7086

Engage ^TM?7086	57	69.5	41	0
						Pellethane?2103-70A	36	25	50	100
8407-g-Amine	5	3.5	7	0
						The Dark grey enriched material	2	2	2	0
Surface energy (dyn/cm)	40	40	39	NM

Thickness (inch)	0.016	0.019	0.02	0.006	0.0090
						Rate of permeation (Perm-inch)	0.014	0.004	0.038	0.128	0.0000
The rate of permeation standard deviation	0.002	0.00005	0.0001	0.015	0.0000
						Penetration degree (perm)	0.878	0.197	1.914	23.3	0.2000
Transmission rates (grain/hour foot ²)	0.355	0.079	0.773	9.284	0.0820

Ultimate tensile strength (MPa) MD	13.5	13.3	17.6
						Elongation (%) MD	605.0	581.3	790.9
Mould C tear strength (N/mm)	69.5	70.3	62.6
						60 degree gloss	4.1	3.84	36.5
120 ℃ of thermal ageings		NM	NM	NM	NM
						Incipient extension	23.48
72hr	23.33
						7 days	NM
14 days	NM
						21 days	NM

						The initial elongation rate	653
72hr	700.8
						7 days	NM
14 days	NM
						21 days	NM

Moisture sees through The data ASTM E 96Imperial method and obtains.

Except showing favorable mechanical performance and glossiness, blend of the present invention also shows extraordinary surface energy.

The dependency of rate of permeation and polyurethane content can be found out through the data mapping of embodiment 10-12 in the his-and-hers watches 10.This linear dependence has been predicted pure Pellethane very exactly ^TM2103-70A rate of permeation, its be about 0.13 (perm-inch, Perm-inch).

Be used to form table 9 with 10 and following table 11 in the present composition (perhaps basically arbitrarily other the present composition) of extrusion sheet also can be used for moisture and water-free dispersion-s.

Aqueous dispersion

Aqueous dispersion can prepare like this: the melt blending present composition as herein described and water in forcing machine, thus produce the stable and uniform dispersion-s that mean particle size is generally about 300nm.The solids content of this dispersion-s is generally 35～50wt% by the gross weight of dispersion-s.With dispersion agent UNICID for example ^TM350 acid are (by solid 6wt%; It is a kind of synthetic C26 carboxylic acid that is converted into sylvite, and can obtain from BakerPetrolite) add to the dispersion-s.Then dispersion-s is applied on Vestolen PP 7052 (BOPP) film of diaxial orientation as casting films, and the surface measurements ability.

Adhesion promotor

The present composition as herein described also can be used as the adhesion promotor of urethane,, extrudes so that artificial turf (or artificial grass filaments) to be provided perhaps with the form of blend with pure form.

For example, compsn of the present invention can be extruded on the band extruding production line and stretch 5 times.The sample band can be tied up then, and with 5 strands each other folded bundle, imitates the bundle of artificial turf silk after forming carpet clustering.Can these bundles be placed mould, again polycondensation glycol-isocyanic ester blend (for example shown in following table 8) injected this mould to the part of bundle.After about 30 minutes, can estimate the adhesivity of resulting polymers sample 25 ℃ of curing to urethane.

Table 8: glycol prescription

Therefore, compsn of the present invention can be used as the adhesion promotor of urethane in artificial turf and other are used, and its reactable introduces in polyolefine, and the manufacturing that the latter is used for artificial turf bunch is entangled with the silk that improves the artificial turf carpet.

Adhesion obtains promoting that said coating is applied on the carpet backing with polyblend through functional group and polyurethane coating reaction.In the carpet backing side, cluster artificial grass filaments/belt surface exposes, and applies said coating on it.Be applicable to that the concentration of adhesion promotor can be 100% of the present composition, also can extend to 10% of the present composition downwards in any Vilaterm or polyacrylic blend that artificial grass filaments is used.

Extrusion sheet

The extrusion sheet that comprises the compsn of code name A-I in the following table is through compounding preparation of compositions on zsk-25, and wherein the temperature distribution at section 1 to section 4 is respectively 140 ℃, 170 ℃, 170 ℃ and 170 ℃.The compsn of dry gained then, and use Killion three sheet production lines to be extruded into the sheet material of 20 mil thick with Maddock mixing screw, the temperature distribution that wherein adopts is 175 ℃, 185 ℃ and 190 ℃.

The test that the sheet material of code name A-I is carried out produces following result

Test	A	B	C	D	E	F	G	H	I
										60 spend the average of 5 readings of gloss-films, (%)	10	7	23	14	13	19	31	18	14
Tearing: thermoplastic-type C-CD is average-tear strength, (lbf/n)	264	253	236	269	308	181	315	320	312
										Tearing: thermoplastic-type C-MD is average-tear strength, (lbf/in)	269	290	280	286	304	253	370	390	372

Test	A	B	C	D	E	F	G	H	I
										Stretching-CD-D638 is average-stress-at-break, (psi)	1708	1201	1893	2805	2640	1626	2575	2140	2567
Stretching-CD-D638 is average-breaking strain, (%)	911	746	744	630	812	740	638	681	589
										Stretching-MD-D638 is average-stress-at-break, (psi)	2580	2435	2785	2351	3366	2588	3961	3464	4168
Stretching-MD-D638 is average-breaking strain, (%)	589	623	751	814	721	686	661	599	592
										Surface energy, (dyn/cm)	34	34	34	34	34	34	30	34	34
Stroke lattice paint adhesiveness test classification of the coating of the PU coating AWOF-0082 of use United Paint, (grade)	5	5	5	5	5	5	5	5	5
										The adhesivity (cohesive failure) of " Dow Great Stuff Insulating Foam ", (qualified/as to lose efficacy)	Lost efficacy	Lost efficacy	Qualified	Lost efficacy	Lost efficacy	Qualified	Qualified	Qualified	Qualified

The extrusion sheet of following embodiment is that the present composition by table 11 forms.All weight percent number averages are based on the gross weight of compsn.

Each component is delivered to respectively or delivered in the hopper of WP-ZSK twin screw extruder with one of dry blends.Addition manner does not influence the character of extrusion sheet.The speed of forcing machine is approximately 500RPM, and zone temperatures is following: about 140 ℃ of section 1=, about 170 ℃ of section 2-8=.When leaving forcing machine,, form the compounding pellet with the line material granulation of extruding.

In the static baking oven of routine in the time of about 80 ℃ with compounding pellet dried overnight, to remove residual moisture.The exsiccant pellet is sent into Killion forcing machine (3 rollers are banked up), and be extruded into the sheet material that thickness is the 20-40 mil.Extrude sheet material used in the table 11, thickness is the 20-40 mil.The speed of forcing machine is approximately 75-100RPM, and zone temperatures is following: section 1=180 ℃, and section 2-4=190 ℃.Flat hanger-style die through 20-40 mil thick and 2 feet wide is extruded compsn with 80lbs/hr, produces about 96s ^-1(for 40 mil thickness) and 385s ^-1The shearing rate of (for 20 mil thickness).Compsn 1,2 and 4 is extruded with 40 mil thickness, and compsn 3 is extruded with 20 mil thickness.This processing provides the extruded film with higher surface energy.

Measure surface energy, thermostability, elongation, tear strength and the glossiness of each film, and be recorded in the following table 11.

Table 11:POE/PELLETHANE ^TM/ compatibilized embodiment

	1	2	3	4
					ENR7086	57	69.5	59.5	51.74
Pellethane?2102-80A	36	25	36	36.26
					Amplify?GR216	5	3.5	2.5
FUSABOND 493D (1%MAH grafting)				10
					Ebony look enriched material	2	2	2	2
	100	100	100

	1	2	3	4
					The surface energy extrusion sheet	36	36	41	32
The surface energy standard is qualified/lost efficacy (＞35 dynes per centimeter, qualified)	Qualified	Qualified	Qualified	Lost efficacy
					Ultimate tensile strength (MPa) MD	22.2	22.9	25.6
Elongation (%) MD	656.9	668.8	619.1
					Mould C tear strength (N/mm)	93.4	91.8	94.4	47.3
60 degree gloss	2.5	5.0	29.9	3.6
					120 ℃ of thermal ageings	NM	NM
Incipient extension (MPa)			38.5	26
					72hr			45.0	NM
7 days			NM	30.8
					14 days			NM	27.6
21 days			NM	28

The initial elongation rate, %			482	600
					72hr			636	NM
7 days			NM	593
					14 days			NM	548
21 days			NM	623

NM=does not measure

The present composition in the last table also shows extraordinary surface energy except showing excellent in mechanical properties and glossiness.

The extrusion sheet that comprises the compsn of code name J-Q in the following table is through compounding preparation of compositions on zsk-25, and wherein the temperature distribution at section 1 to section 4 is respectively 140 ℃, 170 ℃, 170 ℃ and 170 ℃.The compsn of dry gained then, and use Killion three sheet production lines to be extruded into the sheet material of 20 mil thick with Maddock mixing screw, the temperature distribution that wherein adopts is 175 ℃, 185 ℃ and 190 ℃.

The test that the sheet material of code name J-Q is carried out produces following result

Test	J	K	L	M	N	O	P	Q
										60 spend the average of 5 readings of gloss-films, (%)	18	22	20	31	28	25	10	15
Tearing: thermoplastic-type C-CD is average-tear strength, (lbf/in)	250	254	251	275	293	338	258	304
									Tearing: thermoplastic-type C-MD is average-tear strength, (lbf/in)	252	299	327	295	290	380	386	420
Stretching-CD-D638 is average-stress-at-break, (psi)	2307	2283	2088	2806	2763	1543	1506	1819
									Stretching-CD-D638 is average-breaking strain, (%)	822	833	743	815	826	564	542	485
Stretching-MD-D638 is average-stress-at-break, (psi)	2914	3719	3254	3597	3496	4123	2805	3693
									Stretching-MD-D638 is average-breaking strain, (%)	710	769	623	768	756	455	532	434
Surface energy, (dyn/cm)	34	34	34	34	34	30	35	32
									Stroke lattice paint adhesiveness test classification of the coating of the PU coating AWOF-0082 of use United Paint, (grade)	3	5	5	5	5	5	5	5
The adhesivity (cohesive failure) of " Dow Great Stuff Insulating Foam ", (qualified/as to lose efficacy)	Lost efficacy	Lost efficacy	Qualified	Qualified	Qualified	Lost efficacy	Qualified	Qualified

The extrusion sheet that comprises the compsn of code name R-W in the following table is through compounding preparation of compositions on zsk-30, and wherein the temperature distribution at section 1 to section 4 is respectively 140 ℃, 170 ℃, 170 ℃ and 170 ℃.The compsn of dry gained then, and 3/4 " be extruded into the sheet material of 20 mil thick on the Haake forcing machine, the temperature distribution that wherein adopts is 175 ℃, 185 ℃ and 190 ℃.

The test that the sheet material of code name R-W is carried out produces following result

Test	R	S	T	U	V	W
							60 spend the average of 5 readings of gloss-films, (%)	13.6	15.58	7.94	15.64	4.76	6.68
Tearing: thermoplastic-type C-MD is average-tear strength, (lbf/in)	224	241	282	313	230	243
							Stretching Micro ASTM D 1708, (limit-in-mean psi)	343	509	658	1096	530	635
Stretching Micro ASTM D 1708, (average percent elongation)	238	334	363	500	335	496
							Surface energy, (dyn/cm)	35	35	35	35	35	35
Stroke lattice paint adhesiveness test classification of the coating of the PU coating AWOF-0082 of use United Paint, (grade)	5	5	5	5	5	5
							The adhesivity (cohesive failure) of " Dow Great Stuff Insulating Foam ", (qualified/as to lose efficacy)	Qualified	Qualified	Qualified	Lost efficacy	Qualified	Qualified

Injection moulding test piece research

The present composition in the following table prepares through the many block interpolymers of alkene (OBC), SBS 401 and thermoplastic polyurethane by the functionalised polyolefin of the gross weight 5wt% of compsn and various weight percent and type are carried out blend.Said thermoplastic polyurethane TPU is based on the TPU of polycaprolactam polyester glycol and methylene diisocyanate, and density is 1.18g/cm ³, MFR (190 ℃/2.16kg) be 5g/10 minute, and Xiao A hardness is 80.The styrene-butadiene-styrene rubber that SBS 401 makes for Total Petrochemicals, its phenylethylene/butadiene weight ratio is 22: 28wt%, density is 0.93g/cm ³Said functionalised polyolefin is 8407-g-Amine, and reactivity is extruded preparation with the ethylethylenediamine reaction of 3 molar equivalents through MAH grafted Engage 8407 (～0.8wt%MAH, MI～5) for it.In the following table among

sample

1,2 and the 6-8 used OBC be OBC 9100, and used OBC is OBC 9500 among sample 3-5 and the 9-10.

	OBC(wt％)	?SBS?401(wt％)	TPU(wt％)
				1	40	0	55
2	0	60	35
				3	40	0	55
4	0	40	55
				5	25	25	45
6	0	40	55
				7	60	0	35
8	25	25	45
				9	0	60	35
10	60	0	35

The present composition of last table can be injection molded into the thick test piece of about 0.5～1cm usually on the injection moulding apparatus of in shoemaking industry, using always under suitable melt temperature (about usually 160-170 ℃), the mould temperature (about usually 60-80F) that suits and the injection speed that suits.

Sample	Hardness (Shore A)	Density (g/cc)	Crushing load (kg/cm ²)	Elongation (%)	Wearing and tearing (mm ³)	Tear (kg/cm)	Melt index (I5)
								1	73	1.001	17.8	1131	201	43	36
2	63	1	9.9	928	178	37	1.1
								3	76	0.991	12	867	197	51	5
4	68	1.048	12.8	922	96	45	4.5
								5	72	1.008	10.4	874	164	44	5.7
6	67	1.048	15.3	1056	107	44	4.6
								7	75	0.983	9.2	1158	332	43	2.8
8	69	1.004	14.6	1055	179	37	4.8
								9	65	1.002	6.6	705	143	30	1
10	77	0.968	6.3	817	179	42	8.6

Although quite specifically clear in the foregoing embodiments the present invention, this specifies and is used for example description, and should not be construed as the restriction to the invention of describing in the accompanying claims.All USPs are incorporated in this specification sheets with the U.S. Patent application of admitting or the U.S. Patent application of publication by reference.

Claims

1. compsn that comprises following component:

A) the many block interpolymers of at least a alkene, and

B) at least a functionalized polymkeric substance based on alkene,

The wherein said at least a functionalized polymkeric substance based on alkene comprises one or more and this following functional group based on the main chain covalent linkage knot of the polymkeric substance of alkene:

Wherein, R ₁Be bivalent hydrocarbon radical, R ₂Can be contained the substituted monovalence alkyl of heteroatomic group for containing at least two carbon atoms and choosing wantonly; Perhaps

Wherein, R ₁Be bivalent hydrocarbon radical, perhaps by the substituted alkylidene group of one or more alkoxyl groups; Perhaps

R wherein ₁And R ₂Be the C of hydrogen or straight or branched independently ₁-C ₂₀Alkyl; R ₄Bivalent hydrocarbon radical for straight or branched; X is OH or NHR ₅, R wherein ₅Be the alkyl or the hydroxyethyl of straight or branched, and

The many block interpolymers of wherein said alkene are the many block interpolymers of ethylene/alpha-olefin, and this interpretation has one or more following characteristics:

(1) have average block index greater than 0 and at the most 1.0, and greater than 1.3 molecular weight distribution mw/mn;

(2) when utilizing TREF to carry out fractionation, have at least a between 40 ℃ and 130 ℃ the molecule cut of wash-out, it is characterized in that this cut has at least 0.5 and at the most 1 blockiness index;

(3) have 1.7 to 3.5 Mw/Mn, at least one in degree centigrade fusing point Tm and in the density d of gram/cubic centimetre, wherein the numerical value of Tm and d meets following relational expression:

T _m＞-2002.9+4538.5(d)-2422.2(d) ²；

(4) has 1.7 to 3.5 Mw/Mn; And relational expression below the numerical value that it is characterized in that Δ T and Δ H satisfies; Wherein Δ H is the melting heat in J/g, Δ T be in degree centigrade increment, this increment is defined as the highest DSC peak and the peak-to-peak temperature head of the highest CRYSTAF:

As Δ H during greater than 130J/g, Δ T >=48 ℃,

Wherein said CRYSTAF peak utilizes at least 5% cumulative polymer determination, if having discernible CRYSTAF peak less than 5% polymkeric substance, then the CRYSTAF temperature is 30 ℃;

Re＞1481-1629(d)；

(7) it is characterized in that storage modulus G ' (25 ℃) and the storage modulus G ' in the time of 100 ℃ (100 ℃) in the time of 25 ℃, wherein G ' (25 ℃) is 1: 1 to 9: 1 with the ratio of G ' (100 ℃).

2. the compsn of claim 1, the wherein said functionalized polymkeric substance based on alkene is: the ethylene/alpha-olefin interpolymers that (1) is functionalized, wherein this terminal olefin is selected from 1-propylene, 1-butylene, 1-hexene and 1-octene; Perhaps (2) functionalized propylene/ethylene interpretation.

3. claim 1 or 2 compsn, wherein said at least a functionalized polymkeric substance based on alkene comprise one or more with should be based on following functional group of the main chain covalent linkage knot of the polymkeric substance of alkene:

R wherein ₁Be selected from alkylidene group and phenylene, and R wherein ₂Be alkyl or aryl.

4. claim 1 or 2 compsn, wherein said at least a functionalized polymkeric substance based on alkene comprise one or more with should be based on following functional group of the main chain covalent linkage knot of the polymkeric substance of alkene:

R wherein ₁Be selected from down group: ethylidene, propylidene, butylidene.

5. claim 1 or 2 compsn, wherein said at least a functionalized polymkeric substance based on alkene comprise one or more with should be based on following functional group of the main chain covalent linkage knot of the polymkeric substance of alkene:

R wherein ₁For-CH (OCH ₂CH ₂Me) CH ₂-or-adjacent phenylene-CH ₂-.

6. claim 1 or 2 compsn, it also comprises at least a filler.

7. the compsn of claim 6, wherein said filler is a talcum.

8. the compsn of claim 7, wherein said filler is for used at least a amine silane surface modified talcum.

9. claim 1 or 2 compsn, it also comprises at least a thermoplastic polyurethane.

10. the compsn of claim 9, wherein said at least a thermoplastic polyurethane comprise the chemical unit that comes from (1) at least a polyester and (2) at least a aromatics or aliphatic vulcabond.

11. comprising, the compsn of claim 9, wherein said at least a thermoplastic polyurethane come from polyester and 1, two (isocyanato methyl) hexanaphthenes and 1 of 3-, the chemical unit of the mixture of two (isocyanato methyl) hexanaphthenes of 4-.

12. the compsn of claim 9, wherein said at least a thermoplastic polyurethane comprises the monomeric unit that comes from diol, derivatives, and this diol, derivatives comes from the N-octylpyrrolidone.

13. the compsn of claim 9, wherein said at least a thermoplastic polyurethane comprises the monomeric unit that comes from polyethers.

14. the compsn of claim 1 or 2, the amount of wherein said at least a functionalized polymkeric substance based on alkene is less than or equal to 20wt% by the gross weight of compsn.