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EP1126969A1 - Gegenstände hergestellt aus zusammensetzungen von interpolymeren auf basis von alpha-olefinischen und vinyl- oder vinylidenaromatischen und/oder gehinderten aliphatischen oder cycloaliphatischen vinylischen oder vinylidenischen monomeren - Google Patents

Gegenstände hergestellt aus zusammensetzungen von interpolymeren auf basis von alpha-olefinischen und vinyl- oder vinylidenaromatischen und/oder gehinderten aliphatischen oder cycloaliphatischen vinylischen oder vinylidenischen monomeren

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Publication number
EP1126969A1
EP1126969A1 EP99958674A EP99958674A EP1126969A1 EP 1126969 A1 EP1126969 A1 EP 1126969A1 EP 99958674 A EP99958674 A EP 99958674A EP 99958674 A EP99958674 A EP 99958674A EP 1126969 A1 EP1126969 A1 EP 1126969A1
Authority
EP
European Patent Office
Prior art keywords
ethylene
styrene
component
fabricated article
vinyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99958674A
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English (en)
French (fr)
Inventor
Yunwa W. Cheung
Martin J. Guest
William R. Van Volkenburgh
Teresa P. Karjala
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
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Publication date
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Publication of EP1126969A1 publication Critical patent/EP1126969A1/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
    • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
    • C08L23/0838—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with monomers including an aromatic carbocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers

Definitions

  • This invention is related to fabricated articles prepared from polymer compositions which comprise at least one substantially random interpolymer comprising polymer units derived from one or more ⁇ -olefin monomers with specific amounts of one or more vinyl or vinylidene aromatic monomers and/or sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers in combination with minor amounts of one or more thermoplastic polymers which are immiscible with the substantially random interpolymer.
  • the fabricated articles are prepared in a final melt processing step comprising a flow fabrication process which can be characterized by the shear field applied in the process.
  • the blend compositions exhibit a unique mixing behavior and final solid state structure such that, even at low concentrations of the immiscible thermoplastic polymer blend component, the resulting fabricated articles exhibit an unexpected combination of properties included, but not limited to, modulus, high temperature performance and transparency.
  • the fabricated articles can be used in applications including, but not limited to, films, tapes, sheets, fibers, foams, injection molded articles, injection/blow molded articles, injection molded flexible goods, extruded profiles, toys, injection molded toys, housewares, paintable goods, furniture, automotive parts, lawn and garden appliances, small appliances, large appliances, and the like.
  • the generic class of materials covered by ⁇ -olefin/hindered vinylidene monomer substantially random interpolymers and including materials such as ⁇ - olefm vinyl aromatic monomer interpolymers, described in US 5703187, are known in the art and offer a range of material structures and properties which makes them useful for varied applications.
  • the interpolymers can find utility as compatibilizers for blends of polyethylene and polystyrene as described in US 5,460,818.
  • the utility of the interpolymers in film and sheet structures has been further described, for example in WO 95/32095
  • Blend compositions are finding increasingly utility in performance applications which require a combination of properties unavailable in a single polymer.
  • WO 97/115546 and copending US Application No. 08/1 17136 by M. J. Guest, et al., filed on 23 July, 1997 describes blends of substantially random interpolymers;
  • WO 97/15533 describes blends of substantially random interpolymers and polyethylene;
  • copending US Provisional Application No. 60/077663 by S. A. Ogoe et al., filed on 11 March, 1998 describes blends of substantially random interpolymers and polycarbonate; copending US Application No.
  • Blending technology is recognized as being complex, particularly for so-called immiscible polymer/polymer systems. Melt processing operations are often employed to blend polymers and manufacture solid parts from mixed polymer systems. For immiscible polymer-polymer blends, the final solid state properties are known to be dependent not only upon the selection of blend components and composition ratio, but are also determined by the solid state morphology (see for example Quintens et al., Polym. Eng. Sci. Vol 30, pages 1474 et seq. [1990]). The underlying technology is one of morphology development for which the rheological behaviour of the blend components, interfacial characteristics and processing conditions are generally accepted as important (see for example Van Oene, J. Coll. Interface Sci. Vol.
  • Basic descriptors for the types of morphology include matrix-inclusion (or complex occlusion), co-continuous and fibrillar or lamellar structures.
  • matrix-inclusion or complex occlusion
  • co-continuous and fibrillar or lamellar structures In polymer blending technology, it is well known that the addition of a minor volume fraction of a second, immiscible component B to a major volume fraction of component A typically results in an A B matrix/inclusion type morphology. In such a structure, many of the properties such as modulus and upper service temperature are essentially determined by those properties of the matrix phase.
  • articles fabricated under melt processing operations having a critical shear rate of greater than about 30 sec " ' exhibit substantially improved properties if such articles comprise a blend of at least one substantially random interpolymer and minor amounts of one or more thermoplastic polymers which are mutually immiscible.
  • the improved properties include but are not limited to modulus, toughness, upper service temperature, transparency and chemical resistance.
  • the property to be improved can be selected based on a choice of the minor component of the blend. For example the use of polystyrene as component B leads to improvements in modulus and upper service temperature, whereas the use of a high density polyethylene as component B additionally leads to improvements in properties such as chemical resistance.
  • the blend components A and B can have a wide range of molecular weights and molecular weight distributions, and these are selected dependent upon the performance requirements of the final fabricated article.
  • the present invention pertains to fabricated articles made by a high critical shear rate melt processing operation and comprising a blend of at least two polymers which are mutually immiscible, said blend comprising from 55 to 95 wt percent (based on the combined weights of Components A and B) of
  • thermoplastic polymer which is immiscible with Component (A) and is present in an amount of from 5 to 45 wt percent (based on the combined weights of Components A and B);
  • the fabricated articles can be used in applications including, but not limited to, films, tapes, sheets, fibers, foams, injection molded articles, injection/blow molded articles, injection molded flexible goods, extruded profiles, toys, injection molded toys, housewares, paintable goods, furniture, automotive parts, lawn and garden appliances, small appliances, large appliances, and the like.
  • Figure 1 is a graph showing the storage modulus as a function of the shear rate at which the extrudate was extruded at a temperature of Tg + 20°C.
  • any numerical values recited herein include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least 2 units between any lower value and any higher value.
  • the amount of a component or a value of a process variable such as, for example, temperature, pressure, time is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, it is intended that values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc. are expressly enumerated in this specification.
  • one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate.
  • hydrocarbyl as employed herein means any aliphatic, cycloaliphatic, aromatic, aryl substituted aliphatic, aryl substituted cycloaliphatic, aliphatic substituted aromatic, or aliphatic substituted cycloaliphatic groups.
  • hydrocarbyloxy means a hydrocarbyl group having an oxygen linkage between it and the carbon atom to which it is attached.
  • copolymer as employed herein means a polymer wherein at least two different monomers are polymerized to form the copolymer.
  • inte ⁇ olymer is used herein to indicate a polymer wherein at least two different monomers are polymerized to make the inte ⁇ olymer. This includes copolymers, te ⁇ olymers, etc.
  • fabricated article refers to fabricated compositions comprising films, fibers, foams, injection molded articles, injection-blow molded articles and extruded profiles.
  • high shear rate refers to a critical shear rate of greater than or about 30 sec " '.
  • high shear rate processing operation refers to a process for preparing a fabricated article in which the polymer blend is subjected to a high shear rate. Examples of high shear rate processing operations would be film blowing and injection molding.
  • low shear rate refers to a critical shear rate of less than or equal to about 30 sec " ' .
  • low shear rate processing operation refers to a process for preparing a fabricated article in which the polymer blend is subjected to a low shear rate.
  • a low shear rate processing operation would be compression molding.
  • mutant refers to individual components blend components which are immiscible in each other.
  • polymers are considered to be immiscible when, in a blend of the two or more polymers, the individual blend components can still be identified by electron microscopy as discrete domains, or by their characteristic thermal transitions (such as the glass transition, Tg) which can still be discerned.
  • the present invention provides fabricated articles prepared by melt processing a blend of at least two polymers under high shear rate conditions.
  • the blends comprise Component (A) being at least one substantially random inte ⁇ olymer (comprising polymer units derived from one or more ⁇ -olefin monomers with specific amounts of one or more vinyl or vinylidene aromatic monomers and/or sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers) and Component (B) being one or more other thermoplastic polymer components which are immiscible with, and present in minor amounts relative to, Component (A).
  • Component (A) being at least one substantially random inte ⁇ olymer (comprising polymer units derived from one or more ⁇ -olefin monomers with specific amounts of one or more vinyl or vinylidene aromatic monomers and/or sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers)
  • Component (B) being one or more
  • the articles of the present invention meet the criterion that, at temperatures at least 20°C in excess of the blend Tg (DSC), the elastic modulus of the article when prepared under high shear rate conditions is at least twice, preferably three times and more preferably ten times that of the article when prepared under low shear rate conditions.
  • the immiscible thermoplastic polymer components (B) of the blend can include, but is not limited to, one or more styrenic homopolymers or copolymers, ⁇ - olefin homopolymers or copolymers, engineering thermoplastics, styrenic block copolymers, elastomers, or vinyl halide polymers.
  • substantially random in the substantially random inte ⁇ olymer comprising polymer units derived from one or more ⁇ -olefin monomers with one or more vinyl or vinylidene aromatic monomers and/or aliphatic or cycloaliphatic vinyl or vinylidene monomers
  • substantially random means that the distribution of the monomers of said inte ⁇ olymer can be described by the Bernoulli statistical model or by a first or second order Markovian statistical model, as described by J. C. Randall in POLYMER SEQUENCE DETERMINATION, Carbon- 13 NMR Method. Academic Press New York, 1977, pp. 71-78.
  • substantially random inte ⁇ olymers do not contain more than 15 percent of the total amount of vinyl aromatic monomer in blocks of more than 3 units. This means that in the carbon n NMR spectrum of the substantially random inte ⁇ olymer, the peak areas corresponding to the main chain methylene and methine carbons, representing either meso diad sequences or racemic diad sequences, should not exceed 75 percent of the total peak area of the main chain methylene and methine carbons.
  • the substantially random inte ⁇ olymers used to prepare the articles of the present invention include inte ⁇ olymers prepared by polymerizing ethylene and/or one or more ⁇ -olefins with one or more vinyl or vinylidene aromatic monomers and/or one or more sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers, and optionally other polymerizable monomers.
  • Suitable ⁇ -olefins include for example, ⁇ -olefins containing from 3 to 20, preferably from 3 to 12, more preferably from 3 to 8 carbon atoms. Particularly suitable are propylene, butene-1, 4-methyl-l-pentene, heptene-1, hexene-1 or octene-1. Also suitable is ethylene in combination with one or more ⁇ -olefins containing from 3 to 20 carbon atoms, and particularly ethylene in combination with one or more selected from propylene, butene-1, pentene-1, 4-methyl-l-pentene, hexene-1, heptene-1 or octene-1. These ⁇ -olefins do not contain an aromatic moiety.
  • strained ring olefins such as norbornene and C,. 10 alkyl or C 6 . 10 aryl substituted norbornenes, with an exemplary inte ⁇ olymer being ethylene/styrene/norbornene.
  • Suitable vinyl or vinylidene aromatic monomers which can be employed to prepare the inte ⁇ olymers include, for example, those represented by the following formula: Ar
  • R i _ C C(R2) 2
  • R' is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl
  • each R 2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl
  • Ar is a phenyl group or a phenyl group substituted with from 1 to 5 substituents selected from the group consisting of halo, C -alkyl, and C -haloalkyk and n has a value from zero to 4, preferably from zero to 2, most preferably zero.
  • Exemplary vinyl aromatic monomers include styrene, vinyl toluene, ⁇ -methyl styrene. t-butyl styrene, chlorostyrene, including all isomers of these compounds, and the like. Particularly suitable such monomers include styrene and lower alkyl- or halogen-substituted derivatives thereof.
  • Preferred monomers include styrene, ⁇ -methyl styrene, the lower alkyl- (C, - C 4 ) or phenyl-ring substituted derivatives of styrene, such as for example, ortho-, meta-, and para-methylstyrene, the ring halogenated styrenes, para-vinyl toluene or mixtures thereof, and the like.
  • a more preferred aromatic vinyl monomer is styrene.
  • sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene compounds it is meant addition polymerizable vinyl or vinylidene monomers corresponding to the formula:
  • a 1 is a sterically bulky, aliphatic or cycloaliphatic substituent of up to 20 carbons
  • R' is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl
  • each R 2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl
  • R 1 and A 1 together form a ring system.
  • Preferred aliphatic or cycloaliphatic vinyl or vinylidene compounds are monomers in which one of the carbon atoms bearing ethylenic unsaturation is tertiary or quaternary substituted.
  • substituents include cyclic aliphatic groups such as cyclohexyl, cyclohexenyl, cyclooctenyl, or ring alkyl or aryl substituted derivatives thereof, tert-butyl, norbornyl, and the like.
  • Most preferred aliphatic or cycloaliphatic vinyl or vinylidene compounds are the various isomeric vinyl- ring substituted derivatives of cyclohexene and substituted cyclohexenes, and 5-ethylidene-2- norbornene.
  • 1-, 3-, and 4-vinylcyclohexene are particularly suitable.
  • ⁇ -Olefin monomers containing from 3 to 20 carbon atoms and having a linear aliphatic structure such as propylene, butene-1, hexene-1 and octene-1 are not considered as hindered aliphatic monomers.
  • the substantially random inte ⁇ olymers may be modified by typical grafting, hydrogenation, functionalizing, or other reactions well known to those skilled in the art.
  • the polymers may be readily sulfonated or chlorinated to provide functionalized derivatives according to established techniques.
  • One method of preparation of the substantially random inte ⁇ olymers includes polymerizing a mixture of polymerizable monomers in the presence of one or more metallocene or constrained geometry catalysts in combination with various cocatalysts.
  • the substantially random inte ⁇ olymers can be prepared as described in EP-A-0,416,815 by James C. Stevens et al. and US Patent No. 5,703,187 by Francis J. Timmers, both of which are inco ⁇ orated herein by reference in their entirety.
  • Preferred operating conditions for such polymerization reactions are pressures from atmospheric up to 3000 atmospheres and temperatures from -50°C to 200°C. Polymerizations and unreacted monomer removal at temperatures above the autopolymerization temperature of the respective monomers may result in formation of some amounts of homopolymer polymerization products resulting from free radical polymerization.
  • substantially random ⁇ -olefin/vinyl aromatic inte ⁇ olymers can also be prepared by the methods described in JP 07/278230 employing compounds shown by the general formula
  • Cp' and Cp 2 are cyclopentadienyl groups, indenyl groups, fluorenyl groups, or substituents of these, independently of each other;
  • R 1 and R 2 are hydrogen atoms, halogen atoms, hydrocarbon groups with carbon numbers of 1 -12, alkoxyl groups, or aryloxyl groups, independently of each other;
  • M is a group IV metal, preferably Zr or Hf, most preferably Zr; and
  • R 3 is an alkylene group or silanediyl group used to crosslink Cp' and Cp 2 ).
  • the substantially random ⁇ -olefin/vinyl aromatic inte ⁇ olymers can also be prepared by the methods described by John G. Bradfute et al. (W. R. Grace & Co.) in WO 95/32095; by R. B. Pannell (Exxon Chemical Patents. Inc.) in WO 94/00500; and in Plastics Technology, p. 25 (September 1992), all of which are inco ⁇ orated herein by reference in their entirety.
  • inte ⁇ olymers which comprise at least one ⁇ -olefin/vinyl aromatic/vinyl aromatic/ ⁇ -olefin tetrad disclosed in U. S. Application No. 08/708,809 filed September 4, 1996 by Francis J. Timmers et al.
  • These inte ⁇ olymers contain additional signals in their carbon- 13 NMR spectra with intensities greater than three times the peak to peak noise. These signals appear in the chemical shift range 43.70 - 44.25 ppm and 38.0 - 38.5 ppm. Specifically, major peaks are observed at 44.1 , 43.9, and 38.2 ppm.
  • a proton test NMR experiment indicates that the signals in the chemical shift region 43.70 - 44.25 ppm are methine carbons and the signals in the region 38.0 - 38.5 ppm are methylene carbons.
  • these new signals are due to sequences involving two head-to- tail vinyl aromatic monomer insertions preceded and followed by at least one ⁇ -olefin insertion, for example an ethylene/styrene/styrene/ethylene tetrad- wherein the styrene monomer insertions of said tetrads occur exclusively in a 1 ,2 (head to tail) manner.
  • inte ⁇ olymers can be prepared by conducting the polymerization at temperatures of from -30°C to 250°C in the presence of such catalysts as those represented by the formula
  • silahydrocarbyl, hydrocarbylsilyl containing up to 30 preferably from 1 to 20 more preferably from 1 to 10 carbon or silicon atoms or two R groups together can be a C 0 hydrocarbyl substituted 1,3- butadiene; m is 1 or 2; and optionally, but preferably in the presence of an activating cocatalyst.
  • suitable substituted cyclopentadienyl groups include those illustrated by the formula: wherein each R is independently, each occurrence, H, hydrocarbyl, silahydrocarbyl, or hydrocarbylsilyl, containing up to 30 preferably from 1 to 20 more preferably from 1 to 10 carbon or silicon atoms or two R groups together form a divalent derivative of such group.
  • R independently each occurrence is (including where appropriate all isomers) hydrogen, methyl, ethyl, propyl. butyl, pentyl, hexyl, benzyl, phenyl or silyl or (where appropriate) two such R groups are linked together forming a fused ring system such as indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, or octahydrofluorenyl .
  • Particularly preferred catalysts include, for example, racemic-
  • titanium-based constrained geometry catalysts [N-( 1 , 1 -dimethylethyl)- 1 , 1 -dimethyl- 1 - [( 1 ,2,3,4,5- ⁇ )- 1 ,5 ,6.7-tetrahydro-s- indacen-l-yl]silanaminato(2-)-N]titanium dimethyl; (l-indenyl)(tert-butylamido) dimethyl- silane titanium dimethyl; ((3-tert-butyl)(l,2,3,4,5- ⁇ )-l-indenyl)(tert- butylamido) dimethylsilane titanium dimethyl; and ((3-iso-propy ⁇ )(l,2,3,4,5- ⁇ )-l- indenyl)(tert-butyl amido)dimethylsilane titanium dimethyl, or any combination thereof and the like.
  • ⁇ -olefin/vinyl aromatic monomer inte ⁇ olymers such as propylene/styrene and butene/styrene are described in United States patent number 5,244,996, issued to Mitsui Petrochemical Industries Ltd or United States patent number 5,652,315 also issued to Mitsui Petrochemical Industries Ltd or as disclosed in DE 197 11 339 Al to Denki Kagaku Kogyo KK. All the above methods disclosed for preparing the inte ⁇ olymer component are inco ⁇ orated herein by reference.
  • the random copolymers of ethylene and styrene as disclosed in Polymer Preprints Vol 39, No. 1, March 1998 by Toru Aria et al. can also be employed as blend components of the present invention.
  • the immiscible thermoplastic polymer components (B) of the blend can include, but are not limited to, one or more styrenic homopolymers or copolymers, ethylene and/or ⁇ -olefin homopolymers or copolymers, thermoplastic polyolefms, engineering thermoplastics, styrenic block copolymers, elastomers, or vinyl halide polymers.
  • the styrenic homopolymers or copolymers employed as component (B) in the blends of the present invention are polymers of vinyl or vinylidene aromatic monomers and include homopolymers or copolymers of one or more vinyl or vinylidene aromatic monomers, or an copolymer of one or more vinyl or vinylidene aromatic monomers and one or more monomers copolymerizable therewith other than an aliphatic ⁇ -olefin.
  • Suitable vinyl or vinylidene aromatic monomers are represented by the following formula:
  • R' is selected from the group of radicals consisting of hydrogen and alkyl radicals containing three carbons or less
  • Ar is a phenyl group or a phenyl group substituted with from 1 to 5 substituents selected from the group consisting of halo, C M - alkyl, and C -haloalkyl.
  • Exemplary vinyl or vinylidene aromatic monomers include styrene, para-vinyl toluene, ⁇ -methylstyrene, t-butyl styrene, chlorostyrene, including all isomers of these compounds, etc.
  • Styrene is a particularly desirable vinyl aromatic monomer for the vinyl aromatic polymers used in the practice of the present invention.
  • a preferred polymer is atactic polystyrene. While preparing the substantially random inte ⁇ olymer component (A) of the present invention, atactic vinyl aromatic homopolymer may be formed due to homopolymerization of the vinyl aromatic monomer at elevated temperatures. For the pu ⁇ ose of the present invention, the atactic vinyl aromatic homopolymer, typically atactic polystyrene, constitutes at least part of the immiscible blend component (B).
  • Blend Component (B) other than a vinyl or vinylidene aromatic monomer
  • suitable copolymerizable comonomers in Blend Component (B) include, for example, C 4 -C 6 conjugated dienes, especially butadiene or isoprene, n-phenyl maleimide, acrylamide, ethylenically-unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile, ethylenically-unsaturated mono- and difunctional carboxylic acids and derivatives thereof such as esters and, in the case of difunctional acids, anhydrides, such as acrylic acid, C M - alkylacrylates or methacrylates, such as n-butyl aery late and methyl methacrylate.
  • the polymers of vinyl or vinylidene aromatic monomers with other copolymerizable comonomers preferably contain, polymerized therein, at least 50 percent by weight and, preferably, at least 65 percent by weight of one or more vinyl or vinylidene aromatic monomers.
  • styrenic copolymers are styrene/acrylonitrile (SAN) copolymers, styrene/maleic anhydride copolymers (SMA), styrene/methyl methacrylate copolymers (S-MMA) and the rubber modified copolymers such as acrylonitrile/butadiene/styrene copolymer (ABS).
  • the number average molecular weight M n of the styrenic homopolymers and copolymers used as blend components of the present invention is from 1000 to 1,000,000, preferably from 5,000 to 500.000. even more preferably from 10,000 to 350,000, and the molecular weight distribution M M n is from 1.005 to 20.000.
  • Rubber modified vinyl aromatic polymers can be prepared by polymerizing the vinyl aromatic monomer in the presence of a predissolved rubber to prepare impact modified, or grafted rubber containing products, examples of which are described in US patents 3,123,655, 3,346,520, 3,639,522, and 4,409,369 which are herein incorporated by reference.
  • the rubber is typically a butadiene or isoprene rubber, preferably polybutadiene.
  • the rubber modified vinyl aromatic polymer is high impact polystyrene (HIPS).
  • Component (B) may also be a flame resistant rubber modified styrenic blend composition.
  • the flame resistant compositions are typically produced by adding flame retardants to a high impact polystyrene (HIPS) resin.
  • IRPS ignition resistant polystyrene
  • Suitable polymers to be employed as component (B) also include vinyl or vinylidene aromatic polymers having a high degree of isotactic or syndiotactic configuration.
  • a high degree of syndiotactic configuration is meant that the stereochemical structure is mainly of syndiotactic configuration, the stereostructure in which phenyl groups or substituted phenyl group as side chains are located alternately at opposite directions relative to the main chain consisting of carbon-carbon bonds. Tacticity is quantitatively determined by the 13C-nuclear magnetic resonance method, as is well known in the art.
  • the degree of syndiotacticity as measured by 13C NMR spectroscopy is greater than 75 percent r diad, more preferably greater than 90 percent r diad.
  • Suitable examples of syndiotactic polymers include polystyrene, poly(alkylstyrene), poly(halogenated styrene), poly(alkoxystyrene), poly(vinylbenzoate), the mixtures thereof, and copolymers containing the above polymers as main components.
  • Poly(alkylstyrene) includes poly(methylstyrene), poly(ethylstyrene) poly(isopropylstyrene), poly(tert-butylstyrene), etc.
  • Poly(halogenated styrene) includes, poly(chlorostyrene), poly(bromostyrene), and poly(fluorostyrene), etc.
  • Poly (alkoxy styrene) includes, poly (methoxy styrene), poly(ethoxystyrene), etc.
  • Preferred styrenic copolymers having tacticity and employed as component (B) are syndiotactic polystyrene (SPS) which usually has a weight-average molecular weight of 10,000 to 10.000,000, preferably 100.000 to 5,500,000 with a number-average molecular weight of 5,000 to 5,500,000. preferably 50,000 to 2,500,000.
  • SPS syndiotactic polystyrene
  • the syndiotactic polymer has a melting point of 160 to 310°C.
  • the ethylene and/or ⁇ -olefin homopolymers or inte ⁇ olymers employed as blend component (B) in the blends of the present invention are polymers comprising ethylene and/or C 3 -C 20 ⁇ - olefins.
  • the ⁇ -olefin homopolymers and inte ⁇ olymers include polypropylene, propylene/C 4 -C 20 ⁇ - olefin copolymers, polyethylene, and ethylene/C 3 -C 20 ⁇ - olefin copolymers.
  • the inte ⁇ olymers can be either heterogeneous ethylene/ ⁇ -olefin inte ⁇ olymers or homogeneous ethylene/ ⁇ -olefin inte ⁇ olymers, including the substantially linear ethylene/ ⁇ -olefin inte ⁇ olymers.
  • Suitable aliphatic ⁇ -olefin monomers which introduce polar groups into the polymer include, for example, ethylenically unsaturated nitriles such as acrylonitrile, methacrylonitrile.
  • ethacrylonitrile, etc. ethylenically unsaturated anhydrides such as maleic anhydride; ethylenically unsaturated amides such as acrylamide, methacrylamide etc.: ethylenically unsaturated carboxylic acids (both mono- and difunctional) such as acrylic acid and methacrylic acid, etc.; esters (especially lower, for example C,-C 6 , alkyl esters) of ethylenically unsaturated carboxylic acids such as methyl methacrylate, ethyl acrylate, hydroxyethylacrylate, n-butyl acrylate or methacrylate, 2-ethyl-hexylacrylate etc.; ethylenically unsaturated dicarboxylic acid imides such as N-alkyl or N-aryl maleimides such as N-phenyl maleimide, etc.
  • anhydrides such as maleic anhydride
  • Such monomers containing polar groups are acrylic acid, vinyl acetate, maleic anhydride and acrylonitrile.
  • exemplary polymers are ethylene vinyl acetate (EVA) and ethylene vinyl alcohol (EVOH).
  • Halogen groups which can be included in the polymers from aliphatic ⁇ -olef ⁇ n monomers include fluorine, chlorine and bromine; preferably such polymers are chlorinated polyethylenes (CPEs).
  • Heterogeneous inte ⁇ olymers are differentiated from the homogeneous inte ⁇ olymers in that in the latter, substantially all of the inte ⁇ olymer molecules have the same ethylene/comonomer ratio within that inte ⁇ olymer, whereas heterogeneous inte ⁇ olymers are those in which the inte ⁇ olymer molecules do not have the same ethylene/comonomer ratio.
  • heterogeneous inte ⁇ olymers The term “broad composition distribution” used herein describes the comonomer distribution for heterogeneous inte ⁇ olymers and means that the heterogeneous inte ⁇ olymers have a "linear" fraction, multiple melting peaks (i.e., exhibit at least two distinct melting peaks) by DSC and have a degree of branching less than or equal to 2 methyls/1000 carbons in 10 percent (by weight) or more, preferably more than 15 percent (by weight), and especially more than 20 percent (by weight of the polymer).
  • the heterogeneous inte ⁇ olymers also have a degree of branching equal to or greater than 25 methyls/1000 carbons in 25 percent or less (by weight of the polymer), preferably less than 15 percent (by weight), and especially less than 10 percent (by weight of the polymer).
  • the Ziegler catalysts suitable for the preparation of the heterogeneous component of the current invention are typical supported, Ziegler-type catalysts which are particularly useful at the high polymerization temperatures of the solution process.
  • Examples of such compositions are those derived from organomagnesium compounds, alkyl halides or aluminum halides or hydrogen chloride, and a transition metal compound. Examples of such catalysts are described in U.S. Pat Nos. 4,314,912 (Lowery, Jr. et al.), 4,547,475 (Glass et al.), and 4,612,300 (Coleman, III).
  • Suitable catalyst materials may also be derived from a inert oxide supports and transition metal compounds. Examples of such compositions suitable for use in the solution polymerization process are described in U.S. Pat No. 5,420,090 (Spencer et al).
  • the heterogeneous polymer component can be an ethylene and/or ⁇ -olefin homopolymer preferably polyethylene or polypropylene, or, preferably, an inte ⁇ olymer of ethylene with at least one C3-C20 ⁇ -olefin and/or C4-C18 diolefins.
  • Heterogeneous copolymers of ethylene and 1 -butene, ethylene and 1 -pentene, ethylene and 1 -hexene and ethylene and 1 -octene are especially preferred.
  • Such polymers are known as homogeneous inte ⁇ olymers and are characterized by their narrower molecular weight and composition distributions relative to, for example, traditional Ziegler catalyzed heterogeneous polyolefin polymers.
  • Substantially linear ethylene/ ⁇ -olefin polymers and inte ⁇ olymers which can be employed as component (B) of the present invention are herein defined as in U.S. Patent No. 5,272.236 (Lai et al), and in U.S. Patent No. 5,278,272.
  • the homogeneous polymer component can be an ethylene and/or ⁇ -olefin homopolymer preferably polyethylene or polypropylene, or, preferably, an inte ⁇ olymer of ethylene with at least one C3-C20 ⁇ -olefin and/or C4-C18 diolefins. Homogeneous copolymers of ethylene and one or more C3-C8 ⁇ -olefins are especially preferred.
  • component (B) Commercially available products to be employed as component (B) include ultralow density polyethylene (ULDPE) low density polyethylene (LDPE), linear low density polyethylene (LLDPE) medium density polyethylene (MDPE), high density polyethylene (HDPE), polyolefin plastomers. such as those marketed by The Dow Chemical Company under the AFFINITYTM tradename and polyethylene elastomers, such as those marketed under the ENGAGETM tradename by Du Pont Dow Elastomers PLC.
  • the molecular weight of the ethylene homopolymers and inte ⁇ olymers for use in the present invention is conveniently indicated using a melt flow measurement according to ASTM D-1238, Condition 190°C/2.16 kg (formerly known as "Condition (E)" and also known as I 2 ).
  • melt flow rate is inversely proportional to the molecular weight of the polymer. Thus, the higher the molecular weight, the lower the melt flow rate, although the relationship is not linear.
  • the melt flow rate for the ethylene homopolymers and inte ⁇ olymers useful herein is generally from 0.1 grams/10 minutes (g/10 min) to 1000 g/10 min. preferably from 0.5 g/10 min to 200 g/10 min, and especially from 1 g/10 min to 100 g/10 min.
  • the C3 ⁇ -olefin homopolymers or copolymers employed as component (B) in the blends of the present invention are polypropylenes.
  • the polypropylene is generally in the isotactic form of homopolymer polypropylene, although other forms of polypropylene can also be used (e.g., syndiotactic or atactic).
  • Polypropylene impact copolymers e.g., those wherein a secondary in-reactor copolymerization step reacting ethylene with the propylene is employed
  • random copolymers also reactor modified and usually containing 1.5-20 mol percent of ethylene or C4-C8 ⁇ -olefin copolymerized with the propylene, however, can also be used.
  • the melt flow rate for the polypropylene useful herein is generally from 0.1 grams/10 minutes (g/10 min) to 200 g/10 min. preferably from 0.5 g/10 min to 100 g/10 min, and especially from 1 g/10 min to 50 g/10 min.
  • Thermoplastic olefins (TPOs) employed as component (B) are generally produced from propylene homo- or copolymers as described above, or blends of an elastomeric material such as ethylene/propylene rubber (EPM) or ethylene/propylene diene monomer te ⁇ olymer (EPDM) and a more rigid material such as isotactic polypropylene.
  • EPM ethylene/propylene rubber
  • EPDM ethylene/propylene diene monomer te ⁇ olymer
  • Other materials or components can be added into the formulation depending upon the application, including oil, fillers, and cross-linking agents.
  • TPO's can also be used as blend components of the present invention.
  • Engineering thermoplastics which can be employed as blend component (B) include polyoxymethylene-based resins such as acetal; acrylic resins (for example poly(methylmethacrylate, PMMA)); polyamides (for example nylon-4,6, nylon-6, nylon 6,6, and higher nylons), polyimides, polyetherimides, cellulosics, polyesters, poly(arylate); aromatic polyesters (for example polybutylene terephthalate and polyethylene terephthalate, PEN and polycarbonate); liquid crystal polymers; blends, or alloys of the foregoing resins; and other resin types including for example rigid thermoplastic polyurethanes; high temperature polyolefins such as ethylene/norbornene copolymers, polycyclopentanes, its copolymers, and polymethylpentane and its copolymers.
  • polyoxymethylene-based resins such as acetal; acrylic resins (for example poly(methylmethacrylate, PMMA)); polyamides (for example nylon-4,6, nylon-6
  • aromatic polyethers including, for example, the poly(phenylene ether) (PPE) thermoplastic engineering resins which are well known, commercially available materials produced by the oxidative coupling polymerization of alkyl substituted phenols. They are generally linear, amo ⁇ hous polymers having a glass transition temperature in the range of 190°C to 235°C.
  • PPE materials include those represented by the formula:
  • Q is the same or different alkyl group having from 1 to 4 carbon atoms and n is a whole integer of at least 100, preferably from 150 to 1200.
  • preferred polymers are poly(2,6-dialkyl-l,4-phenylene ether) such as poly(2,6-dimethyl-l,4- phenylene ether), poly(2-methyl-6-ethyl-l,4-phenylene ether), poly(2-mefhyl-6-propyl- 1 ,4-phenylene ether), poly-(2,6-dipropyl-l,4-phenylene ether) and poly (2-ethyl-6- propyl-1 ,4-phenylene ether).
  • a more preferred polymer is poly(2,6-dimethyl-l ,4- phenylene ether). These polymers are often sold as blends with polystyrene and high impact polystyrene, and other formulation components.
  • Especially preferred engineering thermoplastics are acetal, polymethylmethacrylate, nylon-6, nylon 6,6, bisphenol A-poly(carbonate), poly(2,6- dimethyl-l,4-phenylene ether), and polybutylene terephthalate and polyethylene terephthalate,
  • Styrenic block copolymers which can be employed as blend component (B) are those having unsaturated rubber monomer units including, but not limited to, styrene- butadiene (SB), styrene-isoprene(SI), styrene-butadiene-styrene (SBS), styrene- isoprene-styrene (SIS), ⁇ -methylstyrene-butadiene- ⁇ -methylstyrene and ⁇ - methylstyrene-isoprene- ⁇ -methylstyrene.
  • SB styrene- butadiene
  • SI styrene-isoprene
  • SI styrene-butadiene-butadiene-styrene
  • SIS styrene-isoprene-styrene
  • the styrenic portion of the block copolymer is preferably a polymer or copolymer of styrene and its analogs and homologs including ⁇ -methylstyrene and ring-substituted styrenes, particularly ring-methylated styrenes.
  • the preferred styrenics are styrene and ⁇ -methylstyrene, and styrene is particularly preferred.
  • Block copolymers with unsaturated rubber monomer units may comprise homopolymers of butadiene or isoprene or they may comprise copolymers of one or both of these two dienes with a minor amount of styrenic monomer.
  • Preferred styrenic block copolymers which can be employed as Component (B) include at least one segment of a styrenic unit and at least one segment of an ethylene-butene or ethylene-propylene copolymer.
  • block copolymers with saturated rubber monomer units examples include styrene/ethylene-butene copolymers, styrene/ethylene-propylene copolymers, styrene/ethylene-butene/styrene (SEBS) copolymers, styrene/ethylene-propylene/styrene (SEPS) copolymers.
  • SEBS styrene/ethylene-butene copolymers
  • SEBS styrene/ethylene-propylene copolymers
  • SEPS styrene/ethylene-propylene/styrene
  • the elastomers which can be employed as blend component (B) include, but are not limited to, rubbers such as polyisoprene, polybutadiene, natural rubbers, ethylene/propylene rubbers, ethylene/propylene diene (EPDM) rubbers, silicone rubbers, styrene/butadiene rubbers and thermoplastic polyurethanes.
  • rubbers such as polyisoprene, polybutadiene, natural rubbers, ethylene/propylene rubbers, ethylene/propylene diene (EPDM) rubbers, silicone rubbers, styrene/butadiene rubbers and thermoplastic polyurethanes.
  • the vinyl or vinylidene halide polymer component of the blends of the present invention include but are not limited to homopolymers and copolymers of vinyl or vinylidene halides with copolymerizable monomers such as ethylene and/or ⁇ -olefins including but not limited to ethylene, propylene, vinyl esters of organic acids containing 1 to 18 carbon atoms, for example vinyl acetate, vinyl stearate and so forth; vinyl chloride, vinylidene chloride, symmetrical dichloroethylene; acrylonitrile, methacrylonitrile; alkyl acrylate esters in which the alkyl group contains 1 to 8 carbon atoms, for example methyl acrylate and butyl acrylate; the corresponding alkyl methacrylate esters; dialkyl esters of dibasic organic acids in which the alkyl groups contain 1 - 8 carbon atoms, for example dibutyl fumarate, diethyl maleate, and so forth.
  • the vinyl or vinylidene halide polymers are homopolymers or copolymers of vinyl chloride or vinylidene chloride.
  • Poly (vinyl chloride) polymers PVC can be further classified into two main types by their degree of rigidity. These are “rigid” PVC and “flexible” PVC. Flexible PVC is distinguished from rigid PVC primarily by the presence of and amount of plasticizers in the resin. Flexible PVC typically has improved processability, lower tensile strength and higher elongation than rigid PVC.
  • PVDC vinylidene chloride homopolymers and copolymers
  • the copolymers with vinyl chloride, acrylates or nitriles are used commercially and are most preferred.
  • the choice of the comonomer significantly affects the properties of the resulting polymer. Perhaps the most notable properties of the various PVDC's are their low permeability to gases and liquids, barrier properties; and chemical resistance.
  • CPVC chlorinated PVC
  • additives such as antioxidants (e.g., hindered phenols such as, for example,
  • Irganox® 1010 a registered trademark of Ciba Geigy
  • phosphites e.g., Irgafos® 168 a registered trademark of Ciba Geigy
  • U.V. stabilizers e.g., polyisobutylene
  • slip agents such as erucamide and/or stearamide
  • antiblock additives colorants, pigments
  • colorants pigments
  • Processing aids which are also referred to herein as plasticizers, can also be included in either blend Component A and/or blend Component B or the overall blend compositions employed to prepare the fabricated articles of the present invention, and include the phthalates, such as dioctyl phthalate and diisobutyl phthalate, natural oils such as lanolin, and paraffin, naphthenic and aromatic oils obtained from petroleum refining, and liquid resins from rosin or petroleum feedstocks.
  • Exemplary classes of oils useful as processing aids include white mineral oil (such as KaydolTM oil (available from and a registered trademark of Witco), and ShellflexTM 371 naphthenic oil (available from and a registered trademark of Shell Oil Company). Another suitable oil is TufloTM oil (available from and a registered trademark of Lyondell).
  • Tackifiers can also be included in either blend Component A and/or blend Component B or the overall blend compositions employed to prepare the fabricated articles of the present invention to alter the processing performance of the polymer and thus can extend the available application temperature window of the articles.
  • a suitable tackifier may be selected on the basis of the criteria outlined by Hercules in J. Simons, Adhesives Age, "The HMDA Concept: A New Method for Selection of Resins", November 1996. This reference discusses the importance of the polarity and molecular weight of the resin in determining compatibility with the polymer.
  • preferred tackifiers will have some degree of aromatic character to promote compatibility, particularly in the case of substantially random inte ⁇ olymers having a high content of the vinyl aromatic monomer.
  • Tackifying resins can be obtained by the polymerization of petroleum and te ⁇ ene feedstreams and from the derivatization of wood, gum, and tall oil rosin.
  • tackifiers include wood rosin, tall oil and tall oil derivatives, and cyclopentadiene derivatives, such as are described in United Kingdom patent application GB 2,032,439A.
  • Other classes of tackifiers include aliphatic C5 resins, polyte ⁇ ene resins, hydrogenated resins, mixed aliphatic-aromatic resins, rosin esters, natural and synthetic te ⁇ enes, te ⁇ ene-phenolics, and hydrogenated rosin esters.
  • fillers are also included as a potential component of the polymer compositions used in the present invention.
  • the fillers can also be included in either blend Component A and/or blend Component B or the overall blend compositions employed to prepare the fabricated articles of the present invention.
  • Representative examples of such fillers include organic and inorganic fibers such as those made from asbestos, boron, graphite, ceramic, glass, metals (such as stainless steel) or polymers (such as aramid fibers) talc, carbon black, carbon fibers, calcium carbonate, alumina trihydrate.
  • glass fibers marble dust, cement dust, clay, feldspar, silica or glass, fumed silica, alumina, magnesium oxide, magnesium hydroxide, antimony oxide, zinc oxide, barium sulfate, aluminum silicate, calcium silicate, titanium dioxide, titanates, aluminum nitride, B 2 O 3 , nickel powder or chalk.
  • organic or inorganic, fiber or mineral, fillers include carbonates such as barium, calcium or magnesium carbonate; fluorides such as calcium or sodium aluminum fluoride; hydroxides such as aluminum hydroxide; metals such as aluminum, bronze, lead or zinc; oxides such as aluminum, antimony, magnesium or zinc oxide, or silicon or titanium dioxide; silicates such as asbestos, mica, clay (kaolin or calcined kaolin), calcium silicate, feldspar, glass (ground or flaked glass or hollow glass spheres or microspheres or beads, whiskers or filaments), nepheline, perlite, pyrophyllite, talc or wollastonite; sulfates such as barium or calcium sulfate; metal sulfides; cellulose, in forms such as wood or shell flour; calcium terephthalate; and liquid crystals. Mixtures of more than one such filler may be used as well.
  • the amount of antioxidant employed is that amount which prevents the polymer or polymer blend from undergoing oxidation at the temperatures and environment employed during storage and ultimate use of the polymers.
  • Such amount of antioxidants is usually in the range of from 0.01 to 10, preferably from 0.05 to 5, more preferably from 0.1 to 2 percent by weight based upon the weight of the polymer or polymer blend.
  • the amounts of any of the other enumerated additives are the functionally equivalent amounts such as the amount to render the polymer or polymer blend antiblocking, to produce the desired result, to provide the desired color from the colorant or pigment.
  • Such additives can suitably be employed in the range of from 0.05 to 50, preferably from 0.1 to 35, more preferably from 0.2 to 20 percent by weight based upon the weight of the polymer or polymer blend. Fillers may suitably be employed in the range 1 -90 wt. percent.
  • the blended polymer compositions used to prepare the fabricated articles of the present invention can be prepared by any convenient method, including dry blending the individual components and subsequently melt mixing or melt compounding in a Haake torque rheometer or by pre-melt mixing in a separate extruder or mill (e.g., a Banbury mixer), or by solution blending or by calendering.
  • the blend components can also be dry blended, without melt blending, followed by part fabrication, either directly in the extruder, injection molding machine, film blowing equipment or mill used to make the finished article,
  • the fabricated articles of the present invention can be made using conventional melt processing operations. Whatever the melt processing operation used, in order to obtain the fabricated articles of the present invention, the melt processing operation should be performed under high shear rate conditions such that the critical shear rate is greater than 30, preferably from 40 to 30,000, even more preferably from 50 to 5,000 sec "1 .
  • Such operations include for example simple bubble extrusion (usually with a high blow-up ratio (BUR)), biaxial orientation processes (such as tenter frames or double bubble processes), simple cast/sheet extrusion, coextrusion, lamination, etc.
  • BUR blow-up ratio
  • Conventional simple bubble extrusion processes also known as hot blown film processes are described, for example, in The Encyclopedia of Chemical Technology. Kirk-Othmer, Third Edition, John Wiley & Sons, New York. 1981 , Vol 16, pp. 416-417 and Vol. 18, pp. 191-192.
  • Biaxial orientation film manufacturing processes such as described in the "double bubble” process of USP 3,456,044 (Pahlke), and the processes described in USP 4,352.849 (Mueller), USP 4,820,557 and 4,837,084 (both to Warren), USP 4,865,902 (Golike et al.), USP 4,927,708 (Herran et al.).
  • USP 4.952,451 (Mueller), and USP 4,963,419 and 5,059,481 both to Lustig et al.
  • the fabricated articles of the present invention can also be rendered pervious or "breathable" by any method well known in the art including by apperturing, slitting, microperforating, mixing with fibers or foams, or the like and combinations thereof. Examples of such methods include, USP 3,156,242 by Crowe, Jr., USP 3.881,489 by Hartwell, USP 3,989,867 by Sisson and USP 5,085,654 by Buell.
  • thermoforming, extrusion coating, profile extrusion, and sheet extrusion melt processing operations are described, for example, in Plastics Materials and Processes, Seymour S. Schwartz and Sidney H. Goodman, Van Nostrand Reinhold Company, New York, 1982, pp. 527-563, pp. 632-647, and pp. 596-602.
  • the fabricated articles of the present invention can be prepared by the primary extrusion process itself or by known post-extrusion slitting, cutting or stamping techniques.
  • Profile extrusion is an example of a primary extrusion process that is particularly suited to the preparation of tapes, bands, ribbons and the like.
  • the substantially random inte ⁇ olymers blend component (A) and/or the immiscible thermoplastic polymer components (B) may also be modified by various cross-linking processes. These include, but are not limited to peroxide-, silane-, sulfur-, radiation-, or azide-based cure systems. A full description of the various cross-linking technologies is described in copending U.S. Patent
  • Dual cure systems which use a combination of heat, moisture cure, and radiation steps, may be effectively employed. Dual cure systems are disclosed and claimed in U. S. Patent Application Serial No. 536,022, filed on September 29, 1995, in the names of K. L. Walton and S. V. Karande, inco ⁇ orated herein by reference. For instance, it may be desirable to employ peroxide crosslinking agents in conjunction with silane crosslinking agents, peroxide crosslinking agents in conjunction with radiation, sulfur-containing crosslinking agents in conjunction with silane crosslinking agents, etc.
  • the polymer compositions used to prepare the fabricated articles of the present invention comprise (A) from 55 to 95. preferably from 65 to 92, more preferably from 70 to 90, even more preferably from 70 to 88 wt%, (based on the combined weights of Component A and the immiscible polymer Component B) of one or more substantially random inte ⁇ olymers of ethylene and /or one or more ⁇ -olefins and one or more vinyl or vinylidene aromatic monomers and/or one or more sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers, and (B) from 5 to 45, preferable from 8 to 35, more preferably from 10 to 30, even more preferably from 12 to 30 wt. percent (based on the combined weights of Component A and the immiscible polymer Component B) of one or more thermoplastic polymer components immiscible with Component (A).
  • Component (B) comprises one or more of a styrenic homopolymer or copolymer, an ethylene and/or ⁇ -olefin homopolymer or inte ⁇ olymer, a thermoplastic olefin. an engineering thermoplastic, a styrenic block copolymer, an elastomer, or a vinyl or vinylidene halide polymer.
  • substantially random inte ⁇ olymers contain from 1 to 65 preferably from 2 to 50, more preferably from 5 to 50 mole percent of at least one vinyl or vinyl or vinylidene aromatic monomer and/or sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer and from 35 to 99, preferably from 50 to 98. more preferably from 50 to 95 mole percent of ethylene and/or at least one aliphatic ⁇ -olefin having from 3 to 20 carbon atoms.
  • the melt index (I 2 ) of the substantially random inte ⁇ olymer used to prepare the fabricated articles of the present invention is greater than about 0.05, preferably of from 0.5 to 200, more preferably of from 0.5 to 100 g/10 min.
  • the molecular weight distribution (M w /M n ) of the substantially random inte ⁇ olymer used to prepare the elastic films of the present invention is from 1.5 to 20, preferably of from 1.8 to 10. more preferably of from 2 to 5.
  • the density of the substantially random inte ⁇ olymer used to prepare the elastic films of the present invention is greater than about 0.900. preferably from 0.930 to 1.045, more preferably of from 0.930 to 1.040, most preferably of from 0.930 to 1.030 g/cm 3 .
  • the fabricated articles of the present invention demonstrate an enhancement in modulus when prepared under high shear rate processing operations as compared to samples prepared under low shear rate processing operations.
  • the elastic modulus of the article prepared under high shear rate processing operations is at least twice, preferably three times and more preferably ten times that of the article prepared under low shear rate processing operations.
  • the fabricated articles of the present invention include films, fibers, foams, injection molded articles, injection-blow molded articles and extruded profiles, with films and injection molded articles being the most preferred embodiments.
  • the molecular weight of the polymer compositions for use in the present invention was conveniently indicated using a melt index measurement according to ASTM D-1238, Condition 190°C/2.16 kg (formally known as "Condition (E)” and also known as 12) was determined. Melt index was inversely proportional to the molecular weight of the polymer. Thus, the higher the molecular weight, the lower the melt index, although the relationship was not linear.
  • the influence of the atactic polystyrene was assumed to be minimal because of the low levels. Also, the melt density of atactic polystyrene and the melt densities of the samples with high total styrene were very similar.
  • the method used to determine the melt density employed a Gottfert melt index machine with a melt density parameter set to 0.7632, and the collection of melt strands as a function of time while the 12 weight was in force. The weight and time for each melt strand was recorded and normalized to yield the mass in grams per 10 minutes. The instrument's calculated I2 melt index value was also recorded. The equation used to calculate the actual melt density is
  • S weight percentage of styrene in the polymer.
  • S weight percentage of styrene in the polymer.
  • the relationship of total styrene to melt density can be used to determine an actual melt index value, using these equations if the styrene content was known.
  • Inte ⁇ olymer styrene content and atactic polystyrene concentration can be determined using proton nuclear magnetic resonance ( ⁇ N.M.R) or by 1 C nuclear magnetic resonance.
  • TCE-d 2 A 0.75 mL aliquot of TCE-d 2 was added by syringe and the tube was capped with a tight-fitting polyethylene cap. The samples were heated in a water bath at 85°C to soften the inte ⁇ olymer. To provide mixing, the capped samples were occasionally brought to reflux using a heat gun.
  • Proton NMR spectra were accumulated on a Varian VXR 300 with the sample probe at 80°C, and referenced to the residual protons of TCE-d 2 at 5.99 ppm. The delay times were varied between 1 second, and data was collected in triplicate on each sample. The following instrumental conditions were used for analysis of the inte ⁇ olymer samples:
  • VXR-300 standard ⁇ : Sweep Width, 5000 Hz
  • the total analysis time per sample was about 10 minutes. Initially, a 'H NMR spectrum for a sample of the polystyrene, StyronTM 680 (available form the Dow Chemical Company, Midland, MI) was acquired with a delay time of one second. The protons were "labeled”: b, branch; a, alpha; o, ortho; m, meta; p, para, as shown in Figure 2.
  • Integrals were measured around the protons labeled in Figure 2; the A' designates aPS. Integral A 7 , (aromatic, around 7.1 ppm) was believed to be the three ortho/para protons; and integral A 66 (aromatic, around 6.6 ppm) the two meta protons.
  • the two aliphatic protons labeled ⁇ resonate at 1.5 ppm; and the single proton labeled b was at 1.9 ppm.
  • the aliphatic region was integrated from about 0.8 to 2.5 ppm and was referred to as A a ,.
  • the theoretical ratio for A 7 1 : A 6 6 : A a was 3: 2: 3, or 1.5: 1 : 1.5, and correlated very well with the observed ratios for the StyronTM 680 sample for several delay times of 1 second.
  • the ratio calculations used to check the integration and verify peak assignments were performed by dividing the appropriate integral by the integral A 66 Ratio A r was A 7 , / A 66 .
  • Region A 66 was assigned the value of 1. Ratio Al was integral A a , / A 66 . All spectra collected have the expected 1.5: 1 : 1.5 integration ratio of (o+p): m: ( ⁇ +b). The ratio of aromatic to aliphatic protons was 5 to 3. An aliphatic ratio of 2 to 1 was predicted based on the protons labeled ⁇ and b respectively in Figure 2. This ratio was also observed when the two aliphatic peaks were integrated separately.
  • the ⁇ NMR spectra using a delay time of one second had integrals C 7 ,, C 66 , and C a , defined, such that the integration of the peak at 7.1 ppm included all the aromatic protons of the copolymer as well as the o &p protons of aPS.
  • integration of the aliphatic region C al in the spectrum of the inte ⁇ olymers included aliphatic protons from both the aPS and the inte ⁇ olymer with no clear baseline resolved signal from either polymer.
  • s c and e c were styrene and ethylene proton fractions in the inte ⁇ olymer, respectively, and S c and E were mole fractions of styrene monomer and ethylene monomer in the inte ⁇ olymer, respectively.
  • the total styrene content was also determined by quantitative Fourier Transform
  • FTIR Infrared spectroscopy
  • ESI 1 The inte ⁇ olymer was prepared in a 400 gallon (1514L) agitated semi- continuous batch reactor.
  • the reaction mixture consisted of approximately 250 gallons (946L) of a solvent comprising a mixture of cyclohexane (85 wt%) & isopentane (15wt%), and styrene.
  • solvent, styrene and ethylene Prior to addition, solvent, styrene and ethylene were purified to remove water and oxygen. The inhibitor in the styrene was also removed. Inerts were removed by purging the vessel with ethylene. The vessel was then pressure controlled to a set point with ethylene. Hydrogen was added to control molecular weight.
  • Temperature in the vessel was controlled to set-point by varying the jacket water temperature on the vessel. Prior to polymerization, the vessel was heated to the desired run temperature and the catalyst components : Titanium: (N-l,l-dimethyl- ethyl)dimethyl(l-(l ,2,3,4,5-eta)-2,3.4.5-tetramethyl- 2,4-cyclopentadien-l- yl)silanaminato))(2-)N)-dimethyl, CAS# 135072-62-7.
  • Tris(pentafluorophenyl)boron, CAS# 001109-15-5, Modified methylaluminoxane Type 3A, CAS# 146905-79-5, were flow controlled, on a mole ratio basis of 1/3/5 respectively, combined and added to the vessel.
  • the polymerization was allowed to proceed with ethylene supplied to the reactor as required to maintain vessel pressure. Hydrogen was added to the headspace of the reactor to maintain a mole ratio with respect to the ethylene concentration.
  • the catalyst flow was stopped, ethylene was removed from the reactor, 1000 ppm of Irganox ,M 1010 anti-oxidant was then added to the solution and the polymer was isolated from the solution. The resulting polymer was isolated from solution by use of a devolatilizing extruder.
  • the process conditions used to prepare ESI 1 were summarized in Table 1 and its properties were summarized in Table 2.
  • ESI #'s 2 - 4 were substantially random ethylene/styrene inte ⁇ olymers prepared using the constrained geometry catalyst, (t-butylamido)dimethyl(tetramethyl- cyclopenta-dienyl)silane-titanium (II) 1,3-pentadiene and the following co-catalyst and polymerization procedures.
  • the solution began to turn milky white.
  • the flask was equipped with a 6" Vigreux column topped with a distillation apparatus and the mixture was heated (140 °C external wall temperature).
  • a mixture of ether and methylcyclohexane was distilled from the flask.
  • the two-phase solution was now only slightly hazy.
  • the mixture was allowed to cool to room temperature, and the contents were placed in a 4 L separatory funnel.
  • the aqueous layer was removed and discarded, and the organic layer was washed twice with H 2 O and the aqueous layers again discarded.
  • the H 2 O saturated methylcyclohexane solutions were measured to contain 0.48 wt percent diethyl ether (Et 2 O).
  • the solution (600 mL) was transferred into a 1 L flask, sparged thoroughly with nitrogen, and transferred into the drybox.
  • the solution was passed through a column (1" diameter, 6" height) containing 13X molecular sieves. This reduced the level of Et 2 O from 0.48 wt percent to 0.28 wt percent.
  • the material was then stirred over fresh 13X sieves (20 g) for four hours.
  • the Et 2 O level was then measured to be 0.19 wt percent.
  • the mixture was then stirred overnight, resulting in a further reduction in Et 2 O level to approximately 40 ppm.
  • the mixture was filtered using a funnel equipped with a glass frit having a pore size of 10- 15 ⁇ m to give a clear solution (the molecular sieves were rinsed with additional dry methylcyclohexane).
  • the concentration was measured by gravimetric analysis yielding a value of 16.7 wt percent.
  • Polymerization ESI #'s 2 - 4 were prepared in a 6 gallon (22.7 L). oil jacketed, Autoclave continuously stirred tank reactor (CSTR). A magnetically coupled agitator with Lightning A-320 impellers provided the mixing. The reactor ran liquid full at 475 psig (3,275 kPa). Process flow was in at the bottom and out of the top. A heat transfer oil was circulated through the jacket of the reactor to remove some of the heat of reaction. At the exit of the reactor was a micromotion flow meter that measured flow and solution density. All lines on the exit of the reactor were traced with 50 psi (344.7 kPa) steam and insulated.
  • Toluene solvent was supplied to the reactor at 30 psig (207 kPa).
  • the feed to the reactor was measured by a Micro-Motion mass flow meter.
  • a variable speed diaphragm pump controlled the feed rate.
  • a side stream was taken to provide flush flows for the catalyst injection line (1 lb/hr (0.45 kg/hr)) and the reactor agitator (0.75 lb/hr ( 0.34 kg/ hr)). These flows were measured by differential pressure flow meters and controlled by manual adjustment of micro-flow needle valves.
  • Uninhibited styrene monomer was supplied to the reactor at 30 psig (207 kpa).
  • the feed to the reactor was measured by a Micro-Motion mass flow meter.
  • a variable speed diaphragm pump controlled the feed rate.
  • the styrene stream was mixed with the remaining solvent stream.
  • Ethylene was supplied to the reactor at 600 psig (4,137 kPa).
  • the ethylene stream was measured by a Micro-Motion mass flow meter just prior to the Research valve controlling flow.
  • a Brooks flow meter/controller was used to deliver hydrogen into the ethylene stream at the outlet of the ethylene control valve.
  • the ethylene/hydrogen mixture combines with the solvent/styrene stream at ambient temperature.
  • the temperature of the solvent/monomer as it enters the reactor was dropped to ⁇ 5 °C by an exchanger with -5°C glycol on the jacket.
  • This stream entered the bottom of the reactor.
  • the three component catalyst system and its solvent flush also entered the reactor at the bottom but through a different port than the monomer stream.
  • Preparation of the catalyst components took place in an inert atmosphere glove box.
  • the diluted components were put in nitrogen padded cylinders and charged to the catalyst run tanks in the process area. From these run tanks the catalyst was pressured up with piston pumps and the flow was measured with Micro-Motion mass flow meters.
  • the stream was condensed with a glycol jacketed exchanger and entered the suction of a vacuum pump and was discharged to a glycol jacket solvent and styrene/ethylene separation vessel. Solvent and styrene were removed from the bottom of the vessel and ethylene from the top.
  • the ethylene stream was measured with a Micro-Motion mass flow meter and analyzed for composition. The measurement of vented ethylene plus a calculation of the dissolved gasses in the solvent/styrene stream were used to calculate the ethylene conversion.
  • the polymer separated in the devolatilizer was pumped out with a gear pump to a ZSK-30 devolatilizing vacuum extruder. The dry polymer exits the extruder as a single strand. This strand was cooled as it was pulled through a water bath. The excess water was blown from the strand with air and the strand was chopped into pellets with a strand chopper.
  • Catalyst A was (t-butylam ⁇ do)d ⁇ methN (II) 1 3-pentad ⁇ ene prepared as described in U S Patent # 5 556 928
  • Cocatalyst B was bis-hydrogenated tallow alkyl meth ⁇ lammomum tetrakis (pentafluorophenyl)borate c a modified methylaluminoxane commercially available from Akzo Nobel as MMAO-3A (CAS# 146905-79-5) d SCCM w as standard cmVmin
  • the residue was slurried in 60 ml of mixed hexanes at about 20 °C for approximately 16 hours. The mixture was cooled to - 25 °C for 1 h. The solids were collected on a glass frit by vacuum filtration and dried under reduced pressure. The dried solid was placed in a glass fiber thimble and solid extracted continuously with hexanes using a soxhlet extractor. After 6 h a crystalline solid was observed in the boiling pot. The mixture was cooled to about -20 °C, isolated by filtration from the cold mixture and dried under reduced pressure to give 1.62 g of a dark crystalline solid. The filtrate was discarded. The solids in the extractor were stirred and the extraction continued with an additional quantity of mixed hexanes to give an additional 0.46 gm of the desired product as a dark crystalline solid.
  • An Ingersoll-Dresser twin screw pump provided the mixing.
  • the reactor ran liquid full at 475 psig (3,275 kPa) with a residence time of approximately 25 minutes.
  • Raw materials and catalyst/cocatalyst flows were fed into the suction of the twin screw pump through injectors and Kenics static mixers.
  • the twin screw pump discharged into a 2" diameter line which supplied two Chemineer-Kenics 10-68 Type BEM Multi- Tube heat exchangers in series.
  • the tubes of these exchangers contained twisted tapes to increase heat transfer.
  • loop flow returned through the injectors and static mixers to the suction of the pump.
  • Heat transfer oil was circulated through the exchangers' jacket to control the loop temperature probe located just prior to the first exchanger.
  • the exit stream of the loop reactor was taken off between the two exchangers.
  • the flow and solution density of the exit stream was measured by a MicroMotion.
  • Solvent feed to the reactor was supplied by two different sources.
  • a fresh stream of toluene from an 8480-S-E Pulsafeeder diaphragm pump with rates measured by a MicroMotion flowmeter was used to provide flush flow for the reactor seals (20 lb/hr (9.1 kg/hr).
  • Recycle solvent was mixed with uninhibited styrene monomer on the suction side of five 8480-5-E Pulsafeeder diaphragm pumps in parallel. These five Pulsafeeder pumps supplied solvent and styrene to the reactor at 650 psig (4,583 kPa).
  • Fresh styrene flow was measured by a MicroMotion flowmeter, and total recycle solvent/styrene flow was measured by a separate MicroMotion flowmeter.
  • Ethylene was supplied to the reactor at 687 psig (4,838 kPa).
  • the ethylene stream was measured by a Micro-Motion mass flowmeter.
  • a Brooks flowmeter/controller was used to deliver hydrogen into the ethylene stream at the outlet of the ethylene control valve.
  • the ethylene/hydrogen mixture combined with the solvent/styrene stream at ambient temperature. The temperature of the entire feed stream as it entered the reactor loop was lowered to 2°C by an exchanger with -10°C glycol on the jacket.
  • Preparation of the three catalyst components took place in three separate tanks: fresh solvent and concentrated catalyst/cocatalyst premix were added and mixed into their respective run tanks and fed into the reactor via variable speed 680-S-AEN7 Pulsafeeder diaphragm pumps.
  • the three component catalyst system entered the reactor loop through an injector and static mixer into the suction side of the twin screw pump.
  • the raw material feed stream was also fed into the reactor loop through an injector and static mixer downstream of the catalyst injection point but upstream of the twin screw pump suction.
  • Polymerization was stopped with the addition of catalyst kill (water mixed with solvent) into the reactor product line after the Micro Motion flowmeter measuring the solution density.
  • a static mixer in the line provided dispersion of the catalyst kill and additives in the reactor effluent stream.
  • This stream next entered post reactor heaters that provided additional energy for the solvent removal flash. This flash occurred as the effluent exited the post reactor heater and the pressure was dropped from 475 psig (3,275 kPa) down to 450 mmHg (60 kPa) of absolute pressure at the reactor pressure control valve.
  • This flashed polymer entered the first of two hot oil jacketed devolatilizers.
  • the volatiles flashing from the first devolatizer were condensed with a glycol jacketed exchanger, passed through the suction of a vacuum pump, and were discharged to the solvent and styrene/ethylene separation vessel. Solvent and styrene were removed from the bottom of this vessel as recycle solvent while ethylene exhausted from the top.
  • the ethylene stream was measured with a MicroMotion mass flowmeter. The measurement of vented ethylene plus a calculation of the dissolved gases in the solvent/styrene stream were used to calculate the ethylene conversion.
  • the polymer and remaining solvent separated in the devolatilizer was pumped with a gear pump to a second devolatizer.
  • the pressure in the second devolatizer was operated at 5 mm Hg (0.7 kPa) absolute pressure to flash the remaining solvent.
  • This solvent was condensed in a glycol heat exchanger, pumped through another vacuum pump, and exported to a waste tank for disposal.
  • the dry polymer ( ⁇ 1000 ppm total volatiles) was pumped with a gear pump to an underwater pelletizer with 6-hole die, pelletized, spin-dried, and collected in 1000 lb boxes.
  • Test parts and characterization data for the inte ⁇ olymers and their blends were generated according to the following procedures:
  • a Dupont DSC-2920 was used to measure the thermal transition temperatures and heat of transition for the inte ⁇ olymers. In order to eliminate previous thermal history, samples were first heated to 200°C. Heating and cooling curves were recorded at 10°C/min. Melting (from second heat) and crystallization temperatures were recorded from the peak temperatures of the endotherm and exotherm, respectively.
  • the initial static force was 120 gm with 2 gm of autotension sensitivity.
  • the static force was stipulated to be greater than the dynamic force by 9percent with a minimum static force of 2 gm.
  • Autostrain was used with a maximum applied strain of 2%, a minimum allowed force of 2 gm, a maximum allowed force of 200 gm, and a 20 percent strain adjustment.
  • Plots of the storage modulus of each of these extrudates showed an increase in storage modulus with increasing shear rate of extrusion. This increase was evident from 4.6 s "1 to 46 s " '. Samples from 100-464 s "1 showed similar behavior and high moduli. This was indicative of a significant change in microstructure of these resins upon extrusion as shown in Figure 1 :
  • Films were prepared by standard methods using a 1.25 inch Killion extruder extruder with a 12/6/6 24:1 L/D screw operating at a melt temperature of about 415 °F with a 3" in diameter die and a 40 mil die gap. In all cases the shear rates used to fabricate the films were in the range of 50 - 100 sec " '.
  • the extrusion conditions for the various samples were summarized in Table 8.
  • Zone #2 set Pt . °F (°C) 370 370 325
  • Zone #3 set Pt . °F (°C) 380 380 351
  • a blend of 70 weight percent of a substantially random inte ⁇ olymer (ESI # 5) and 30 weight percent of a styrene acrylonitrile copolymer was fabricated into cast film and a compression molded plaque. Pellets of each blend component were tumble blended, and poured into the hopper of a 2 inch diameter, Killion extruder with a 30:1 L:D ratio screw. Fabricated sheet was formed by extrusion through -a 14 inch wide, coat hanger type flat die with a 15 mil (.015 in.) die gap. Film was collected on a polished roll stack and haul-off unit at a rate of approximately 10 lb./hr. Shear rate was estimated to be 100-200 /sec. The results of the Tg and elastic modulus testing as a function of temperature were summarized in Table 10.
  • Examples 2-5 show that the individual blend components were mutually immiscible as demonstrated by the presence of a discernible Tg of the ethylene styrene inte ⁇ olymer component under high and low shear rate melt processing conditions.
  • the Examples also demonstrate the enhancement in modulus for fabricated articles prepared under high shear rate conditions (i.e. the films in this case) as compared to samples prepared under low shear rate conditions (i.e. the plaques in this case). All Examples meet the criterion that, at temperatures at least 20°C in excess of the blend Tg (DSC), the Elastic modulus of the article prepared under high shear rate conditions was at least twice, preferably three times and more preferably ten times that of the article prepared under low shear rate conditions.

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EP99958674A 1998-11-06 1999-10-26 Gegenstände hergestellt aus zusammensetzungen von interpolymeren auf basis von alpha-olefinischen und vinyl- oder vinylidenaromatischen und/oder gehinderten aliphatischen oder cycloaliphatischen vinylischen oder vinylidenischen monomeren Withdrawn EP1126969A1 (de)

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US20040101689A1 (en) 2002-11-26 2004-05-27 Ludovic Valette Hardener composition for epoxy resins
US7855316B2 (en) * 2002-12-20 2010-12-21 Kimberly-Clark Worldwide, Inc. Preferentially stretchable laminates with perforated layers
CN101062601B (zh) * 2006-04-28 2010-11-24 财团法人工业技术研究院 阻气结构
US8993681B2 (en) 2011-07-14 2015-03-31 Exxonmobil Research And Engineering Company Dendritic ethylene polymers and processes for making
CN103724782A (zh) * 2013-12-10 2014-04-16 芜湖佳诚电子科技有限公司 一种综合性良好的无卤阻燃聚乙烯电缆料及其制备方法
CN105504739A (zh) * 2014-09-24 2016-04-20 沈阳宏伟塑料制品有限公司 一种无卤阻燃abs/pc合金树脂及其制备方法
JP7288505B2 (ja) 2018-10-30 2023-06-07 チャイナ ペトロレウム アンド ケミカル コーポレーション 水添スチレン・共役ジエン共重合体及びその発泡材料並びに使用
CN109627745A (zh) * 2018-12-27 2019-04-16 武汉德航联合科技有限公司 一种用于跑道的填充颗粒及其制备方法
CN114736511B (zh) * 2022-04-29 2023-11-21 浙江新力新材料股份有限公司 一种低模垢耐高温有卤阻燃增强高温尼龙材料及其制备方法

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CA2198136A1 (en) * 1994-09-02 1996-03-14 Dow Global Technologies Inc. Thermoset elastomers
KR20000035968A (ko) * 1996-09-04 2000-06-26 그레이스 스티븐 에스. 바닥, 벽 또는 천장 커버링재
US5739200A (en) * 1996-12-17 1998-04-14 The Dow Chemical Company Plasticizied α-olefin/vinylidene aromatic monomer of hindered aliphatic or cycloaliphatic vinylidene monomer interpolymers
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