CN101151325A

CN101151325A - Organosiloxane compositions

Info

Publication number: CN101151325A
Application number: CNA2006800101858A
Authority: CN
Inventors: G·拉维纳罗; I·梅顿; J·维利米; R·德雷克; T·迪特梅尔曼
Original assignee: Dow Corning Corp
Current assignee: Dow Silicones Corp
Priority date: 2005-04-06
Filing date: 2006-04-03
Publication date: 2008-03-26
Anticipated expiration: 2026-04-03
Also published as: CN101151324B; CN101146856A; CN101146868A; CN101151329B; CN101151325B; CN101151324A; CN101146868B; CN101151329A; CN101146856B; GB0506939D0

Abstract

A coatable sealant composition comprising a moisture curable composition capable of cure to an elastomeric body comprising (a) an extended polymer comprising (i) an organosiloxane polymer of the formula X-A-X<1> where X and X<1> are independently selected from silyl groups containing hydroxyl or hydrolysable groups selected from -SiOH3, -(R<a>)SiOH2, -(R<a>)2SiOH, -R<a>Si(OR)2, -Si(OR)3, -R<a>2SiOR and -R<a> 2S.

Description

Organosiloxane compositions

[0001] the present invention relates in the presence of thinner one or more and comprise to small part and contain the polymkeric substance of polymer chain of organic based polysiloxane or the chain extension of oligopolymer, with the polymkeric substance of producing dilution and the composition that contains resulting polymers.

[0002] rheological property of uncured polymkeric substance mainly is the function of its viscosity.The viscosity of uncured polymkeric substance is directly related with the length (being normally defined the polymerization degree (dp)) of the molecular weight of this polymkeric substance and polymer chain, and usually, the viscosity of polymkeric substance is low more, and the extruded velocity of uncured composition that then contains this polymkeric substance is high more.The composition that the viscosity of uncured polymkeric substance is still mixed this polymkeric substance is the major influence factors of the several physical performance of encapsulant composition for example, when with this composition of after fixing.

[0003] it is known being cured as elastomerics solid organosiloxane compositions, and can produce this composition, at room temperature, in the presence of moisture or applying under the heat situation and solidify.Typically, have the poly-diorganosiloxane based polyalcohol of reactive terminal group and suitable silane (or siloxanes) based cross-linker by in the presence of one or more fillers and curing catalysts, mixing, acquisition in the presence of moisture, these compositions of solidified at room temperature.Typically, these compositions are to be exposed to atmospheric moisture following time curable single part composition forms or in curable two portions composition forms preparation when mixing under the indoor conditions in room temperature.

[0004] important use of above-described curable composition is its purposes as sealing agent.In being used as sealing agent, importantly composition has the performance of blend, the performance of described blend made before solidifying it can be applied to junction between the substrate surface that it can operate with paste form within it, so that the slick material that comes to the surface to be provided, the described slick material that comes to the surface will remain on the position of its distribution, be solidified into up to it and adhere to the lip-deep elastomerics of adjacent base.Typically, the design encapsulant composition enough solidifies apace, and so that sufficient sealing to be provided in a few hours, but speed makes the material that is applied in to be processed into required structure with instrument soon after applying.Usually prepare gained solidified sealing agent, to have intensity and the elasticity that is suitable for related specific connection.

[0005] mineral filler is incorporated into usually require in the elastic composition of the polymkeric substance that contains organic based polysiloxane to obtain useful to tear, the modulus properties under hardness, elongation and 100% elongation.The rheological property of uncured elastomer depends on performance (in filler is present in composition time) for example concentration and the structure of filler, and the interaction degree of polyalcohol-filling material and the viscosity of polymkeric substance of filler.Usually, contain uncured organopolysiloxane and randomly contain the viscosity of composition of filler low more, the extruded velocity of then uncured composition is high more.The result requires the application of high extruded velocity, for example uncured sealing agent (it is in use manually extruded with sealant gun or analogue usually) typically needs to use low viscous polymkeric substance (for example under 25 ℃,＜100000mPa), to guarantee suitable composition extruded velocity for manually finally using.

[0006] physicals of gained cured compositions comprises elongation and the modulus under 100% elongation, be in the necessary building and transportation industry to the demand of sealing agent with low modulus and high elongation rate therein, these two performances are for being even more important the sealing agent that uses in connecting that for example expands.

[0007] therefore, although the molecular weight of known increase polymkeric substance will improve some physicals of sealing agent, typically, the peak viscosity that uses in present prescription is not more than about 150000mPa.s in practice under 25 ℃.Reach 1,000 although discussed in the prior art 25 ℃ of following viscosity, the organopolysiloxane polymkeric substance of 000mPa.s uses the polymkeric substance with this viscosity can not control in practice and economically.Therefore, although the molecular weight of known increase polymkeric substance will improve some performance of sealing agent, typically, the peak viscosity that uses in present prescription is not more than about 150000mPa.s in practice under 25 ℃.

[0008] increasing the employed a kind of method of polymkeric substance chain length is " chain extension ", wherein after finishing initial polyreaction, in order further to increase the dp and the molecular weight of polymkeric substance, will have reactive dual functional intermediate to polymer terminal group and join in the resulting polymers.In sealing agent is used, the chainextender molecule can with polymer reaction, meanwhile, solidify said composition by interacting with linking agent, wherein need carefully to select chainextender, so that the speed of response between polymkeric substance and the chainextender is faster than the reaction between polymkeric substance and the linking agent.Under the situation that the sealing agent class is used, its advantage is that the viscosity of the uncured composition of maintenance is being suitable for using sealant gun or analogue manually to apply composition levels, and after applying encapsulant composition and being incorporated in the air, effective dp and molecular weight increase take place during cure stage.

[0009] suitable chainextender is considered to generate with the polymer end radical reaction polymkeric substance of increment.Although typically this can involve any suitable chemistry, the chain extension of this base polymer involves one of two kinds of reaction schemes usually, i.e. addition and condensation chain extension.

[0010] in US 3341486, in conjunction with silanol stopped polysiloxane and two and three aminooxy silane or siloxanes, to be provided at the composition that atmospheric moisture exists following not only chain extension but also crosslinked room temperature vulcanizable (RTV).In US4071498, mix and to contain monovalent hydrocarbon or halohydrocarbon residue and each molecule and on average have at least one and be bonded on the Si-siloxanes and methyl ethylene two (ε-Ji Neixianan base) silane of OH base.Isolating gained organopolysiloxane has compared with the high molecular weight of organopolysiloxane of beginning and contains methyl vinyl siloxane unit.US4614760 discloses a kind of single part silicone elastomer composition that flows or easily extrude, and it prepares by the organo-peroxide that mixes hydroxy-end capped poly-diorganosiloxane, has the dual functional silane of two amide group and be suitable for sulphurated siliastic.After applying, composition is exposed under the moisture, with the activation chain extending reaction.US5914382 discloses and has made α, the method for poly-(diorganosiloxane) chain extension of Ω-dihydroxyl, and this method comprises makes low-molecular-weight α, Ω-dihydroxyl poly-(diorganosiloxane) and phosphoric acid ester and/or H ₃PO ₄Reaction.EP0909778 disclose by add can chain extension again can the silanization organopolysiloxane nitrogenous silylating reagent and nitrogenous silylating reagent that can chain extension, the organopolysiloxane that is had the hydroxyl of at least one and silicon bonding by each polymer molecule prepares the organopolysiloxane of chain extension, thereby produces the organopolysiloxane of chain extension.US2004/0122199 discloses a kind of organopolysiloxane composition, it comprise two end groups by with the hydroxy-end capped organopolysiloxane of silicon bonding, at least a dialkyl amido methyl alkyl dialkoxy silicane chainextender and/or its partial hydrolystate, (d) at least a isocyanuric acid ester deactivator, softening agent randomly, silane crosslinker and/or one or more quicken the catalyzer of the Si-OH radical reaction on silane crosslinker and the polymkeric substance.EP0651022 discloses curable organic radical siloxane composition, and it comprises the organopolysiloxane polymkeric substance with vinyl ends, contains the silane with two Si-H bases or chainextender, linking agent and the platinum based catalyst of short chain siloxanes.

[0011]] in the prescription of the siloxanes composition that is used as the self-vulcanizing sealing agent, conventional practice is, other by blend in the polymkeric substance of described or each increment compound (hereinafter referred to as " processing aid ") and/or plasticized compound (hereinafter referred to as " softening agent ") and pre-preparation and the composition becomes to assign to comprise to play the additive of " increment " and/or " plasticising " siloxane sealant composition effect.

[0012] uses processing aid (being also referred to as extender or extender plasticizer sometimes), dilute encapsulant composition and do not having to make sealing agent have more competitiveness economically basically under the performance situation of remarkable negative impact sealant dispensing basically.In siloxane sealant composition, introduce one or more processing aids and not only reduce the total cost of product, and can influence the performance of the uncured and/or solidified silicone encapsulants of gained.Adding processing aid can influence rheological, binding property and the transparency properties of silicone encapsulants to a certain extent energetically, and the elongation at break that can cause cured product increases and hardness descends, and these two kinds of performances can significantly improve the life-span of solidified sealing agent, and condition is that processing aid does not lose by for example evaporating or ooze out from the solidified sealing agent.

[0013] adds softening agent (being called primary plasticizer in other cases) in polymer composition, in final polymer-based carbon product, to provide characteristic, with flexibility and the toughness that increases final polymer composition.This realizes by the second-order transition temperature (Tg) that reduces the cured polymer composition usually, so under the situation of for example sealing agent, when applying sealing agent to substrate and when solidifying, usually improve the elasticity of sealing agent, elastic raising has locomotivity conversely in the connection that forms by silicone encapsulants, and the probability of the bonding point that forms between sealing agent and substrate fracture significantly descends.Typically use softening agent also to reduce the modulus of sealant dispensing.Softening agent can reduce population unit's cost of sealing agent, but this is not the purposes that it is mainly planned, and some softening agent are expensive really, and may increase the unit cost of the sealant dispensing that they use within it.Plasticizer volatility tends to usually less than processing aid, and typically is incorporated in the polymer composition with liquid or low melting point solid (it will become compatibility liquid in the course of processing) form.Typically, for the siloxanes composition, softening agent is not have reactive short chain siloxanes, for example has the polydimethylsiloxane of three organic radical siloxy-end groups, and wherein organic substituent for example is the combination of methyl, vinyl or phenyl or these groups.The common viscosity of this polydimethylsiloxane is about 5 to about 100,000mPa.s.Can use compatible organic softening agent in addition, example comprises: the phthalic acid dialkyl, wherein alkyl can be straight chain and/or side chain and contain 6-20 carbon atom, for example: dioctyl phthalate (DOP), dihexyl, two the ninth of the ten Heavenly Stems ester, didecyl ester, two allantois acid esters and other phthalic ester; Adipic acid ester, azelate, oleic acid ester and sebate; Polyvalent alcohol, for example ethylene glycol and derivative thereof; Organophosphate, for example Tritolyl Phosphate and/or triphenylphosphate; Viscotrol C; Tung oil; The ester of lipid acid and/or lipid acid.

[0014] processing aid both need fully with composition in rest part compatible, and maintain under the temperature (for example room temperature) under it non-volatile as far as possible at gained solidified sealing agent.Yet, find that although in for some time in storage process, when applying sealing agent and at least, the processing aid of some propositions is effective, about its purposes, have the problem of several known.These problems comprise:

(i) UV stability, when long-term exposure in UV-light following time, contain the solidified sealing agent variable color of processing aid;

(ii) poor with the consistency of polymer composition (for example encapsulant composition), thus along with time lapse, cause them from sealing agent, to ooze out, and this is the negative impact cured product, for example the physics of sealing agent and aesthstic performance and life-span; With

Substrate around (iii) polluting, wherein processing aid is exuded to from composition in the described substrate.

[0015] for example the method in the encapsulant composition is by the composition that only is mixed together all pre-preparation with suitable consumption and interpolation in proper order for the polymer composition that processing aid and/or softening agent are incorporated into that uses in industry, and for example polymkeric substance, linking agent, catalyzer, filler and described or each processing aid and/or softening agent are formed.With organic radical polymer phase ratio, the consistency of other composition is remarkable bigger problem in organic processing aid and/or softening agent and the silica alkyl polymer composition, the siloxane polymer that processing aid and/or softening agent are introduced in it tends to become high heavy-gravity polymkeric substance, with opposite with the organic radical polymkeric substance, but the chemical property relative consistency of silica alkyl polymer has remarkable influence.Compatibility determines to be incorporated into processing aid and/or the plasticizer dosage in the polymer composition effectively.Typically, this processing aid that especially causes introducing remarkable lower aq with comparing of may expecting is in composition, this be because processing aid not fully well physics be not mixed in the polymer composition, especially with composition in the preformed polymkeric substance that is generally largest component except filler less than physical mixed fully well.Softening agent and the processing aid compatibility problem in silicone polymers combination is since being known this industry since introducing organic processing aid always, known to the inventor, up to the organic radical processing aid of the present invention by proposing to accelerate, just solved this problem, wherein each organic radical processing aid can't physically be mixed in the encapsulant composition with the consumption of about 30wt% of processing aid and polymkeric substance total amount.

[0016] in history, do not have reactive siloxanes for example the end capped poly-diorganosiloxane of trialkylsilkl (for example end capped polydimethylsiloxane of trimethyl silyl (PDMS)) at first in the siloxanes sealing agent as processing aid and/or softening agent, this is because they chemically similar, and have good consistency.

[0017] wide in range various organic compound and composition reduce siloxane sealant composition as processing aid cost has been proposed.These materials are categorized as two groups usually: high volatile volatile processing aid and low volatility processing aid.

[0018] composition that contains the high volatile volatile processing aid can contain for example toluene or dimethylbenzene.High-volatile these compounds cause many shortcomings in sealant dispensing, comprising high shrinking percentage (because high VOLUME LOSS that solvent evaporation causes), combustibility, VOC (volatile organic content), unwanted component mark, health and safety problem etc.

[0019] select low volatility processing aid (being sometimes referred to as the processing aid of higher molecular weight), it is intended that has the consistency good with polymkeric substance in encapsulant composition.The gained sealing agent is called as " sealing agent of increment " and demonstrates usually than the much bigger performance of sealing agent acceptance of diluting.The processing aid of these higher molecular weights can completely or partially substitute the PDMS softening agent in the prescription.

[0020] low-molecular-weight polyisobutene (PIB) has been proposed as processing aid in DE2364856 and DE3217516.Yet because consistency is limited, the maximum scope that therefore can join the PIB processing aid in the acetoxyl group silicone encapsulants prescription typically is 25-30wt%.Higher addition causes that processing aid is exuded on the surface, and makes the solidified encapsulant surface be clamminess.Phosphoric acid ester is disclosed in DE2802170 and DE2653499 as the potential processing aid.

[0021] mineral oil fractions (for example isoparaffin) and polyoxyethylene alkylphenyl for example heavy alkylate (after the refinery distilled oil residual alkylating aromatic material) also be suggested as processing aid.These and other organic compound and mixture as the processing aid material proposition of siloxane sealant composition are disclosed in following issued patents:

GB2041955 discloses dodecylbenzene and the purposes of other alkylaromatic hydrocarbon as organic processing aid.GB2012789 discloses the purposes of trioctyl phosphate as the part surrogate of PDMS.DE3342026 and DE3342027 disclose the purposes of the ester of mono carboxylic acid of aliphatic series as processing aid.EP0043501 has proposed for example purposes of hexanaphthene, isohexane and isooctadecane of 0.2 to 15% side chain of encapsulant composition weight and/or cyclic alkane.EP0801101 discloses the purposes of paraffin oils (molecular weight＞180) in conjunction with one or more Alkylaromatics.EP0842974 discloses the purposes of alkyl cyclohexane class (molecular weight＞220).WO99/66012 and WO00/27910 disclose and have contained one or more aliphatic liquid polymerses and oil, the organic oil, alkyl phosphate, polyalkylene glycol of petroleum derivation, poly-(propylene oxide), hydroxyethylation alkylphenol, dithio dialkyl phosphonic acid ester, poly-(iso-butylene), poly-(alpha-olefin) and composition thereof oil resistant silicone composition as processing aid.

[0022] in recent years, the industrial alkane that uses further is as processing aid.EP0885921 discloses the purposes of the paraffins mixture that contains 60-80% paraffinic hydrocarbons and 20-40% alicyclic hydrocarbon and maximum 1% aromatic carbon atom.EP0807667 discloses similar processing aid, its all or part of alkane oil that contains 36-40% cyclic alkane oil and 58-64% acyclic alkanes oil that comprises.WO99/65979 discloses grease-proof encapsulant composition, and it especially comprises the softening agent that can contain paraffinic hydrocarbons or alicyclic ring hydrocarbon ils and composition thereof.EP1481038 disclose contain greater than the 60wt% alicyclic hydrocarbon, many ring greases of 20wt% cyclic hydrocarbon and ASTM D-86 boiling point are the purposes of 235 ℃-400 ℃ hydrocarbon fluid at least.EP1252252 discloses the use processing aid, and described processing aid comprises based on 100 weight part hydrocarbon having greater than 40 weight part cyclic alkane with less than the hydrocarbon fluid of 60 weight part monocycle alkane.EP1368426 discloses the encapsulant composition that uses with alkyd paint, and it contains the liquid alkane " processing aid " that preferably contains greater than the 40wt% cyclic alkane.

[0023] as mentioned above, a root problem that uses extender material be they lack with uncured siloxane sealant composition in the consistency of each component, thereby typically cause being separated in the storage process and in interested whole temperature ranges, from the solidified sealing agent, ooze out.Usually find, after solidifying, the sealing agent that contains processing aid and/or softening agent can ooze out described processing aid and/or softening agent, thereby causes the remarkable decline of solidified sealant lifetime, and this is a lower boiling especially general feature of processing aid for example＜100 ℃.Although preparation person is interested is to mix the processing aid of high capacity in its encapsulant composition, but the physical mixed processing aid material of advocating in all above-mentioned documents and other composition are hindered because of the consistency that especially lacks high-viscosity polymer, and wherein the thickness performance of polymeric constituent is that the processing aid that mixes large volume hinders to the physics in the encapsulant composition.Therefore usually find, can be incorporated into the combination that processing aid consumption in the encapsulant composition depends on employed processing aid or processing aid, typically between 20 to 40wt%.

[0024] although many organic processing aid potentializations set forth above, they all have problem usually.Although for example the alkylbenzene processes auxiliary agent has the performance combination that looks suitable, promptly high boiling point, with the good consistency of poly-diorganopolysiloxaneand polymeric matrix (thereby causing the solidified silicone encapsulants), low environmental influence, low vapour pressure well to good transparency (with so low contraction), to the positive influence (contraction of reduction) of rheological property.Yet when being exposed to artificial or natural climate following time, the sealing agent of alkylbenzene increment tends to yellowing quite apace.After long-term Weather, the sealing agent of these increments continues yellowing, and also loses its transparency.Adopt other processing aid, for example under the situation of phosphoric acid ester or polyisobutene, this problem can not occur.

[0025] in addition, have very that the polymkeric substance of high-polymerization degree can cause several favourable performances although in the siloxanes prescription, use, snappiness for example, but the viscosity of this polymkeric substance is so big usually (promptly, silicone rubber compounds), so that for for example filler, linking agent, processing aid and/or the softening agent blend of other composition, become uncontrollable fully, perhaps require the mixing roll of the expensive very high-shear of operation.Therefore since the industry midium or long term, need to develop the very high silica alkyl polymer of the easy introducing polymerization degree and avoid the method for the expensive equipment of needs in the composition simultaneously.

[0026] inventor has now developed a kind of chain extension astoundingly and has comprised the novel method that contains the polymkeric substance of organic based polysiloxane main chain to small part, this method is involved in the preparation of polymkeric substance, pass through chain extension, mix the thinner that comprises processing aid and/or softening agent, the compounding problem of avoiding the polymkeric substance of this viscosity to run into usually simultaneously.Compare with the material of prior art, new and favourable performance are provided for the product that contains this polymkeric substance by the polymkeric substance of the above this dilution that obtains.

[0027] according to the present invention, the method that contains organic based polysiloxane polymkeric substance of the chain extension of preparation dilution is provided, this method comprises the steps:

(a) in the presence of diluent materials, appropriate catalyst and optional end-capping reagent, make preformed polymkeric substance and can with the chainextender reaction of the end group reaction of this polymkeric substance, described chainextender is selected from:

(i) diethylamide base silane, diacetoxy silane, dichlorosilane, diamino silanes, (wherein each amino has one or two N-H key with respect to each nitrogen), dialkoxy silicane, diamide base silane, six organic radical disilazanes, two ketoximinosilanes;

(ii) the polymerization degree is that 2-25 and each molecule have at least two acetamidos or acetoxyl group or amino or alkoxyl group or amide group or the substituent polydialkysiloxane of ketoxime base,

(iii) alpha-aminoalkyl dialkoxy alkyl silane, wherein alkyl and alkoxyl group contain 1-6 carbon atom,

(iv) structure is ZMe ₂SiO (Me ₂SiO) _ySiMe ₂Z or ZMe ₂Si-Y-SiMe ₂The compound of Z, wherein Z is a heterocycle Si-N base, Y is selected from-(CR ₂) _m-or-C ₆H ₄-bivalent hydrocarbon radical, y be 0 or integer and m be that 2-6 (comprising end value) and R are univalence hydrocarbyls;

(v) two alkenyl silanes, two hydrogen silanes,

(vi) the polymerization degree is the polydialkysiloxane that 2-25 and each end group have at least one Si-alkene base key,

(vii) the polymerization degree is the polydialkysiloxane that 2-25 and each end group have at least one Si-H key; With

(b) optionally, this chain extension technology of quencher;

Wherein diluent materials is retained in the polymkeric substance that contains organic based polysiloxane of gained dilution basically.

[0028], provide a kind of polymkeric substance that contains organic based polysiloxane of chain extension of the dilution that can obtain by the method that comprises the steps according to the present invention:

(a) in the presence of diluent materials, appropriate catalyst and optional end-capping reagent, make the preformed polymkeric substance that contains organic based polysiloxane and can with the chainextender reaction of the end group reaction of described polymkeric substance, described chainextender is selected from:

(i) diethylamide base silane, diacetoxy silane, diamino silanes (wherein each amino has one or two N-H key with respect to each nitrogen), dialkoxy silicane, diamide base silane, six organic radical disilazanes, two ketoximinosilanes;

(v) two alkenyl silanes, two hydrogen silanes,

(b) optionally, this chain extension technology of quencher;

[0029] notion as used herein " contains, comprises " and uses on its most wide in range meaning, it be meant and include wording " comprising, " and " by ... form ".The plan that contains the polymkeric substance of organic radical siloxane refer to each molecule contain the unitary polymkeric substance of a plurality of organopolysiloxanes and plan be included in only contain basically in the polymer chain polymkeric substance of organic based polysiloxane group or wherein main chain in chain, contain organic based polysiloxane base and for example polymkeric substance of organic polymer group simultaneously.Except as otherwise noted, all given viscosity numbers are measured under 25 ℃ temperature.For the application's purpose, " replacement " is meant that the one or more hydrogen atoms in alkyl are replaced by another substituting group.This substituent example includes but not limited to: halogen atom, for example chlorine, fluorine, bromine and iodine; The group of halogen atom-containing, for example chloro methyl, perfluoro butyl, trifluoroethyl and nine fluorine hexyls; Sauerstoffatom; The group that contains Sauerstoffatom, for example (methyl) vinylformic acid and carboxyl; Nitrogen-atoms; The group of nitrogen atom, amido functional group for example, amide group functional group and cyano functional group; Sulphur atom; With the group of sulfur atom-containing, for example sulfydryl.

[0030] preferably, blended polymkeric substance parent material is miscible or miscible at least basically and more specifically miscible or miscible at least basically with the polymerisate of intermediate reaction product and final chain extension with it at first thinner and they.Term " miscible basically thinner " intend being included in the polymerization process with monomer and/or oligopolymer and/or reaction mixture fully or most of miscible thinner, therefore can be included in the low-melting solid that in reaction mixture, becomes compatibility liquid in the polymerization technique process.

[0031] in one embodiment of the invention, but preformed polymeric constituent used in the present invention is the polymkeric substance that contains polysiloxane that comprises at least two condensation groups, but most preferably the condensation group is terminal hydroxyl or hydrolyzable group.Preferably, the general formula of polymkeric substance is:

X ¹-A-X ²(1)

X wherein ¹And X ²Be independently selected from the silyl and the A that contain hydroxyl or hydrolysable group and be selected from polymkeric substance or copolymer molecule chain or the siloxanes/organic block copolymer chain that contains siloxanes.Hydroxyl and/or hydrolyzable substituent radicals X ¹Or X ²Example comprise-SiOH ₃,-(R ^a) SiOH ₂,-(R ^a) ₂SiOH ,-R ^aSi (OR ^b) ₂,-Si (OR ^b) ₃,-R ^a ₂SiOR ^bOr-R ^a ₂Si-R ^c-SiR ^d _p(OR ^b) _3-p, each R wherein ^aRepresent univalence hydrocarbyl independently, alkyl for example especially has the alkyl of 1-8 carbon atom, (and preferable methyl); Each R ^bAnd R ^dBase is alkyl or alkoxyl group independently, and alkyl wherein has maximum 6 carbon atoms suitably; R ^cBe bivalent hydrocarbon radical, it can be disconnected by one or more siloxanes spacers with maximum 6 Siliciumatoms; With the numerical value of p be 0,1 or 2.

[0032] or, X ¹And X ²Can comprise all and the group of suitable chain extension molecule experience addition class reaction that preferably, the reaction of addition class is a hydrosilylation reactions, and X ¹With X ²All contain silicon-hydrogen bond or contain the undersaturated organic group of 2-6 carbon atom, for example alkenyl, alkynyl, acrylate-based and/or alkyl acrylate ester group.Most preferably in this embodiment, X ¹And X ²Be alkenyl, preferred vinyl especially wherein.The X of small proportion (＜20%) ¹Base can comprise trialkylsilkl, wherein preferably methyl or ethyl of each alkyl.

[0033] example of suitable siloxanes A is to comprise those that gather the diorganosiloxane chain in formula (1).Therefore, group A preferably includes the siloxane unit of formula (2):

-(R ⁵ _sSiO _(4-s)/2)-(2)

Each R wherein ⁵Be organic group independently, for example have the alkyl of 1-18 carbon atom, have the alkyl of the replacement of 1-18 carbon atom, or have the-oxyl of maximum 18 carbon atoms, the mean value of a is 1-3, preferred 1.8-2.2.Preferably, R ⁵Be randomly by one or more halogen atoms for example the alkyl with 1-10 carbon atom and the s that replace of chlorine or fluorine be 0,1 or 2.Radicals R ⁵Specific examples comprise methyl, ethyl, propyl group, butyl, vinyl, cyclohexyl, phenyl, tolyl, the propyl group that is replaced by chlorine or fluorine, for example 3,3,3-trifluoro propyl, chloro-phenyl-, β-(perfluoro butyl) ethyl or chloro cyclohexyl.Suitably, at least some and preferred whole R basically ⁵Base is a methyl.

[0034] the group A in the compound of formula (1) can comprise any suitable siloxanes or siloxanes/organic molecule chain, condition is to make resulting polymers (according to the present invention, under the situation that does not have thinner) viscosity under 25 ℃ reaches 20,000,000mPa.s (promptly, nearly or even greater than the unit of 200,000 formulas (2)).In a preferred embodiment, for all chain units, A be straight chain organopolysiloxane molecular chain (that is, s=2).Preferable material has the poly-diorganosiloxane chain of general formula (3):

-(R ⁵ ₂SiO) _t-(3)

Each R wherein ⁵As defined above, and the numerical value of preferable methyl and t for reaching at least 200,000.Under the situation that does not have thinner, the viscosity of suitable polymers under 25 ℃ reaches 20,000,000mPa.s, but when preparing under the situation that has thinner, under 25 ℃, the order of magnitude of viscosity is generally 1000-100,000mPa.s, and this is because there is thinner in polymeric matrix.

Therefore [0035] the unitary polysiloxane that preferably contains formula (2) is to have as above X ¹And X ²Definition with the terminal hydroxy group of silicon bonding or use the poly-diorganosiloxane of the hydrolyzable organic end group with the silicon bonding of moisture.In structure (2), the poly-diorganosiloxane that contains this structural unit can be homopolymer or multipolymer.But the mixture with poly-diorganosiloxane of difference of condensation end group also is suitable.

[0036] under the situation of poly-diorganosiloxane multipolymer, polymer chain can comprise the block by the described cellular chain preparation of following formula (2), wherein two R ⁵Base:

Be alkyl (preferably all being methyl or ethyl)

Alkyl and phenyl

Alkyl and fluoro propyl group

Alkyl and vinyl

Alkyl and hydrogen base.

Typically, at least one block comprises wherein two R ⁵Base all is siloxane units of alkyl.

[0037] although A organopolysiloxane molecular chain preferably, but or A contains the segmented copolymer main chain of block that at least one formula (2) is described the siloxane groups of type, and the organic constituent that contains any suitable organic radical main polymer chain, for example the organic polymer main chain can comprise the polystyrene of polystyrene for example and/or replacement, for example poly-(alpha-methyl styrene), poly-(vinyl vinyl toluene), diolefine gather (to trimethyl silyl vinylbenzene) and poly-(to trimethyl silyl-alpha-methyl styrene).Other organic constituent that can be incorporated in the main polymer chain can comprise the end capped low polyphenylene of alkynes, the end capped aromatic polysulfones oligopolymer of vinyl benzyl, aromatic polyester, aromatic polyester base monomer, polyalkylene, urethane, aliphatic polyester, aliphatic polyamide and aromatic poly and analogue.

[0038] yet, in A most preferred organic radical polymer blocks may be polyoxy alkylidene be the basis block, described block typically with siloxanes by the hydrosilylation reactions bonding, introduce chainextender of the present invention afterwards.This polyoxy alkylidene block preferably includes with average formula (C _nH _2n-O-) _yThe expression by multiple oxygen base alkylidene unit (C _nH _2nThe oxygen base alkylidene group polymkeric substance of-main straight chain O-) formed, wherein n is that integer 2-4 (comprising end value) and y are at least 4 integer.The number-average molecular weight scope of each polyoxyalkylene polymers block can be about 300 to about 10,000.In addition, oxygen base alkylidene unit is not necessarily identical in whole polyoxy alkylidene monomers, and can be different unit.The polyoxy alkylidene block for example can be by oxygen base ethylidene unit (C ₂H ₄-O-), oxygen base propylidene unit (C ₃H ₆-O-) or oxygen base butylidene unit (C ₄H ₈-O-) or its mixture form.Preferably, the polyoxyalkylene polymers main chain is made up of oxygen base ethylidene or oxygen base propylidene unit basically.

[0039] other polyoxy alkylidene block can comprise for example unit of following structure:

-[-R ^e-O-(-R ^f-O-) _h-Pn-CR ^g ₂-Pn-O-(-R ^f-O-) _q-R ^e]-

Wherein Pn is 1,4-phenylene, each R ^eIdentical or different and for having the bivalent hydrocarbon radical of 2-8 carbon atom, each R ^fIdentical or different and be ethylidene or propylidene, each R ^gIdentical or different and be that hydrogen atom or methyl and each subscript h and q are that scope is the positive integer of 3-30.

[0040] can use the method according to this invention to prepare any suitable method of polymkeric substance.Thinner, chainextender and catalyzer can add in the polymkeric substance according to any order.In preferred a selection, initial mixed chain extender and catalyzer and polymkeric substance, and when the viscosity that detects reaction mixture increases, then adopt the thinner that adds to begin chain extending reaction.Continue to mix, up to the time point place if necessary in quencher/catalyst neutralisation, the viscosity of products therefrom becomes constant or along with the time begins to descend.

[0041] can use the molecular weight of end-capping reagent telomerized polymer and/or increase functional group.End-capping reagent is that the mode and the conduct of the reactivity/polymkeric substance chain length of controlling polymers introduced functional group to the interior mode of resulting polymers.Suitable end-capping reagent comprises that number-average molecular weight scope for example is the polysiloxane more than 160, especially has the polydimethylsiloxane of one or more functional groups such as hydroxyl, vinyl or hydrogen.The functional group that uses end-capping reagent to introduce is included in the alternative end group on the polymkeric substance, for example with the hydrogen base of silicon bonding, alkenyl, hydrolysable group for example hydroxyl, alkoxyl group and acetoxyl group.Can use end-capping reagent to introduce and optionally subsequently the hydrolysable group of reaction is comprised-SiOH ₃,-(R ^a) SiOH ₂,-(R ^a) ₂SiOH ,-R ^aSi (OR ^b) ₂,-Si (OR ^b) ₃,-R ^a ₂SiOR ^bOr-R ^a ₂Si-R ^c-SiR ^d _p(OR ^b) _3-p, each R wherein ^a, R ^b, R ^d, R ^c, p as previously mentioned.Water also serves as end-capping reagent, and it introduces hydroxy functional group.

[0042] preferably, described or each thinner is one or more processing aids and/or softening agent.Usually, do not plan to be chemically bonded on monomer/oligomer parent material or intermediate or the final polymerisate according to thinner used in the present invention.Yet, can be between polymeric reaction products and thinner, preferably, at thinner with along some chemical bonding and/or reversible interaction take place between the substituting group of main polymer chain rather than polymer terminal group, so that between polymkeric substance and thinner, form cross-linked network, thereby when in encapsulant composition for example, using, provide the polymer product that may not cause the thinner loss so and/or shrink.For the sake of clarity, the term in this paragraph " chemical bonding " is intended finger-type and is become covalent linkage or similar chemical bond, rather than chemical interaction only, for example hydrogen bonding etc.

[0043] can use any suitable processing aid and/or the combination of softening agent or processing aid and/or softening agent.These comprise following independent each of enumerating or with other combine:

The end capped polydialkysiloxane of trialkylsilkl, wherein each alkyl can be identical or different, and comprise 1-6 carbon atom, but preferable methyl, preferably its viscosity is 100-100 under 25 ℃, 000mPa.s, be 1000-60 most preferably 25 ℃ of following viscosity, 000mPa.s;

Polyisobutene (PIB),

Phosphoric acid ester, trioctyl phosphate for example,

Polyoxyethylene alkylphenyl,

Straight chain and/or branched alkylbenzene, heavy alkylate for example, dodecylbenzene and other alkylaromatic hydrocarbon,

The ester of mono carboxylic acid of aliphatic series;

The phthalic acid dialkyl, wherein alkyl can be straight chain and/or side chain, and contains 6-20 carbon atom, for example the dioctyl ester of phthalic acid, dihexyl, two the ninth of the ten Heavenly Stems ester, didecyl ester, two allantois acid esters and other ester;

Adipic acid ester, azelate, oleic acid ester and sebate;

Tung oil,

The ester of lipid acid and/or lipid acid,

Polyvalent alcohol is ethylene glycol and derivative thereof for example,

Organophosphate, for example Tritolyl Phosphate and/or triphenylphosphate and/or Viscotrol C.

Single unsaturated hydrocarbons of straight or branched for example contains alkene or its mixture of the straight or branched of 12-25 carbon atom; And/or

The mineral oil fractions that contains straight chain (for example n-paraffin) mineral oil, side chain (isoparaffin) mineral oil, ring-type (being called as alicyclic hydrocarbon in the prior art) mineral oil and composition thereof.Can use any suitable compatible mineral oil, example comprises single unsaturated hydrocarbons of straight or branched, for example contains at least 12 for example alkene or its mixtures of the straight or branched of 12-25 carbon atom; And/or contain the mineral oil fractions of straight chain (for example n-paraffin) mineral oil, side chain (isoparaffin) mineral oil, ring-type (in some prior aries, being called as alicyclic hydrocarbon) mineral oil and composition thereof.Preferably, each molecule of employed hydrocarbon comprises at least 10, preferably at least 12 and most preferably greater than 20 carbon atoms.

[0044] preferred processing aid comprises mineral oil fractions, alkyl alicyclic compound and alkylbenzene, uses comprising polyoxyethylene alkylphenyl with for some, and its end group does not have reactive polydialkysiloxane to polymkeric substance.Can optionally use this compound in the present invention, but the preferred initial boiling point of employed compound is greater than 200 ℃ (ASTM D-86).

[0045] any suitable mixture of mineral oil fractions can be used as extender in the present invention, but especially preferred high molecular extender (for example number-average molecular weight＞220).Example comprises:

Alkyl cyclohexane (molecular weight＞220);

Contain 1-99%, preferred 15-80% n-paraffin and/or isoparaffin (straight or branched paraffinic hydrocarbons) and 1-99%, preferred 85-20% cyclic hydrocarbon (alicyclic hydrocarbon) and maximum 3%, alkane of preferred maximum 1% aromatic carbon atom and composition thereof.Cyclic alkane (alicyclic hydrocarbon) can contain ring-type and/or polynuclear hydrocarbon.Can use any suitable mixture of mineral oil fractions, for example contain following mixture:

(i) 60-80% paraffinic hydrocarbons and 20-40% alicyclic hydrocarbon and maximum 1% aromatic carbon atom;

(ii) 30-50%, preferred 35-45% alicyclic hydrocarbon and 70-50% paraffinic hydrocarbons and/or isoparaffinic oil;

(iii) contain greater than the 60wt% alicyclic hydrocarbon, many ring greases of 20wt% cyclic hydrocarbon and ASTM D-86 boiling point be greater than 235 ℃ hydrocarbon fluid at least;

(iv) have greater than 40 weight part alicyclic hydrocarbon with less than the hydrocarbon fluid of 60 weight part paraffinic hydrocarbonss and/or isoparaffin based on the hydrocarbon of 100 weight parts.

[0046] preferably, mineral oil based extender or its mixture comprise at least one following parameter:

(i) molecular weight is greater than 150, most preferably greater than 200;

(ii) play initial boiling point and be equal to or greater than 230 ℃ (according to ASTM D86);

(iii) viscosity density constant value is less than or equal to 0.9 (according to ASTM 2501);

(iv) each molecule on average has at least 12 carbon atoms, and most preferably each molecule has 12-30 carbon atom;

(v) aniline point is equal to or greater than 70 ℃, and most preferably aniline point is 80-110 ℃ (according to ASTMD 611);

(vi) alicyclic hydrocarbon content is the 20-70wt% of extender and the paraffinicity (according to ASTM D 3238) that the mineral oil based extender has the 30-80wt% of extender;

(vii) pour point is-50 to 60 ℃ (according to ASTM D 97);

(viii) the kinematic viscosity under 40 ℃ is 1-20cSt (according to ASTM D 445);

(ix) proportion is 0.7-1.1 (according to ASTM D 1298);

(x) under 20 ℃, refractive index is 1.1-1.8 (according to ASTM D 1218);

(xi) density under 15 ℃ is greater than 700kg/m ³(according to ASTM D 4052); And/or

(xii) flash-point is greater than 100 ℃, more preferably greater than 110 ℃ (according to ASTM D 93);

(xii) Saybolt color is (according to ASTM D 156) at least+30;

(xiv) water-content is less than or equal to 250ppm (according to ASTM D 6304);

(xv) sulphur content is less than 2.5ppm (according to ASTM D 4927).

[0056] the fit for service benzene compound comprises heavy alkylate alkylbenzene or alkyl alicyclic compound.The example that can be used as the aryl compound that the alkyl of processing aid and/or softening agent replaces is to have aryl and molecular weight to be at least 200 compound, particularly by the alkyl and the benzene of other substituting group replacement possibly.Disclose the example of this processing aid in U.S. Patent No. 4312801, its content is introduced by reference at this.Available general formula (I), (II), (III) and (IV) represent these compounds.

R wherein ⁶Be the alkyl chain of 1-30 carbon atom, R ⁷-R ¹⁶In each be independently selected from hydrogen, alkyl, alkenyl, alkynyl, halogen, haloalkyl, nitrile, amine, acid amides, ether for example alkyl oxide or ester for example carbalkoxy and n are integer 1-25.

[0048] especially, have general formula (I), wherein R according to the employed processing aid of the inventive method ⁷, R ⁸, R ⁹, R ¹⁰And R ¹¹In each be hydrogen, and R ⁶Be C ₁₀-C ₁₃Alkyl.The source that this compound is particularly useful is so-called " heavy alkylate ", and it can reclaim from refinery after the oil distillation.Usually under being 230-330 ℃ temperature, scope distills and heavy alkylate is present in the cut residual after light ends distills.

[0049] example of alkyl alicyclic compound is the hexanaphthene that molecular weight surpasses 220 replacement.Disclose this examples for compounds in EP0842974, its content is introduced by reference at this.This compound can be represented with logical formula V:

R wherein ¹⁷Be alkyl with straight or branched of 1-25 carbon atom, and R ¹⁸With R ¹⁹Be independently selected from hydrogen or C _1-25The straight or branched alkyl.

[0050] consumption that can be included in the thinner in the composition depends on a plurality of factors, the application target of composition for example, the molecular weight of related thinner etc.Depend on these factors, according to polymer product of the present invention can contain 5-70%w/w thinner (based on polymkeric substance and thinner in conjunction with weight).Yet usually, the molecular weight of thinner is high more, and the amount of accepting in composition is more little.Typical composition contains the thinner of maximum 70%w/w.More suitably polymer product comprises the straight chain thinner of 30-60%w/w, and when thinner is heavy alkylate, more preferably 25-35%w/w.

[0051] chainextender can be that foregoing will the generation with polymer reaction has any suitable molecule of the reaction product of polymkeric substance chain length (being dp and molecular weight) greatly.Preferably, chainextender is silane or the short chain siloxanes (being that mean chain length is 2 to about 25) with design and two reactive terminal groups of the end group of preformed polymkeric substance reaction.

[0052] but for the pre-formation polymkeric substance with hydroxyl or condensation end group, suitable chainextender for example comprises:

Diethylamide base silane, for example dialkyl group diethylamide base silane or alkenyl alkyl diethylamide base silane, especially methyl ethylene two (N-methylacetamide base) silane or dimethyl two (N-methylacetamide base) silane; Diacetoxy silane, for example dialkyl group diacetoxy silane and alkyl chain thiazolinyl diacetoxy silane; Diamino silanes, for example dialkyl group diamino silanes or alkyl chain thiazolinyl diamino silanes, especially wherein each amino has those of a Si-N key and two N-C keys; Dialkoxy silicane, for example dimethoxy dimethylsilane and di ethoxy di methyl-monosilane; The polymerization degree is that 2-25 and each molecule have at least two acetamidos or acetoxyl group or amino or alkoxyl group or amide group or the substituent polydialkysiloxane of ketoxime base, and wherein each alkyl comprises 1-6 carbon atom independently; Six organic basic ring three silazane, eight organic radical cyclotetrasilazanes; Diamide base silane, for example dialkyl group diamide base silane or alkyl chain thiazolinyl diamide base silane; Two ketoximinosilanes, for example dialkyl group two ketoximinosilanes and alkyl chain thiazolinyl two ketoximinosilanes; α-aminoalkyl dialkoxy alkyl silane, wherein alkyl and alkoxyl group contain 1-5 carbon atom, alpha-amino group methyl dialkoxy methyl-monosilane for example, especially preferred is that wherein aminomethyl is N, those of N-dialkyl amino methyl;

Chainextender with the silicon compound form of following general formula:

ZMe ₂SiO (Me ₂SiO) _ySiMe ₂Z or ZMe ₂Si-Y-SiMe ₂Z

Wherein Z, Y, y and m are as previously mentioned.

[0053] specific examples of chainextender comprises the alkenyl alkyl dialkoxy silicane, vinyl methyl dimethoxysilane for example, vinyl ethyl dimethoxy silane, the vinyl methyldiethoxysilane, vinyl ethyl diethoxy silane, alkenyl alkyl two oximino silanes, vinyl methyl two oximino silanes for example, vinyl ethyl two oximino silanes, vinyl methyl two oximino silanes, vinyl ethyl two oximino silanes, alkenyl alkyl diacetoxy silane, vinyl methyl diacetoxy silane for example, vinyl ethyl diacetoxy silane and alkenyl alkyl dihydroxyl silane, vinyl methyl dihydroxyl silane for example, vinyl ethyl dihydroxyl silane, vinyl methyl dihydroxyl silane, vinyl ethyl dihydroxyl silane, aminomethyl phenyl dimethoxy silane, dibutoxy diacetoxy silane, alkyl chain thiazolinyl two (N-alkyl acetamido) silane, for example methyl ethylene two (N-methylacetamide base) silane and methyl ethylene two (N-ethyl acetamide base) silane; Dialkyl group two (N-arylacetamide base) silane, for example dimethyl two (N-methylacetamide base) silane; With dimethyl two (N-ethyl acetamide base) silane; Two (the N-arylacetamide base) silane of alkyl chain thiazolinyl, for example two (the N-arylacetamide base) silane of methyl ethylene two (phenyl acetanilide,Phenacetylaniline base) silane and dialkyl group, for example dimethyl two (phenyl acetanilide,Phenacetylaniline base) silane, two (the N-methylacetamide base) silane of methyl ethylene, methyl hydrogen diacetoxy silane, two (the N-diethyl aminooxy) silane of dimethyl and two (sec-butyl amino) silane of dimethyl.Employed chainextender also comprises above two or more any combination.

[0054] for the preformed polymkeric substance with alkenyl or Si-H end group that is suitable for coming by the hydrosilylation route addition reaction, chainextender for example comprises:

The silane that contains two alkenyls, two hydrogen silanes, the polymerization degree be 2-25 and relatively each end group have the poly-diakyl silane of at least one Si-alkene base key, the polymerization degree be 2-25 and relatively each end group have the polydialkysiloxane of at least one Si-H key and wherein each alkyl comprise 1-6 carbon atom independently;

The organic radical silicon compound of following general formula:

Wherein R as previously mentioned, j is 1,2 or 3, k be 0 or 1 and j+k be 2 or 3.

It can exemplify the compound of following formula: (ViMe ₂SiO) ₂SiVi (OMe) ₁(ViMe ₂SiO) ₁SiVi (OMe) ₂, (ViMe ₂SiO) ₂SiVi (OEt) ₁(ViMe ₂SiO) ₁SiVi (OEt) ₂, (ViMe ₂SiO) ₃Si (OMe) ₁, (ViMe ₂SiO) ₂Si (OMe) ₂, (ViMe ₂SiO) ₃Si (OEt) ₁(ViMe ₂SiO) ₂Si (OEt) ₂Vi as used herein represents vinyl, and Me represent methylidene and Et represent ethyl.

[0055] the employed catalyzer of reaction decision catalysis chain extending reaction by carrying out.Composition further comprises condensation catalyst.The reaction that chain extension involved therein is under the situation of condensation reaction, can use any suitable condensation catalyst, make the polymer composition chain extension, comprising tin, lead, antimony, iron, cadmium, barium, manganese, zinc, chromium, cobalt, nickel, titanium, aluminium, gallium or germanium and Zirconium-base catalyst, organotin metal catalyst and or can use the 2-ethylhexoate of iron, cobalt, manganese, lead and zinc for example.Preferred organotin, titanic acid ester and/or zirconate are catalyst based.

[0056] chain extending reaction that contains oximino silane or acetoxysilane uses tin catalyst to be used for solidifying usually, tartrate triethyltin for example, stannous octoate, oleic acid tin, naphthoic acid tin, three-2 ethyl hexanoic acid butyl tin, butyric acid tin, three suberic acid carboxymethoxyl phenyltins, three acetic acid (ceroate) isobutyl-tin and two organic tin salts, particularly dicarboxylic acid two organo-tin compounds, for example dibutyl tin dilaurate, two butyric acid tin methides, dimethanol two fourth tin, oxalic acid two fourth tin, two neodecanoic acid tin methides, dibenzoic acid two fourth tin, stannous octoate, two neodecanoic acid tin methides, two sad two fourth tin.Wherein especially preferred dibutyl tin dilaurate, oxalic acid two fourth tin.

[0057] for the composition that contains the alkoxysilane group extender compounds, preferred catalyzer is titanic acid ester or zirconate compound.This titanic acid ester can comprise general formula Ti[OR ²¹] ₄Compound, each R wherein ²¹Can be identical or different, and to represent unit price primary, the second month in a season or uncle's aliphatic hydrocarbyl, described alkyl can be the straight or branched alkyl that contains 1-10 carbon atom.Randomly, titanic acid ester can contain the part unsaturated group.Yet, R ²¹Preferred embodiment include but not limited to methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl and the secondary alkyl of side chain, for example 2,4-dimethyl-3-amyl group.Preferably, as each R ²¹When identical, R ²¹Be the secondary alkyl of sec.-propyl, side chain or tertiary alkyl, the especially tertiary butyl.

[0058] example comprises that the titanic acid ester of tetrabutyl titanate, titanium isopropylate or chelating or zirconate (can be and any suitable sequestrant alkyl acetylacetonate for example, for example methyl or ethylacetoacetone(EAA,HEAA) thing chelating), for example two (acetylacetone based) titanic acid ester of di-isopropyl, two (ethylacetoacetone(EAA,HEAA) base) titanic acid ester of di-isopropyl, two (ethyl acetoacetic acid) diisopropoxy titanium and analogue.In EP1254192, disclose the further example of appropriate catalyst, be introduced into by reference at this.Employed catalyst consumption depends on employed curing system, but typically is the 0.01-3% of whole composition weights.

[0059] preferably, catalyst component (d) exists with the consumption of about 0.1-3% of composition weight, and under the situation of using sequestrant, the consumption that component (d) can be bigger exists.

[0060] be under the situation of addition reaction in the reaction between polymkeric substance and the chainextender, addition reaction is hydrosilylation reactions preferably, wherein selected catalyzer can comprise any suitable hydrosilylation catalysts, and the platinum metals that for example is selected from platinum, rhodium, iridium, palladium or the ruthenium catalyst is catalyst based.The catalyzer that can be used for catalysis present composition solidified platinum group metal can be become known for catalysis and silicon bonded hydrogen atom and and the silicon bonded alkenyl between any in the catalyst for reaction.As the preferred platinum group metal of carrying out present composition solidified catalyzer by hydrosilylation is platinum based catalyst.Some preferred platinum base hydrosilylation catalysts that are used to solidify the present composition are platinum, platinic compound and platinum complex.Representative platinic compound comprises Platinic chloride, six hydration Platinic chlorides, platinum dichloride and contains the complex compound of this compound that lower molecular weight contains the organopolysiloxane of vinyl.Other hydrosilylation catalysts that is suitable for using in the present invention comprises for example rhodium catalyst, for example [Rh (O ₂CCH ₃) ₂] ₂, Rh (O ₂CCH ₃) ₃, Rh ₂(C ₈H ₁₅O ₂) ₄, Rh (C ₅H ₇O ₂) ₃, Rh (C ₅H ₇O ₂) (CO) ₂, Rh (CO) [Ph ₃P] (C ₅H ₇O ₂), RhX ⁴ ₃[(R ³) ₂S] ₃, (R ² ₃P) ₂Rh (CO) X ⁴, (R ² ₃P) ₂Rh (CO) H, Rh ₂X ⁴ ₂Y ² ₄, H _aRh _bAlkene _cCl _d, Rh (O (CO) R ³) _3-n(OH) _n, X wherein ⁴Be hydrogen, chlorine, bromine or iodine, Y ²Be for example methyl or ethyl, CO, C of alkyl ₈H ₁₄Or 0.5C ₈H ₁₂, R ³Be alkyl, cycloalkyl or aryl, and R ²Be the group that alkyl, aryl or oxygen replace, a is 0 or 1, and b is 1 or 2, and c is that integer 1-4 (comprising end value) and d are 2,3 or 4, and n is 0 or 1.Also can use any suitable iridium catalyst, for example Ir (OOCCH ₃) ₃, Ir (C ₅H ₇O ₂) ₃, [Ir (Z ⁴) (En) ₂] ₂, [Ir (Z ⁴) (Dien)] ₂, Z wherein ⁴Be chlorine, bromine, iodine or alkoxyl group, En is that alkene and Dien are cyclooctadiene.

[0061] one of most important aspect of the present invention is the following fact: by polymer, polymer in the presence of thinner, resulting polymers/processing aid and/or polymer/plasticizer mixture have significantly lower viscosity with comparing of common expection in whole polymerization technique, this is because when polymerization, and viscosity reduces thinner and is present in the polymeric blends.Be appreciated that concerning polymerization technique process according to the present invention, even when only for example the thinner of 5-20wt% exists on a small quantity, also be this situation.For example use the standard technology of the polymkeric substance that is mixed together thinner and filler and pre-preparation, people typically only can be 80,000mPa.s polymkeric substance in mix the thinner of about 28wt%, this is because when using the polymkeric substance of big viscosity, the problem that existence is relevant with processing and blend.Therefore,, blend problem and employed for alternate application will be avoided, resulting polymers can be used for the organopolysiloxane sizing material of the millions of mPa.s of common use by before polymerization, introducing thinner.

[0062] method of the present invention makes and can use significantly a large amount of thinners in conjunction with the polymkeric substance that causes having the viscosity that can not take in the past because of handling problem.The thinner that can realize depends on the miscible degree of thinner in polydimethylsiloxane with siloxanes ratio mutually and vice versa.Find that miscible degree depends in part on the molecular weight of polydimethylsiloxane at least.

[0063] the various improved various physical features of prescription that the user provides the polymkeric substance that contains dilution of the present invention are returned in this combination, and the elasticity of more than products therefrom, this is because used the polymkeric substance with the polymkeric substance chain length/viscosity that can not use up to now.Application comprises sealant dispensing, formulation for coating material, be used for the organopolysiloxane sizing compound formula of the high-consistency that high consistency rubber uses and the alkylsiloxane fluidic dispersion of using at the personal care product.

[0064] according to the present invention, provide preparation can be solidified into elastomeric moisture cured method for compositions, this method comprises the steps:

(i) but use and to contain condensation, the end-capping reagent of preferred hydroxyl or hydrolysable group prepares the polymkeric substance that contains organic based polysiloxane of the chain extension of foregoing dilution,

(ii) the organopolysiloxane polymkeric substance of compounding gained dilution with (i) this organopolysiloxane polymkeric substance is had reactive suitable crosslinking agents, (ii) suitable condensation catalyst and optional (iii) filler.

The X of small proportion (＜20%) randomly ¹Base can comprise trialkylsilkl, wherein preferably methyl or ethyl of each alkyl.

[0065] in one embodiment, use the single part of this method preparation or two portions organopolysiloxane encapsulant composition.Two portions composition comprises the polymkeric substance and the filler (optionally) of dilution and catalyzer and linking agent is provided in second section in first part, just before using, mix with suitable ratio (for example 1: 1 to 10: 1).Can in the first part of composition or second section, provide the extra additive of the following stated, but preferably in second section, add.

[0066], provide and can be solidified into elastomeric moisture cured composition by what the method that comprises the steps obtained according to the present invention:

(ii) the organopolysiloxane polymkeric substance of compounding gained dilution with (i) this organopolysiloxane polymkeric substance is had reactive suitable crosslinking agents, (ii) suitable condensation catalyst and (iii) filler randomly.

[0067] the further embodiment according to the present invention provides to be solidified into elastomeric moisture cured composition, and said composition comprises:

But having of a) can obtaining as previously described is no less than two polymkeric substance that contain organic based polysiloxane with the chain extension of the dilution of the condensation group (preferred hydroxyl or hydrolysable group) of silicon bonding;

B) each molecule have at least two to (a) but in the condensation group have the siloxanes and/or the silane crosslinker of reactive group;

C) randomly one or more fillers and

D) suitable curing catalysts.

[0068] preferably, the general formula according to the component of polymer in the polymkeric substance of dilution of the present invention is:

X ¹-A-X ²(1)

Wherein A, X ¹And X ²As previously mentioned.Preferably, the number-average molecular weight of polymkeric substance produced according to the invention (Mn) greater than 132,000 and the polymerization degree greater than 1800, this measures according to ASTMD5296-05, wherein with respect to the molecular weight determination of equivalent gravimetric value of polystyrene.

[0069] can use any suitable crosslinking agent.Employed (b) linking agent preferably contains the silane compound of hydrolysable group in the described in front moisture cured composition.These comprise the hydrolysable group that contains with the silicon bonding, for example one or more silane or the siloxanes of acyloxy (for example acetoxyl group, hot acyloxy and benzoyloxy), ketoxime base (for example dimethyl ketone oximido and isobutyl ketone oximido), alkoxyl group (for example methoxyl group, oxyethyl group, propoxy-) and alkenyl oxy (for example pseudoallyl oxygen base and 1-ethyl-2-methyl ethylene oxygen base).

[0070] under the situation of siloxanes linking agent, molecular structure can be straight chain, side chain or ring-type.

[0071] but each molecule of linking agent can have two but preferably have 3 or 4 with the condensation group of silicon bonding (preferred hydrolysable group).When linking agent is a silane and when each molecule of silane has 3 hydrolysable group with the silicon bonding, the 4th group is non-hydrolysable and the organic group silicon bonding suitably.The organic group of these and silicon bonding is randomly by the halogen alkyl that replaces of fluorine and chlorine for example suitably.This 4th examples of groups comprises alkyl (for example methyl, ethyl, propyl group and butyl), cycloalkyl (for example cyclopentyl and cyclohexyl), alkenyl (for example vinyl and allyl group), aryl (for example phenyl and tolyl), aralkyl (for example 2-styroyl) and the group that obtains by all or part hydrogen that replaces with halogen in the aforementioned organic group.Yet preferred the 4th organic group with the silicon bonding is methyl.

[0072] silane and the siloxanes that can be used as linking agent comprises alkyltrialkoxysilaneand, for example methyltrimethoxy silane (MTM) and Union carbide A-162, alkenyl trialkoxy silane, for example vinyltrimethoxy silane and vinyltriethoxysilane, isobutyl-Trimethoxy silane (iBTM).Other suitable silane comprises ethyl trimethoxy silane, vinyltriethoxysilane, phenyltrimethoxysila,e, alkoxyl group trioximido silane, alkenyl trioximido silane, 3,3,3-trifluoro propyl Trimethoxy silane, methyl triacetoxysilane, vinyltriacetoxy silane, the ethyl triacetoxysilane, dibutoxy diacetoxy silane, phenyl three propionyloxy silane, methyl three (methyl ethyl ketone oximido) silane, vinyl three (methyl ethyl ketone oximido) silane, methyl three (methyl ethyl ketone oximido) silane, methyl three (different propenyloxy group) silane, vinyl three (different propenyloxy group) silane, ethyl polysilicate, the orthosilicic acid n-propyl, ethyl orthosilicate, dimethyl tetrem acyloxy sily oxide.Employed linking agent also can comprise any combination of above two or more.

[0073] consumption that is present in the linking agent in the composition depends on the molecular weight of the special properties of linking agent and especially selected molecule.Composition contains suitably compares the linking agent of stoichiometric amount at least with above-described polymer materials.Composition can contain for example linking agent of 2-30w/w%, but is generally 2-10w/w%.The acetoxyl group linking agent typically can 3-8w/w%, and the consumption of preferred 4-6w/w% exists, and the oximido linking agent that has higher molecular weight usually typically accounts for 3-8w/w%.

[0074] composition further comprises the condensation catalyst of front in type described in the chain extension of the polymkeric substance with OH or hydrolyzable end group.

[0075] composition of the present invention can contain other conventional for silicone encapsulants and analogue composition as optional ingredients.For example composition contains one or more fine reinforcing fillers usually, the for example pyrolysis of high surface area and precipitated silica, comprising rice hull ash and on certain degree lime carbonate, and/or one or more extra non-reinforcing filler, for example quartz of Fen Suiing, diatomite, barium sulfate, ferric oxide, titanium dioxide and carbon black, talcum, wollastonites.Can use other filler except above-described to comprise for example kaolin, aluminium hydroxide, magnesium hydroxide (brucite), graphite, copper carbonate malachite, nickelous carbonate zaratite (zarachite), barium carbonate witherite and/or Strontium carbonate powder strontianite for example for example for example for example of aluminite, calcium sulfate (dehydrated gyp-), gypsum, calcium sulfate, magnesiumcarbonate, clay separately.

[0076] silicate in the group of aluminum oxide, next free olivine group, garnet group, silico-aluminate, cyclosilicate, chain silicate and sheet silicate composition.Olivine group comprises silicate minerals, such as but not limited to forsterite and Mg ₂SiO ₄The garnet group comprises the silicate minerals of pulverizing, such as but not limited to vogesite, Mg ₃Al ₂Si ₃O ₁₂, hessonite and Ca ₂Al ₂Si ₃O ₁₂Silico-aluminate comprises the silicate minerals of pulverizing, such as but not limited to sillimanite, Al ₂SiO ₅, mullite, 3Al ₂O ₃2SiO ₂, kyanite and Al ₂SiO ₅The cyclosilicate group comprises silicate minerals, such as but not limited to trichroite and Al ₃(Mg, Fe) ₂[Si ₄AlO ₁₈].The chain silicate group comprises the silicate minerals of pulverizing, such as but not limited to wollastonite and Ca[SiO ₃].

[0077] the sheet silicate group comprises silicate minerals, such as but not limited to mica, K ₂Al ₁₄[Si ₆Al ₂O ₂₀] (OH) ₄, pyrophyllite, Al ₄[Si ₈O ₂₀] (OH) ₄, talcum, Mg ₆[Si ₈O ₂₀] (OH) ₄, serpentine is asbestos, kaolinite, Al for example ₄[Si ₄O ₁₀] (OH) ₈And vermiculite.

[0078] in addition, can be for example with lipid acid or fatty acid ester stearate for example, perhaps carry out the surface treatment of filler with organosilanes, organopolysiloxane or organic radical silazane, six alkyl disilazanes or short chain siloxane glycol, make filler hydrophobic, and therefore handle and obtain and the uniform mixture of other sealant compositions than being easier to.The surface treatment of filler makes that the silicate minerals of pulverizing is wetting by siloxane polymer easily.The filler of these surface modifications is not agglomerating, and can be incorporated in the siloxane polymer equably.This causes the improved normal temperature mechanical property of uncured composition.In addition, surface-treated filler obtains than the conductivity that is untreated or starting material are low.

[0079] when using, the ratio of this filler depends on required performance in forming elastomer compositions and solidified elastomerics.In per 100 parts by weight polymer (not comprising the thinner part), the filler content in the composition is maintained at about 5 to about 800 weight part scopes usually, preferred 25-400 weight part.

[0080] other composition in the composition be can be included in and composition solidified the promotor for example metal-salt of carboxylic acid and amine, rheology modifier, adhesion promotor, pigment, thermo-stabilizer, fire retardant, UV stablizer, chainextender, conduction and/or heat conductive filler, cured modified dose, mycocide and/or biocide and analogue (they can be suitably exist with the consumption of 0-8.0wt%) included but not limited to be used to quicken.Be appreciated that some additives comprise greater than in the enumerating of a kind of additive.This additive has the ability that can work on all different modes of mentioning.Be sometimes referred to as the water scavenging agent of deactivator, isocyanic ester for example, for example NSC 87419, isophorone diisocyanate and hexamethylene diisocyanate can be included in the composition, but preferably do not use them.

[0081] rheologic additive comprises: based on the silicone organic copolymers of the polyvalent alcohol of polyethers or polyester, for example at described in the EP0802233 those; Be selected from polyoxyethylene glycol, polypropylene glycol, ethoxyquin Viscotrol C, oleic acid b-oxide, alkylphenol b-oxide, oxyethane (EO) and the multipolymer of propylene oxide (PO) and the nonionogenic tenside in the silicone-polyether copolymer; And silicone glycols.

[0082] any suitable adhesion promotor can be incorporated in the encapsulant composition of the present invention.These can comprise for example organoalkoxysilane, for example aminoalkyl organoalkoxysilane, epoxy group(ing) alkylalkoxy silane, for example 3-glycidoxy-propyltrimethoxy silane and mercaptoalkyl alkoxy silane and γ-An Bingjisanyiyangjiguiwan.Can use in addition and contain silica-based isocyanuric acid ester, for example 1,3,5-three (trialkoxysilyl alkyl) isocyanuric acid ester.Further suitable adhesion promotor is for example for example 3-aminopropyl trimethoxysilane and the alkylalkoxy silane reaction product of methyltrimethoxy silane, epoxy group(ing) alkylalkoxy silane, mercapto alkylalkoxy silane and derivative thereof for example randomly of 3-glycidoxy-propyltrimethoxy silane and the amino organoalkoxysilane that replaces of epoxy group(ing) alkylalkoxy silane.

[0083] thermo-stabilizer can comprise carboxylate salt, hydration cerium (cerium hydrate), barium zirconate, titanium oxide, cerium octoate, zirconium caprylate and the porphyrin of ferric oxide and carbon black, iron.

[0084] fire retardant for example can comprise carbon black, W 4600 and silicate for example wollastonite, platinic compound.

[0085] conductive filler material can comprise carbon black, metallic particles for example silver granuel, any suitable conducting metal oxide filler, for example the titanium dioxide powder of tin and/or antimony processing has been used on its surface, the potassium titanate powder that has handled with tin and/or antimony on its surface, the zinc oxide that has handled with aluminium with stannic oxide and its surface of antimony processing on its surface.

[0086] heat conductive filler can comprise: metallic particles, for example powder, thin slice and collargol, copper, nickel, platinum, gold, aluminium and titanium; Metal oxide, especially aluminum oxide (Al ₂O ₃) and beryllium oxide (BeO), magnesium oxide, zinc oxide, zirconium white; Ceramic packing, for example single wolfram varbide, silicon carbide and aluminium nitride, boron nitride and diamond.

[0087] can use any suitable mycocide and biocide; these comprise the benzimidazole carbamate that N-replaces; the benzimidazolyl-carbamate; 2-benzimidazolyl-Urethylane for example; 2-benzimidazolyl-urethanum; 2-benzimidazolyl-carbamic acid isopropyl ester; N-{2-[1-(N; the N-formyl-dimethylamino) benzimidazolyl-] } Urethylane; N-{2-[1-(N; the N-formyl-dimethylamino)-6-tolimidazole base] Urethylane; N-{2-[1-(N; the N-formyl-dimethylamino)-5-tolimidazole base] Urethylane; N-{2-[1-(N-methylamino formyl radical) benzimidazolyl-] } Urethylane; N-{2-[1-(N-methylamino formyl radical)-6-tolimidazole base] } Urethylane; N-{2-[1-(N-methylamino formyl radical)-5-tolimidazole base] } Urethylane; N-{2-[1-(N; the N-formyl-dimethylamino) benzimidazolyl-] } urethanum; N-{2-[2-(N-methylamino formyl radical) benzimidazolyl-] } urethanum; N-{2-[1-(N; the N-formyl-dimethylamino)-6-tolimidazole base] urethanum; N-{2-[1-(N-methylamino formyl radical)-6-tolimidazole base] } urethanum; N-{2-[1-(N; the N-formyl-dimethylamino) benzimidazolyl-] } carbamic acid isopropyl ester; N-{2-[1-(N-methylamino formyl radical) benzimidazolyl-] } carbamic acid isopropyl ester; N-{2-[1-(N-propyl group formamyl) benzimidazolyl-] } Urethylane; N-{2-[1-(N-butyl formamyl) benzimidazolyl-] } Urethylane; N-{2-[1-(N-propyl group formamyl) benzimidazolyl-] } carboxylamine methoxyl group ethyl ester; N-{2-[1-(N-butyl formamyl) benzimidazolyl-] } carboxylamine methoxyl group ethyl ester; N-{2-[1-(N-propyl group formamyl) benzimidazolyl-] } carboxylamine ethoxy base ethyl ester; N-{2-[1-(N-butyl formamyl) benzimidazolyl-] } carboxylamine ethoxy base ethyl ester; N-{1-(N; N-dimethylamino methanoyl) benzimidazolyl-} Urethylane; N-{2-[N-methylamino methanoyl] benzimidazolyl-} Urethylane; N-{2-[1-(N-butyl carbamoyloxy) benzimidazolyl-] } Urethylane; N-{2-[1-(N-propyl group carbamoyloxy) benzimidazolyl-] } carboxylamine ethoxy base ethyl ester; N-{2-[1-(N-butyl carbamoyloxy) benzimidazolyl-] } carboxylamine ethoxy base ethyl ester; N-{2-[1-(N; the N-formyl-dimethylamino)-6-chloro benzimidazole base] Urethylane and N-{2-[1-(N; the N-formyl-dimethylamino)-6-nitrobenzimidazole base] Urethylane; 10; the two phenoxy group arsine (trade(brand)names: Vinyzene of 10`-oxygen base; OBPA); two iodo methyl p-methylphenyl sulfones; thionaphthene-2-cyclohexyl methane amide-S; the S-dioxide; N-(fluorine dichloromethane sulfenyl) phthalic imidine (trade(brand)name: Fluor-Folper; Preventol A3); benzimidazolyl-2 radicals-aminocarbamic acid methyl esters (trade(brand)name: Carbendazim; Preventol BCM); two (2-pyridylthio-1-oxidation) zinc (vancide ZP); 2-(4-thiazolyl)-benzoglyoxaline; N-phenyl-iodo propargyl carbamate; N-octyl group-4-isothiazoline-3-ketone; 4; 5-two chloro-2-n-octyls-4-isothiazoline-3-ketone; N-butyl-1; 2-benzisothiazole-3-ketone and/or three  azoles based compounds, for example tebuconazole (tebuconazol) is in conjunction with argentiferous zeolite.

[0088] the composition composition of room temperature vulcanizable preferably is because they under the situation that is not having heating, at room temperature solidify.

[0089] can use any suitable mixing equipment, by mixing each composition, the preparation composition.Can optionally add other component.For example can be by the polysiloxane with hydroxyl or hydrolysable group and employed any organic radical silicon softening agent or the filler that is mixed together increment, and mix the pre-composition of it and linking agent and catalyzer, thereby prepare preferred one-part moisture gas cured compositions.Can UV stablizer, pigment and other additive be joined in the mixture in any required stage.

[0090] after mixing, can be under anhydrous basically condition, for example in the container of sealing, storage composition is up to requiring use.

[0091] for sealant dispensing, polymerization obtains several advantages in the presence of thinner.About rheology, owing to exist thinner to cause to increase the polymkeric substance chain length, this will compensate the dilution dosage that exists in the sealing agent of dilution, Just because of this, the viscosity of the polymkeric substance of dilution is significantly higher than if thinner is joined the viscosity that is obtained in the employed standard polymers in present sealant dispensing, the latter's viscosity for example is 80000-100 under 25 ℃, 000mPa.s.The modulus that the gained sealing agent is lower means that in addition more moving is possible in junction to be sealed, the loss of thinner takes place even its degree makes, then the caused effective modulus that exists of high-molecular weight polymer that can be prepared according to the methods of the invention can compensate the stress that causes because of the sealing agent contraction.The product of the inventive method obtains excellent processing advantage, and this is because when the molecular weight of considering polymkeric substance, the polymkeric substance of dilution has due to the quite low viscosity.

[0092] therefore, further in, the invention provides spatial method between two unit of sealing, described method comprises and applies above-described composition and cause or allows composition curing.Suitable unit comprises aforesaid glazing structure or building unit, and these form further aspect of the present invention.

[0093] the applicant finds, and sealant dispensing according to the present invention provides very elastomeric sealing agent to the user after solidifying, and this is because use the polymkeric substance (when there is not viscosity under the thinner situation in people's consideration) of high chain length/viscosity.This sealing agent provides significantly the elongation at break greater than 650%.

[0094] in one embodiment, use the single part of this method preparation or two portions organopolysiloxane encapsulant composition.Two portions composition comprises the polymkeric substance and the filler (optionally) of dilution and comprise catalyzer and linking agent in second section in first part, just before using, mix with suitable ratio (for example 1: 1 to 10: 1).The extra additive of the following stated can be provided in first part's second section of composition, but preferably in second section, add.

[0095] but the special problem that the industry of siloxanes sealing agent must tackle is to produce the solidified encapsulant surface of japanning.Typically, be impossible (, also being seldom in reality) adopting under most of present solidified silicone encapsulants prescription situations even have.Yet, the applicant finds, (the highly-filled sealant dispensing of the high molecular weight silicone polymkeric substance that for example＜15wt%) dilutes in organic compound is japanning easily to contain low levels, this is because there is the silicone compounds of low ratio in prescription, and this is impossible typically, because these high-molecular weight polymers have run into processing and mixed questions and the elongation poor performance relevant with highly-filled sealing agent.Test shows, but the sealant dispensing of described japanning and acrylic acid or the like filler are quite or improve to some extent, and are to have suitable value therefore because they have reduced existing siloxanes amount.

[0096] in the extra embodiment of the present invention; a kind of method of producing the surface with the condensation cured silicone elastomer of hardened protective coating coating is provided; this method comprises that the composition with the foregoing method according to the present invention is exposed under the moisture; up to obtaining the solidified surface of elastomer; and form uniform matting; on at least a portion solidified surface of elastomer, be applied to hardenable protective coating compositions under the envrionment conditions afterwards; wherein wetting surface that it will be applied thereto of protective coating compositions and generation do not have the film of flaw basically, allow the protective coating compositions sclerosis afterwards.

[0097] the further advantage of the polymkeric substance by the inventive method preparation is that after polymerization was finished, they contained the very annular siloxane of low levels.

[0098] in the present invention further uses, comes from viscosity that the polymkeric substance of the dilution of polymerization technique can use and in the fluid that 4 to 100mPa.s volatility or non-volatile low molecular weight contain organic based polysiloxane, disperse in personal care application.Preferably, in this application, thinner is the end capped polydialkysiloxane softening agent of trialkylsilkl.

[0099] volatile siloxane is low viscosity dialkylsiloxane (typically dimethyl siloxane) fluid suitably, described fluid preferably contain dimethyl siloxane units and randomly trimethicone unit and preferred viscosity under 25 ℃ less than about 10mPa.s.Low viscous dialkylsiloxane fluid can be that the polymerization degree is that the cyclic polysiloxanes or the polymerization degree of 3-10 is 1-10, preferred 1 to 5 line style silicone compounds.

[0100] the cyclopolysiloxane compound is by The Cosmetics, Toiletries andFragrance Association, and Inc., Washington, D.C. (CTFA) address is continued to use name " CYCLOMETHICONE ".The two is transparent liquid cyclopolysiloxane and line style siloxanes, and colourless basically, nontoxic, non-greasy and not stimulating.In makeup, these volatility alkylsiloxane fluids are non-stimulated to skin, and demonstrate the spreadability of raising and wipe easily when using and open.After using, the material evaporation, thus do not stay resistates.

[0101] when under open indoor atmosphere, at diameter of its periphery carrying is the center of the No.1 circular filter paper of 185mm when placing the 1g alkylsiloxane fluid useful according to the present invention, and this fluid does not stay any resistates basically after at room temperature 30 minutes.Representative linear alkyl siloxane fluid comprises that boiling point is the octamethyltrisiloxane that 99.5 ℃ hexamethyldisiloxane and boiling point are 152 ℃.The representative cyclic alkyl siloxane fluid that is suitable for the application comprises that boiling point is the decamethylcyclopentaandoxane that 133 ℃ hexamethyl cyclotrisiloxane, octamethylcyclotetrasiloxane that boiling point is 171 ℃ and boiling point are 205 ℃.These alkylsiloxane fluids can use separately or use in conjunction with two or more independent fluidic form of mixtures.Alkylsiloxane fluidic mixture causes the evaporation behavior to be different from any independent alkylsiloxane fluidic volatile materials.Alkylsiloxane fluid and preparation method thereof is that known in the art and this fluid is commercially available.

[0102] in some cases, can wish with the one or more methyl in other group substituted alkyl siloxane fluid.Therefore can there be substituting group, for example has the alkyl of 2-12 carbon atom, aryl, amido, vinyl, hydroxyl, haloalkyl, aralkyl and acrylate-based with 6-10 carbon atom.

[0103] contains and be dispersed in the present composition that alkylsiloxane flows the blend of intravital diluted polymer and can contain the tensio-active agent that is selected from negatively charged ion and the amphoterics in addition.Surfactant system should provide acceptable foam levels on hair, and can clean hair, and can comprise one or more water soluble detergents, i.e. negatively charged ion or amphoterics.Suitable anionic detergent comprises sulfonated and sulfation alkyl, aralkyl and alkaryl anionic detergent, alkyl succinate, alkyl sulfo succinate and N-alkyl sarcosine salt.Particularly preferably be alkyl and aralkyl vitriolic sodium, magnesium, ammonium and single-, two-and triethanolamine salt and alkylaryl sulfonate.Alkyl in the washing composition has about 12-21 of total carbon atom usually, can be undersaturated, and the preferred fat alkyl.Vitriol can be the sulfuric acid ether that each molecule contains 1-10 oxyethane or propylene oxide units.Preferably, sulfuric acid ether contains 2-3 ethylene oxide unit.

[0104] typical anionic detergent especially comprises Sodium Lauryl Sulphate BP/USP; the bay ether sodium sulfate; Texapon Special; triethanolamine lauryl sulfate; C14-16 alkene sulfonic acid sodium; C12-15 alkyl polyoxyethylene ether ammonium sulfate (ammonium salt of the sulfation polyglycol ether of the mixture of synthetic C12-15 Fatty Alcohol(C12-C14 and C12-C18)); the myristyl ether sodium sulfate; Zetesol AP; single oleoyl amido disodium sulfosuccinate; lauryl sulfo-succinic acid ammonium; Sodium dodecylbenzene sulfonate; Witco 1298 Soft Acid trolamine and N-sodium N-lauroyl sarcosinate.Most preferred anionic detergent is a lauryl sulfate, especially the monoethanolamine of lauryl sulfate, trolamine, ammonium and sodium salt.Zetesol NL also very suitably is used in the composition of the present invention.

[0105] tensio-active agent that is divided into the class ampholytic detergent usually especially comprises N-cocamidopropyl ethyl-N hydroxyethyl-N-carboxymethylamino sodium acetate, N-(cocamidopropyl ethyl)-N-(2-ethoxy-c acidic group) alanine sodium, coco betaine, N-cocamidopropyl propyl-dimethyl glycine and N-lauryl-N-carboxymethyl-N-(2-hydroxyethyl) ethylene diamine.Other suitable ampholytic detergent comprises for example for example 3-(dodecyl dimethyl ammonium)-third-1-sulfonate and 3-(tetradecyl Dimethyl Ammonium) second-1-sulfonate of α-(tetradecyl Dimethyl Ammonium) second inner salt, β-(hexadecyl diethyl ammonium) third inner salt and γ-(dodecyl dimethyl ammonium) fourth inner salt and sultaine class of season type cycloimidate, betaines.

[0106] composition of the present invention can contain nonionogenic tenside.Nonionogenic tenside of the present invention is selected from fatty acid alkyl amide and amine oxide surfactant.Fatty acid alkyl amide is by making alkanolamine, and for example the reaction of monoethanolamine, diethanolamine, monoisopropanolamine or diisopropanolamine (DIPA) and lipid acid or fatty acid ester forms acid amides and the nonionogenic tenside that obtains.Provide hydrophobic part in the nonionogenic tenside by the fatty acid hydrocarbon chains that has 10-21 carbon atom usually.The fatty acid alkyl amide tensio-active agent for example comprises: fatty diglycollic amide, for example Unimac 5680 diglycollic amide, lauric acid diethyl amide, capric acid diglycollic amide, coconut fatty acid diglycollic amide, linolic acid diglycollic amide, tetradecanoic acid diglycollic amide, oleic acid diethyl amide and Stearic acid diethanolamine salt; Fatty monoethanol amide, for example coconut fatty acid single ethanol amide; With lipid acid list isopropanol amide, the single isopropanol amide of oleic acid list isopropanol amide and lauric acid for example.

[0107] amine oxide is to form the known nonionogenic tenside that amine oxide obtains by tertiary amine oxide usually.They are also sometimes referred to as the polarity nonionogenic tenside.Amine oxide surfactant for example comprises: N-alkyl amine oxide, for example N-coco dimethyl amine oxide, N-lauryl dimethyl amine oxide, N-myristyl dimethyl amine oxide and N-stearyl dimethyl amine oxide; N-acyl group amine oxide, for example N-cocamidopropyl propyl-dimethyl amine oxide and N-butter amidopropyl dimethyl oxidation amine; With N-alkoxyalkyl amine oxide, for example two (2-hydroxyethyl) C12-15 alkoxyl group propyl group amine oxides.Usually provide hydrophobic part in the amine oxide surfactant by the fat hydrocarbon chain that contains 10-21 carbon atom.

[0108] for purpose of the present invention, preferred alkylolamide and amine oxide surfactant.Usually, fatty diglycollic amide and N-alkyl dimethyl amine oxide are preferred in the composition of the present invention.Particularly preferably be fatty diglycollic amide and N-alkyl dimethyl amine oxide, wherein fat hydrocarbon chain contains 10-18 carbon atom.For example particularly preferred ionic surfactant pack is drawn together lauric acid diethyl amide, N-lauryl dimethyl amine oxide, lauric acid amide of ethanol, tetradecanoic acid diglycollic amide and oleic acid diethyl amide.

[0109] also can comprise the surfactant material of extra kind, for example positively charged ion and zwitterionics, with at length listed representative compounds in the U.S. Patent No. of submitting in February 20 nineteen ninety 4902499, think at this by with reference to being introduced into.

[0110] other auxiliary agent can be joined and comprise that being dispersed in alkylsiloxane flows in the composition of the present invention of blend of intravital diluted polymer, these auxiliary agents comprise that for example thickening material, spices, tinting material, ionogen, pH control composition, profoamer and suds-stabilizing agent, biocide, antioxidant, ultraviolet absorbers and medicine.For example preferably in composition, use thickening material sometimes, to promote applying composition to hair with hand.The preferred thickening material that uses capacity is to provide exquisite more effect.Be 6000-12 for example at 25 ℃ of range of viscosities of measuring down, 000mPa.s.Suitable thickening especially comprises sodiun alginate, gum arabic, polyoxyethylene, guar gum, Rhoximat RH 148, derivatived cellulose (methylcellulose gum for example, methylhydroxypropylcellulose, hydroxypropylcellulose, poly-propyl group Natvosol), starch and starch derivative (as hydroxyethyl amylose starch and amylose starch), Viscogum BE, ionogen (for example sodium-chlor or ammonium chloride), carbohydrate (for example fructose and glucose), derivative (for example PEG-120 methyl glucoside dioleate) with carbohydrate.

[0111] spices that can use in composition of the present invention is acceptable spices on the makeup.Can use tinting material usually, to give the composition color.Although do not require, preferably in composition of the present invention, use acid to regulate pH in the 5-9 scope, perhaps more preferably in the 6-8 scope.Any water soluble acid for example carboxylic acid or mineral acid is suitable.For example suitable acid comprises mineral acid for example hydrochloric acid, sulfuric acid and phosphoric acid, and monocarboxylic acid is for example succsinic acid, hexanodioic acid and citric acid of acetate, lactic acid or propionic acid and poly carboxylic acid for example.

[0112] if the extra amendment of hope for specific purpose then can add them.For example can add any known organic cation hair conditioning component.Can use in the present invention provides some of hair modification positively charged ions to regulate the quaternary nitrogen derivative that component comprises ether of cellulose, the homopolymer of dimethyl diallyl ammonium chloride, the multipolymer of acrylamide and dimethyl diallyl ammonium chloride, by the acrylic or methacrylic acid deutero-homopolymer or the multipolymer that contain the cationic nitrogen functional group that links to each other with polymkeric substance by ester or amido linkage, N, N`-two (2, the 3-epoxypropyl) polycondensation product of piperazine or piperazine-two-acrylamide and piperazine, poly-(neohexene ammonium chloride)-α, ω-two (triethanol ammonium) muriate, and vinyl pyrrolidone and multipolymer with acrylate of quaternary nitrogen functional group.In U.S. Patent No. 4240450, disclose above-mentioned cationic organic polymer and other material in more detail, be introduced into by reference at this, so that further describe cationic organic polymer.Also can use the amendment of other kind, for example the monomer quaternary amine.

[0113] can require sanitas, with spendable representative sanitas comprise about 0.1-0.2wt% such as following compound: formaldehyde, dihydroxymethyl T10,5-bromo-5-nitro-1, the mixture of 3-two  alkane, methyl p-hydroxybenzoate and propyl ester and this benzoic ether and Sodium dehydroacetate, xitix and Imidurea.

[0114] also can prepare to contain and be dispersed in the present composition that alkylsiloxane flows the blend of intravital diluted polymer and comprise in addition as for example long-acting curly hair system or hair dyeing and use required dyestuff, tinting material, reductive agent, neutralizing agent and sanitas.Available several different forms apply active prescription, comprising for example emulsion, gel, mousse, aerosol and spray with as amendment and shampoo.The suitable carriers fluid that activeconstituents can comprise carrier and be used for hair nursing prescription is a water, and the fluid such as alcohol (being ethanol or Virahol) is as the hydrocarbon of solvent oil and halohydrocarbon for example trichloroethane, annular siloxane and aerosol propellants.

[0115] when composition is intended being used for aerosol applications, can comprise propellant gas, for example carbonic acid gas, nitrogen, nitrous oxide, volatile hydrocarbon such as butane, Trimethylmethane or propane, with chlorination or fluorinated hydrocarbons such as Refrigerant 12 and dichloro tetrafluoro ethane, or dme.

[0116] products therefrom is forms such as ointment, frost, gel, paste, foam, aerosol.They can be present in medicine, in medicine and/or the treatment articles, anodyne for example, narcotic, anti-acne agents, antiseptic-germicide, anti-yeast agent, anti-mycotic agent, antiviral agent, anti-dandruff agent, anti-dermatitis agent, the relieving itching agent, antiemetic, anti-motion sickness medicine, anti-inflammatory agent, anti-keratinization of epidermis agent, the resist drying skin agent, antiperspirant, antipsoriatic, the agent of seborrhea dermatitis, hair conditioner, hair conditioner, antiaging agent, anti-wrinkle agent, anti-asthmatic, the anti-bronchoconstriction agent, sun-screening agent, antihistamine, skin whitener, depigmenting agent, Wound-healing agent, VITAMIN, corticosteroid, tannin or hormone.This series products commonly used comprises hair care product; for example shampoo, hair conditioner, hair coloring agent, hair fixing formulation example are as typing emulsion and hair spray and long-acting curly hair preparation; skin care products; face or health pulvis, kermes, eye shadow, informer, shower particle or pellet, lipstick, moistening agent, makeup, hand and body lotions, covering agent, die mould powder, foundation cream and sun-proof care products sunscreen formulas for example for example.

[0117] in the still further embodiment of the present invention, diluted polymer of the present invention can be incorporated in the full-bodied rubber composition.

[0118] according to the present invention, the method for preparing rubber composition is provided, this method comprises the steps:

[0119] but randomly with containing the end-capping reagent of alkenyl condensation group, silyl-hydride or trimethyl silyl and use the siloxanes thinner, prepare the polymkeric substance that contains organic based polysiloxane of foregoing dilution; Compounding contains polymkeric substance and one or more enhancings and/or the non-reinforcing filler and the solidifying agent of the organopolysiloxane of gained dilution.

[0119] in embodiments of the invention, can use the combination of foregoing any filler or filler.In per 100 parts by weight polymer (not comprising the thinner part), the content of filler is maintained at about 5 to about 200 weight part scopes in the composition usually.

[0120] requires aforesaid solidifying agent, and the compound that can use herein comprises organo-peroxide, dialkyl for example, the diphenyl peroxide base, benzoyl peroxide, peroxidation 1, the 4-dichloro-benzoyl, peroxidation 2, the 4-dichloro-benzoyl, di-t-butyl peroxide, dicumyl peroxide, t-butylperoxyl benzoate, peroxidation monochloro benzoyl, di-t-butyl peroxide, 2, two (t-butylperoxy)-2 of 5-, the 5-dimethylhexane, the tert-butyl peroxide trimethylammonium, the tertiary butyl-tertiary butyl-uncle's triphenyl superoxide, 1, two (t-butylperoxy)-3 of 1-, 3,5-trimethyl-cyclohexane and t-butylperoxyl benzoate.Only peroxide-based solidifying agent is benzoyl peroxide, peroxidation 2,4 dichloro benzene formyl, di-t-butyl peroxide and dicumyl peroxide.In the combination of per 100 parts of polymkeric substance, filler and optional additive, use maximum 10 parts this organo-peroxides.0.2 to 2 part of superoxide of preferred use.

[0121] also can replace organo-peroxide to solidify as solidifying agent and/or crosslinked composition of the present invention in conjunction with the organic radical hydrogen siloxane, provide and contain at least two most polymers molecules that are suitable for the crosslinked unsaturated group of organic radical hydrogen siloxane by hydrosilylation reaction catalyst.These groups typically are alkenyl, most preferably vinyl.In order to carry out the curing of the present composition, each molecule of organic radical hydrogen siloxane must contain greater than two and silicon bonded hydrogen atom.Each molecule of organic radical hydrogen siloxane can contain for example about 4-20 Siliciumatom, and the viscosity under 25 ℃ is maximum about 10Pa.s.That exist in the organic radical hydrogen siloxane and the organic group silicon bonding can comprise the replacement and the unsubstituted alkyl of 1-4 carbon atom, and described alkyl does not contain olefinic or acetylene series unsaturated link(age) in addition.

[0122] for the application's purpose, " replacement " is meant that the one or more hydrogen atoms in alkyl are replaced by another substituting group.This substituent example includes but not limited to: halogen atom, for example chlorine, fluorine, bromine and iodine; The group of halogen atom-containing, for example chloro methyl, perfluoro butyl, trifluoroethyl and nine fluorine hexyls; Sauerstoffatom; The group that contains Sauerstoffatom, for example (methyl) vinylformic acid and carboxyl; Nitrogen-atoms; The group of nitrogen atom, for example amido functional group; Amide group functional group, and cyano functional group; Sulphur atom; With the group of sulfur atom-containing, for example sulfydryl.

[0123] preferably, hydrosilylation catalysts can be foregoing any hydrosilylation catalysts, but preferred platinum based catalyst.

[0124], consumption can be equivalent to few hydrosilylation catalysts and join in the composition of the present invention to 0.001 weight part elemental platinum group metal in per 1,000,000 parts of (ppm) compositions.Preferably, the concentration of hydrosilylation catalysts can provide the equivalent of 1ppm elemental platinum group metal at least in composition.Provide the catalyst concn that is equivalent to about 3-50ppm elemental platinum group metal normally preferred consumption.

[0125] or solidifying agent can be condensation catalyst, this be because can by condensation reaction in conjunction with have at least two and preferred at least three can with the siloxanes and/or the silane crosslinker of the group of hydroxyl or hydrolysable group reaction, solidify and/or crosslinked composition of the present invention, contain at least two foregoing condensation groups that are suitable for described linking agent reaction but condition is the most polymers molecule.

[0126] optional additives that is used for the high consistency rubber composition can comprise following one or more: rheology modifier, pigment, tinting material, antiadhesives, adhesion promotor, thermo-stabilizer, whipping agent, fire retardant, conduction and/or heat conductive filler and siccative, each in them are preferably as previously mentioned.

[0127] other optional ingredients that can be incorporated in the high-consistency properties-correcting agent comprises treatment agent, peroxide cure auxiliary agent, acid acceptor and UV stablizer.

[0128] the uncured performance of using treatment agent to come modified silicon rubber, for example green strength or processibility, these treatment agents are sold by Dow Corning Corporation as SILASTIC  HA-1, HA-2 and HA-3 with the extensive stock name.

[0129] use the peroxide cure auxiliary agent to come the performance such as tensile strength, elongation, hardness, compression set, rebound resilience, binding property and dynamic deflection of modified solidified rubber.These can comprise two or the acrylate of trifunctional, for example Viscoat 295 and ethylene glycol dimethacrylate, cyanacrylate, triallylcyanurate, polyhutadiene oligopolymer and analogue.Silyl-hydride functional siloxane also can be used as the curing that auxiliary agent comes the peroxide catalyzed of modified silicon rubber.

[0130] acid acceptor can comprise magnesium oxide, lime carbonate, zinc oxide and analogue.

[0131] the ceramifying agent also can be described as the ash content stablizer, and comprises silicate, for example wollastonite.

[0132] can be by the rubber composition of any suitable path of preparing embodiment of the present invention, for example a preferred route is at first by heating pyrolytic silicon dioxide, the treatment agent of silicon-dioxide and the organopolysiloxane polymkeric substance of dilution of the present invention, preparation silicon rubber base-material.From first mixing roll, take out the silicon rubber base-material, and transfer in second mixing roll, in per 100 weight part silicon rubber base-materials, add the non-enhancing of about 150 weight parts or increment filler, for example crushed quartz usually at this.Typically, for example solidifying agent, pigment and tinting material, thermo-stabilizer, antiadhesives, softening agent and adhesion promotor are fed in second mixing roll with other additive.In second preferred route, organopolysiloxane polymkeric substance and any required filler of the present invention's dilution are added that any required treatment agent is fed in the reactor, and mix, the aforesaid further additive that will comprise solidifying agent then is fed in the same reactor and further mixing.

[0133] other potential application of the present invention comprise dilution polymkeric substance in hotmelt, pressure sensitive adhesive, the encapsulants of solar cell and requiring uses any other purposes in using of organopolysiloxane sizing material.

[0134] by embodiment the present invention is described.For the purpose of comparison, employed thinner is the commercially available processing aid that is called as HYDROSEAL  G250H in these two embodiment, the mineral oil fractions (n-paraffin 7%/isoparaffin 51% and alicyclic hydrocarbon 42%) of the hydrotreatment that a kind of Total Fina produces.

Embodiment 1-uses the chain extension of dibutyl acetoxysilane

The production of polymkeric substance

[0135] be 80 with 50g 25 ℃ of following viscosity, the end capped polydimethylsiloxane of the dimethyl hydroxyl of 000mPa.s is placed in the suitable containers.0.2g dibutoxy diacetoxy silane (DBDAc) and 500ppm weight (with respect to polymkeric substance) the oxalic acid two fourth tin catalysts water with stoichiometric amount is added, with the acetoxyl group of hydrolysis on DBDAc.When one detects the initial viscosity increase, immediately the 50g processing aid is incorporated in the reaction mixture, and follows the tracks of viscosity change, reach maximum value up to product viscosity.

Sealant dispensing

[0136] adopts 86.485% polymkeric substance, the methyl triacetoxysilane of 5wt% and 50% mixture of producing as mentioned above of ethyl triacetoxysilane linking agent, the 8wt% pyrolytic silicon dioxide, 0.5wt% poly-(PO) is (rheology modifier) and 0.015% oxalic acid, two fourth tin catalysts (EO), the sealing agent of preparation resulting polymers.Table 1 shows the performance of sealing agent.

[0137] carry out bond test (7dRT), show that permission was solidified 7 days under 23 ℃ and 50% relative humidity after, the sealing agent bead successfully is bonded on the normal glass plate.After the set time section, with 90 ° of tractive beads, assessment binding property and evaluation as described below destroy:

0: adhesion failure (poor adhesion)

1: interface or mixed mode (bonding/interior poly-) destruction-acceptable binding property

2: cohesive failure-binding property is good

[0138] carries out bond test (7H ₂O), show that permission was solidified 7 days under 23 ℃ and 50% relative humidity and subsequently in water after 7 days, the sealing agent bead successfully is bonded on the normal glass plate.With the same tractive sealing agent bead in the bond test (7dRT).

[0139] by fills suitable containers (avoiding introducing gas enclosure) with sealing agent, the suitable time period of sealing agent that under room temperature (about 23 ℃) and about 50% relative humidity, comprises in the curing vessel, be cured degree of depth test, how far sealing agent hardens below the surface in 24 hours and 72 hours to be determined at.After appropriate curing time, take out sample from container, and measure the height of solidified sample.

Table 1

Standard performance	Method
Standard performance	Method			Surface drying time (min)	ASTM D2377-94	24
Penetration degree (mm/10*3sec)	ASTM D217-97	170		Surface drying time (min)	ASTM D2377-94	24
Penetration degree (mm/10*3sec)	ASTM D217-97	170		Curing depth 24 hours (mm/24h)		1.5
Curing depth 72 hours (mm/72h)		1.7		Curing depth 24 hours (mm/24h)		1.5
Curing depth 72 hours (mm/72h)		1.7		Proportion (kg/l)	ASTM D1475-98	0.94
Tensile strength (sheet material 2mm) (MPa)	ASTM D412-98a	0.6		Proportion (kg/l)	ASTM D1475-98	0.94
Tensile strength (sheet material 2mm) (MPa)	ASTM D412-98a	0.6		Elongation at break (%)	ASTM D412-98a	1047
100% modulus (MPa)	ASTM D 638-97	0.13		Elongation at break (%)	ASTM D412-98a	1047
100% modulus (MPa)	ASTM D 638-97	0.13		Hardness	(Shore A) ASTM D2240-97	5
				Hardness	(Shore A) ASTM D2240-97	5

Bond test		7dRT	7H ₂O
Bond test		7dRT	7H ₂O		Glass	2	2

Claims

1. method that contains organic based polysiloxane polymkeric substance for preparing the chain extension of dilution, this method comprises the steps:

(i) diethylamide base silane, diacetoxy silane, dichlorosilane, wherein each amino has diamino silanes, dialkoxy silicane, diamide base silane, six organic radical disilazanes, two ketoximinosilanes of one or two N-H key with respect to each nitrogen;

(iv) structure is ZMe ₂SiO (Me ₂SiO) _ySiMe ₂Z or ZMe ₂Si-Y-SiMe ₂The compound of Z, wherein Z is a heterocycle Si-N base, Y is selected from-(CR ₂) _m-or-C ₆H ₄-bivalent hydrocarbon radical, y be 0 or integer and m be 2-6, comprise that end value and R are univalence hydrocarbyls;

(v) two alkenyl silanes, two hydrogen silanes,

(vi) the polymerization degree be 2-25 and relatively each end group have the polydialkysiloxane of at least one Si-alkene base key,

(vii) the polymerization degree be 2-25 and relatively each end group have the polydialkysiloxane of at least one Si-H key; With

(b) optionally, this chain extension technology of quencher;

2. the process of claim 1 wherein that the general formula of preformed polymkeric substance is:

X ¹-A-X ²

X wherein ¹And X ²Be independently selected from the silyl that contains hydroxyl or hydrolysable group, it is selected from-SiOH ₃,-(R ^a) SiOH ₂,-(R ^a) ₂SiOH ,-R ^aSi (OR ^b) ₂,-Si (OR ^b) ₃,-R ^a ₂SiOR ^bOr-R ^a ₂Si-R ^c-SiR ^d _p(OR ^b) _3-p, each R wherein ^aRepresent univalence hydrocarbyl independently, alkyl for example especially has the alkyl of 1-8 carbon atom; Each R ^bAnd R ^dBase is alkyl or alkoxyl group independently, and alkyl wherein has maximum 6 carbon atoms suitably; R ^cBe bivalent hydrocarbon radical, it can be disconnected by one or more siloxanes spacers with maximum 6 Siliciumatoms; With the numerical value of p be 0,1 or 2 and A be the polymer chain that contains siloxanes.

3. the method for claim 2 is characterized in that the polymer chain A that contains siloxanes is selected from siloxane polymer chain, silicone copolymers chain and siloxanes/organic segmented copolymer chain.

4. claim 2 or 3 method, wherein employed catalyzer is selected from the zirconate and the organo-tin compound of titanic acid ester, chelated titanates, zirconate, chelating.

5. the process of claim 1 wherein that the general formula of preformed polymkeric substance is:

X ¹-A-X ²

X wherein ¹And X ²Be independently selected from the silyl that contains at least one Si-H key and A and be the polymer chain that contains siloxanes that is selected from siloxane polymer chain, silicone copolymers chain and siloxanes/organic segmented copolymer chain and each molecule of chainextender comprise can with X ¹And X ²Two unsaturated substituting groups of interior Si-H key reaction.

6. the process of claim 1 wherein that the general formula of preformed polymkeric substance is:

X ¹-A-X ²

X wherein ¹And X ²Be independently selected from and contain at least one unsaturated substituent silyl and A and be selected from siloxane polymer chain, silicone copolymers chain and siloxanes/organic segmented copolymer chain and chainextender and comprise and being suitable for and X ¹And X ²In two Si-H keys of unsaturated substitution reaction.

7. claim 4 or 5 method, wherein each unsaturated group is that alkenyl and catalyzer are hydrosilylation catalysts.

8. the method for aforementioned any one claim, wherein said/or each thinner be processing aid or softening agent.

9. the method for aforementioned any one claim, wherein thinner is selected from one or more in following: the end capped polydialkysiloxane of trialkylsilkl, wherein each alkyl can be identical or different and be comprised 1-6 carbon atom, but preferable methyl, preferably its viscosity is 100-100 under 25 ℃, 000mPa.s; Polyisobutene (PIB); Phosphoric acid ester; Polyoxyethylene alkylphenyl; The alkyl phenyl ester of the straight chain of mono carboxylic acid of aliphatic series and/or side chain.

10. any one method of claim 1-7, wherein thinner be selected from following one or more, contain the straight or branched list unsaturated hydrocarbons of 12-25 carbon atom, for example alkene of straight or branched, or its mixture; And/or contain the mineral oil fractions of straight chain (n-paraffin) mineral oil, side chain (isoparaffin) mineral oil and/or ring-type (alicyclic hydrocarbon) mineral oil and composition thereof.

11. the method for aforementioned any one claim, wherein the polymkeric substance that contains organic based polysiloxane of the chain extension of thinner and dilution is miscible at least basically.

12. the polymkeric substance that contains organic based polysiloxane of the chain extension of the dilution that can obtain by the method for aforementioned any one claim.

13. one kind prepares and can be solidified into elastomeric moisture cured method for compositions, has reactive suitable crosslinking agents, suitable condensation catalyst and optional filler but this method comprises the steps: to mix the polymkeric substance that contains organic based polysiloxane and the polymkeric substance that contains organic based polysiloxane to the chain extension of this dilution of the chain extension of the dilution that comprises the condensation group that can be by any one acquisition of claim 1-3.

14. the preparation of claim 12 can be solidified into elastomeric moisture cured method for compositions, wherein linking agent is that to contain one or more silane of acyloxy, ketoxime base or siloxanes and catalyzer be tin catalyst.

15. the preparation of claim 13 can be solidified into elastomeric moisture cured method for compositions, wherein linking agent is that to contain one or more silane of alkoxyl group and alkenyl oxy or siloxanes and catalyzer be the titanic acid ester or the zirconate of titanic acid ester or zirconate or chelating.

16. any one preparation of claim 12-14 can be solidified into elastomeric moisture cured method for compositions, described composition comprises the reinforcing filler that one or more are fine in addition, the for example pyrolytic silicon dioxide of high surface area, precipitated silica and lime carbonate, and/or increment filler, for example crushed quartz, diatomite, barium sulfate, ferric oxide, titanium dioxide, carbon black, talcum or wollastonite.

17. one kind can be solidified into elastomeric moisture cured composition, said composition comprises:

A. have and be no less than 2 polymkeric substance that contain organic based polysiloxane with the chain extension of the dilution of the hydroxyl of silicon bonding or hydrolysable group

B. each molecule has at least two siloxanes and/or silane crosslinkers that hydroxyl in this polymkeric substance or hydrolysable group had reactive group

C. one or more fillers and

D. suitable curing catalysts.

18. the encapsulant composition of claim 13 is wherein according to any one the organopolysiloxane of method preparation dilution of claim 1-3.

19. the solidified sealing agent of a japanning, it comprises claim 15 or 16 any one cured compositions.

20. a solidified sealing agent, it comprises that elongation at break is greater than 700% claim 1 or 15 cured compositions.

21. one kind can be solidified into elastomeric moisture cured composition, said composition can by compounding according to claim 1-8 any one method preparation dilution the organopolysiloxane polymkeric substance with this organopolysiloxane polymkeric substance is had reactive suitable crosslinking agents, suitable condensation catalyst and optional filler and obtains to form single part or two portions organopolysiloxane encapsulant composition.

22. comprising, spatial method between two unit of a sealing, described method apply claim 12,15 or 16 any one compositions in described space and cause or allows said composition curing.

23. a sealing agent, it comprises the composition of claim 15 or 16.

24. glazing structure or building unit, it comprises the sealing agent that is obtained by any one composition of claim 1-17.

25. the purposes of polymkeric substance in sealing agent according to the polymkeric substance increment that contains organic based polysiloxane of the chain extension of the dilution of any one preparation of claim 1-3.

26. composition, it comprises the polymkeric substance that contains organopolysiloxane of the chain extension of the dilution that can obtain according to any one method of claim 1-3, wherein after finishing polymerization, will contain viscosity and be the extra thinner of fluidic that 4 to 100mPa.s volatility or non-volatile low molecular weight contain organic based polysiloxane and join in the composition.

27. the composition of claim 25, it comprises that in addition one or more tensio-active agents, washing composition, thickening material, spices, tinting material, ionogen, pH control composition, profoamer and suds-stabilizing agent, biocide, antioxidant, ultraviolet absorbers and medicine dyestuff, reductive agent, neutralizing agent and sanitas.

28. the purposes of the composition of claim 25 or 26 in medicine, medical treatment and/or therapeutic composition.

29. the composition of claim 25 or 26 is at the preparation medicine, purposes in medical treatment and/or the treatment product is used for one or more following application: anodyne, narcotic, anti-acne agents, antiseptic-germicide, anti-yeast agent, anti-mycotic agent, antiviral agent, anti-dandruff agent, anti-dermatitis agent, the relieving itching agent, antiemetic, anti-motion sickness medicine, anti-inflammatory agent, anti-keratinization of epidermis agent, the resist drying skin agent, antiperspirant, antipsoriatic, the agent of seborrhea dermatitis, hair conditioner, hair conditioner, antiaging agent, anti-wrinkle agent, anti-asthmatic, the anti-bronchoconstriction agent, sun-screening agent, antihistamine, skin whitener, depigmenting agent, Wound-healing agent, VITAMIN, corticosteroid, tannin or hormone.

30. a pharmaceutical composition, it comprises composition and the physiology and/or the pharmaceutically acceptable carrier of claim 25 or 26.

31. the pharmaceutical composition of claim 29 is used for topical application, it comprises ointment, frost, gel, paste, foam or aerosol.

32. a hair care product, it comprises the composition of claim 25 or 26.

33. a method for preparing rubber composition, this method comprises the steps:

But randomly prepare any one the polymkeric substance that contains organic based polysiloxane of dilution of claim 1-11 with containing the end-capping reagent of alkenyl condensation group, silyl-hydride or trimethyl silyl and siloxanes thinner;

Organopolysiloxane polymkeric substance and one or more enhancings and/or the non-reinforcing filler and the solidifying agent of compounding gained dilution and be selected from the additive of choosing wantonly in rheology modifier, pigment, tinting material, antiadhesives, adhesion promotor, whipping agent, fire retardant and the siccative.

34. the method for claim 33, wherein solidifying agent is to be selected from dialkyl, diphenyl peroxide base, benzoyl peroxide, peroxidation 1,4-dichloro-benzoyl, peroxidation 2,4-dichloro-benzoyl, di-t-butyl peroxide, dicumyl peroxide, t-butylperoxyl benzoate, peroxidation monochloro benzoyl, di-t-butyl peroxide, 2, two (t-butylperoxy)-2 of 5-, one or more organo-peroxides in 5-dimethylhexane, tert-butyl peroxide trimethylammonium, the tertiary butyl-tertiary butyl-uncle's triphenyl superoxide and the t-butylperoxyl benzoate.

35. the method for claim 33, wherein polymkeric substance comprises that unsaturated group and solidifying agent are that hydrosilylation reaction catalyst is in conjunction with the organic radical hydrogen siloxane.

36. the method for claim 33, wherein each molecule of organic radical hydrogen siloxane comprises 4-20 Siliciumatom, and the viscosity under 25 ℃ is maximum about 10Pa.s.

37. the method for claim 33, wherein hydrosilylation catalysts is that the platinum metals that is selected from platinum, rhodium, iridium, palladium or the ruthenium catalyst is catalyst based.