CN101151329B - Organosiloxane compositions - Google Patents

Abstract

The present invention relates to a moisture curable composition capable of cure to an elastomeric body comprising (a) a diluted polymer comprising (i) a silicon containing polymer of the formula X-A-X<1> where X and X<1> are independently selected from silyl groups which contain one or more condensable substituents per group and A is a polymeric chain having a number average molecular weight (Mn) of at least 132000 and a degree of polymerisation of at least 1800. (ii) an organic extender and/or plasticiser which diluted polymer is obtained by polymerisation in the presence of the said organic extender and/or plasticiser (b) a suitable cross-linking agent which comprises at least two groups which are reactable with the condensable groups in the diluted polymer, (c) a suitable condensation catalyst and optionally (d) one or more fillers.

Description

Organosiloxane compositions

The present invention relates to encapsulant composition, but it comprises in the presence of extender and/or softening agent polymeric, has the high molecular silicon-containing polymer of condensation end group.

The rheological property of uncured polymer mainly is the function of its viscosity.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 viscosity of uncured polymkeric substance is directly related with the length (being normally defined the polymerization degree (dp)) of the molecular weight of polymkeric substance and polymer chain.The viscosity of uncured polymer also is the composition major influence factors of the several physical performance of encapsulant composition for example of mixing this polymkeric substance, when with this composition of after fixing.

The organosiloxane compositions that is solidified into Hookean body is known, and can produce this composition, at room temperature, solidify solidifying in the presence of the moisture or applying under the heat.Typically, by in the presence of one or more fillers and curing catalysts, mix and to have the poly-diorganosiloxane based polyalcohol of reactive terminal group and suitable silane (or siloxanes) based cross-linker, acquisition at room temperature, in the presence of moisture these compositions of solidified.Typically with at room temperature be exposed to atmospheric moisture following time curable single part composition or when under room temperature and pressure, mixing curable two portions composition forms prepare these compositions.

An important use of above-described curable compositions is that it is used 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 therein with paste form, 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, and 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.

The normal requirement is incorporated into mineral filler in the elastic composition that comprises the polymkeric substance that contains organic based polysiloxane, with obtain useful to tear, 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, uncured contain organic based polysiloxane 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 examples of high extruded velocity such as uncured sealing agent (it is in use manually extruded with sealant gun or analogue usually) typically to need to have low viscosity (for example under 25 ℃,＜100000mPa), to guarantee suitable composition extruded velocity for manually finally using.

The 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.

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 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 ℃.

A kind of molecular weight that is used for increasing polymkeric substance keeps enough low extruded velocity simultaneously so that the method that said composition can be extruded with craft such as for example sealant gun is to provide chainextender in uncured composition.With the polymkeric substance of chainextender and pre-preparation with all other composition component are mixed and with air tight manner storage said composition.Owing to select chainextender, known it with the speed of response of polymer terminal group than with composition in the speed of response of the linking agent that provides fast, so the molecular weight of polymkeric substance increases during contact wetting.The case description of this method is at US6833407, US4020044, US2004/0122199 and US5300612.

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

Use extender (being also referred to as processing aid or extender plasticizer sometimes) to 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.In siloxane sealant composition, introduce one or more extenders 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 extender 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 extender does not lose by for example evaporating or ooze out from the solidified sealing agent.

Add 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 that this is not its purposes of mainly planning and some softening agent is expensive really, may increase the unit cost of the sealant dispensing that they use within it.Plasticizer volatility is usually less than extender, 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 viscosity of this polydimethylsiloxane is generally 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 is ethylene glycol and derivative thereof for example; Organophosphate, for example Tritolyl Phosphate and/or triphenylphosphate; Viscotrol C; Tung oil; The ester of lipid acid and/or lipid acid.

Usually, softening agent is easier to be compatible with polymer composition more much lower with volatility than extender, obviously more may stay in the polymeric matrix with relatively large after therefore solidifying.

Extender 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 the storage process, when applying sealing agent and for some time at least afterwards, the extender of some propositions is effective, about its purposes, has 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 extender;

(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 with negative impact cured product for example physics and the aesthstic performance and the life-span of sealing agent; With

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

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 extender and/or softening agent are incorporated into that uses in industry, and for example polymkeric substance, linking agent, catalyzer, filler and described or each extender and/or softening agent are formed.With organic radical polymer phase ratio, the consistency of other composition is remarkable bigger problem in organic extender and/or softening agent and the silica alkyl polymer composition, the siloxane polymer that extender 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 extender and/or the plasticizer dosage in the polymer composition effectively.Typically, this extender that especially causes introducing remarkable lower aq with comparing of may expecting is in composition, this be because extender not fully well physics be not mixed in the polymer composition, especially with composition in except filler, be generally largest component preformed polymkeric substance less than physical mixed fully well.Softening agent and the extender compatibility problem in silicone polymers combination has been known in this industry since introducing organic extender always, known to the inventor, up to the organic radical extender of the present invention, just solved this problem by proposing to accelerate.

DE3342026 discloses the method that involves preformed organopolysiloxane polymkeric substance of a part of physical blending together and some or all of softening agent.Exemplified in an embodiment and used 20 ℃ of following viscosity about only 80,000mPa.s α, alpha, omega-dihydroxy polydimethyl siloxane physical blending polymkeric substance and softening agent, so problem of having avoided the inventor to emphasize, and this problem will run in the technology of using the full-bodied polymkeric substance of this physical blending, wherein this blending technology will involve and long-time section ground use very expensive mixing equipment to obtain the blend that looks suitable, thereby make the infeasible economically and most probable of this technology not provide suitable blend.

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 extender and/or softening agent, this is because they chemically similar, and have good consistency.

Wide in range various organic compound and composition reduce siloxane sealant composition as extender cost has been proposed.These materials are categorized as two groups usually: high volatile volatile extender and low volatility extender.

The composition that contains the high volatile volatile extender 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.

Select low volatility extender (being sometimes referred to as the extender of higher molecular weight), its be intended that have with encapsulant composition in the good consistency of polymkeric substance.The extender of these higher molecular weights can completely or partially substitute the PDMS softening agent in the prescription.

Low-molecular-weight polyisobutene (PIB) has been proposed as extender in DE2364856 and DE3217516.Yet because consistency is limited, the maximum scope that therefore can join the PIB extender in the acetoxyl group silicone encapsulants prescription typically is 25-30wt%.Higher addition causes that extender 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 extender.

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

GB2041955 discloses dodecylbenzene and the purposes of other alkylaromatic hydrocarbon as organic extender.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 extender.EP0043501 has proposed to be the side chain of the 0.2-15% of encapsulant composition weight and/or the cyclic alkane purposes of hexanaphthene, isohexane and isooctadecane for example.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).WO 99/66012 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 extender.

In recent years, the industrial alkane that uses further is as extender.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 extender, 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 to use and has comprised based on 100 weight part hydrocarbon having greater than 40 weight part cyclic alkane with less than the extender of 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 " extender " that preferably contains greater than the 40wt% cyclic alkane.

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 that after solidifying, the sealing agent of increment can ooze out extender, thereby causes the remarkable decline of solidified sealant lifetime, this is a lower boiling especially general feature of processing aid for example＜100 ℃.Although preparation person is interested is to mix the extender of high capacity in its encapsulant composition, but the physical mixed extender 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 extender that mixes large volume hinders to the physics in the encapsulant composition.Therefore usually find, can be incorporated into the combination that extender consumption in the encapsulant composition depends on employed extender or extender, typically between 20 to 40wt%.

Although many organic extender potentializations set forth above, they all have problem usually.Although for example the alkylbenzene extender has the performance combination that looks suitable, promptly high boiling point, with the good consistency of poly-diorganosiloxane polymeric matrix (thereby it is good in good transparency to cause the solidified silicone encapsulants to have), low environmental influence, low vapour pressure (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 extender, for example under the situation of phosphoric acid ester or polyisobutene, this problem can not occur.

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, extender 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 and will almost can not provide the homogeneous dispersion of composition components (especially filler and extender and/or softening agent) in polymkeric substance.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.

According to the present invention, provide a kind of and can be solidified into elastomeric moisture cured composition, it comprises:

(a) Xi Shi polymkeric substance, the polymkeric substance of described dilution comprises

(i) silicon-containing polymer of following formula

X-A-X ¹

Wherein X and X ¹Be independently selected from each group but to contain the substituent silyl of one or more condensations and A be number-average molecular weight (Mn) at least 132000 and the polymerization degree be at least 1800 polymer chain,

(ii) organic extender and/or softening agent

The polymkeric substance of described dilution be by have described organic extender and/or softening agent in the presence of polyreaction obtain;

(b) suitable crosslinking agent, but it comprise at least two can with the group of condensation radical reaction in the polymkeric substance of dilution,

(c) suitable condensation catalyst and optional

(e) one or more fillers.

Notion as used herein " contains, comprises " to be used on its most wide in range meaning, it be meant and include wording " comprising, " and " by ... form "

For the sake of clarity, term " monomer " and derivative thereof are meant monomer or the oligopolymer parent material that relates in the polymerization technique herein.

Preferably, blended monomer parent material is miscible or miscible at least basically and more specifically miscible or miscible at least basically with intermediate polymeric reaction product and final polymerisate with it at first each thinner and/or softening agent and they." miscible basically extender and/or softening agent " intend being included in the polymerization process with monomer and/or reaction mixture fully or most of miscible thinner and/or softening agent, therefore can be included in the low-melting solid that in reaction mixture, becomes compatibility liquid in the polymerization technique process.

The polymkeric substance that contains organic radical siloxane intend referring to each molecule contain the polymkeric substance of a plurality of organopolysiloxane groups 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.

The polymkeric substance of dilution comprises polymeric constituent, it is that number-average molecular weight (Mn) is at least 132 according to the present invention, 000 and the polymerization degree be at least 1800 silicon-containing polymer, wherein molecular weight is measured by D5296-05 and is calculated with respect to polystyrene molecular weight equivalent.With regard to organopolysiloxane polymer, M _nValue is 132000 to be equivalent to weight-average molecular weight (M _w) be 198,000 and common 25 ℃ of following viscosity greater than 1000000mPas.

Preferred silicon-containing polymer is the polymkeric substance that contains organic radical siloxane, and it preferably has following general formula

X ¹-A-X ² (1)

X wherein ¹And X ²But siliceous suitably condensation group and A are siloxane polymer chain, organic polymer chain, silicone copolymers chain or siloxanes/organic segmented copolymer chains.

Each X ¹Or X ²But group contains suitable condensation substituting group, and it is through selecting to react via condensation reaction with selected linking agent.For fear of doubt, condensation reaction is the reaction that causes eliminating between the reactant of low molecular weight by-products such as water, ammonia or methyl alcohol etc.

But the condensation end group of polymkeric substance and this reaction between the linking agent are most preferably relevant with the interaction of the compound with hydroxyl and/or hydrolyzable end group usually, and they can react to each other and discharge for example water or methyl alcohol etc.Yet following enumerating pointed out admissible other of the solidification process of composition of the present invention reacted to each other:

1) condensation of organic radical halo silyl and organic radical alkoxysilyl,

2) condensation of organic radical halo silyl and organic radical acyloxy silyl,

3) condensation of organic radical halo silyl and organosilanes alcohol,

4) condensation of organic radical halo silyl and silanol,

5) condensation of organic radical hydrogen silyl and organosilanes alcohol radical,

6) condensation of organic radical alkoxysilyl and organic radical acyloxy silyl,

7) condensation of organic radical alkoxysilyl and organosilanes alcohol radical,

8) condensation of amino silyl of organic radical and organosilanes alcohol,

9) condensation of organic radical acyloxy silyl and silanol base,

10) condensation of organic radical acyloxy silyl and organosilanes alcohol,

11) condensation of organic radical oximido silyl and organosilanes alcohol radical,

12) condensation of organic radical alkene oxygen base silyl and organosilanes alcohol,

13) contain the silicone compounds and the silicone compounds condensation that contains at least one alkoxysilane-functional group of one or more hydrogen silane functional group, thereby generate the hydrocarbon by product.

Yet preferred X ¹Or X ²Be the end capped or hydrolyzable substituent silyl of hydroxyl, for example-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 separated by one or more siloxanes spacers with maximum 6 Siliciumatoms; With the numerical value of p be 0,1 or 2.Preferably, X ²And/or X ¹It is hydrolyzable group in the presence of moisture.

In one embodiment, the X of certain proportion (maximum 20%) ²Base can be a trialkylsilkl.

In general formula (1), the example of the suitable polymer chain A that contains siloxanes is to comprise those that gather the diorganosiloxane chain.Therefore, group A preferably includes the siloxane unit of formula (2),

-(R ⁵ _sSiO _(4-s)/2)- (2)

Wherein each R5 is organic group independently, for example has the alkyl of 1-18 carbon atom, has the alkyl of the replacement of 1-18 carbon atom, or has the-oxyl of maximum 18 carbon atoms, and 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.

Polymer chain A in the compound of general formula (1) can comprise any suitable siloxanes or siloxanes/organic molecule chain, provide resulting polymers (according to the present invention, under the situation that does not have thinner) viscosity under 25 ℃ reaches at least 20,000,000mPa.s (promptly, the polymerization degree (dp) up to or even greater than the unit of 200,000 formulas (2)).In a preferred embodiment, for all chain units, polymer chain 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 be maximum 200,000.Under the situation that does not have extender, the viscosity of suitable polymers under 25 ℃ is at least 20,000,000mPa.s, but when preparing under the situation that has extender, the order of magnitude 25 ℃ of following viscosity is generally 1000-100,000mPa.s, and this is because there is extender in polymeric matrix.Poly-diorganosiloxane can be homopolymer or multipolymer.But the mixture of the different poly-diorganosiloxanes with condensation end group also is suitable.

Although polymer chain A preferably only is the organopolysiloxane chain, but polymer chain A can or contain the segmented copolymer chain of block that at least one formula (2) is described the siloxane groups of type, with 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), poly-(to trimethyl silyl vinylbenzene) and gather (to trimethyl silyl-alpha-methyl styrene).Other organic constituent that can be incorporated in the polymer chain A 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.

Yet most preferred organic radical polymer blocks may be that polyoxy alkylidene is the block on basis in A.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.

Other polyoxy alkylidene block can comprise for example unit of following structure:

-[-R ^e-O-(-R ^f-O-) _p-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 p and q are that scope is the positive integer of 3-30.In addition, A can only comprise organic based polyalcohol chain, and A can comprise top at the disclosed any organic polymer chain of segmented copolymer in this case.

Can use any suitable extender or the extender of combination conduct in the polymkeric substance of increment of extender.These comprise following independent each of enumerating or with other combine:

The end capped polydialkysiloxane of trialkylsilkl, wherein alkyl methyl preferably;

Polyisobutene (PIB)

Phosphoric acid ester, for example trioctyl phosphate

Polyoxyethylene alkylphenyl

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

The ester of mono carboxylic acid of aliphatic series

Nonreactive short chain siloxanes

Straight or branched list unsaturated hydrocarbons for example contains alkene or its mixture of the straight or branched of 12-25 carbon atom; 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.Preferably, each molecule of employed hydrocarbon comprises 5-25 carbon atom.

Preferred extender comprises mineral oil fractions, alkyl alicyclic compound and alkylbenzene, comprising polyoxyethylene alkylphenyl.

Other preferred mineral oils extender comprises alkyl alicyclic compound and alkylbenzene, comprising polyoxyethylene alkylphenyl.

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 (number-average 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 polycyclic 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 the alicyclic hydrocarbon greater than 60wt%, many ring greases of 20wt% cyclic hydrocarbon and ASTM D-86 boiling point are 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.

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) on average at least 12 carbon atoms, most preferably each molecule 1 2-30 carbon atom of each molecule;

(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 that the 20-70wt% of extender and mineral oil based extender have the paraffinicity (according to ASTM D 3238) for extender 30-80wt%;

(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);

(xiii) 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).

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 extender 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 extender 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.

Especially, have general formula (I), wherein R according to the employed extender 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.

The 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.

The 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 few more.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.

Most preferably extender comprises mineral oil fractions.

Can use any suitable crosslinking agent, condition is the condensation reaction that it can participate in polymkeric substance.The linking agent (b) that is used for foregoing moisture cured composition preferably contains the silane or the silicone compounds of at least two and preferred at least three hydroxyls and/or hydrolysable group.These comprise and containing and the hydrolysable group of 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).

Under the situation of siloxanes linking agent, molecular structure can be straight chain, side chain or ring-type.

Each molecule of linking agent can have two but preferably have three or four with the condensation group of silicon bonding but (preferred hydrolysable group).When linking agent is a silane and when each molecule of silane has three 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.

Can be used as the silane of linking agent and siloxanes and comprise for example for example vinyltrimethoxy silane and vinyltriethoxysilane, isobutyl-Trimethoxy silane (iBTM) of methyltrimethoxy silane (MTM) and Union carbide A-162, alkenyl trialkoxy silane of alkyltrialkoxysilaneand.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.

The 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% exist, and the oximido linking agent that has higher molecular weight usually typically accounts for 3-8w/w%.

Composition further comprises condensation catalyst.Depend on desired curing speed for being included in the catalyzer of selecting in the specific siloxane sealant composition.Can use any suitable condensation catalyst to come curing composition, comprising tin, lead, antimony, iron, cadmium, barium, manganese, zinc, chromium, cobalt, nickel, titanium, aluminium, gallium or germanium and Zirconium-base catalyst, organotin metal catalyst for example perhaps can use the 2-ethylhexoate of iron, cobalt, manganese, lead and zinc.Preferred organotin, titanic acid ester and/or zirconate are catalyst based.

The siloxane sealant composition 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 carboxyl p-methoxy-phenyl tin, 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.

For the composition that contains alkoxy silane cross linked immunomodulator compounds, preferred curing catalysts is titanic acid ester or zirconate compound.This titanic acid ester can comprise general formula Ti[OR ²²] ₄Compound, each R wherein ²²Can 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 ²²Preferred 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 ²²When identical, R ²²Be the secondary alkyl of sec.-propyl, side chain or tertiary alkyl, the especially tertiary butyl.Example comprises the titanic acid ester or the zirconate of tetrabutyl titanate, titanium isopropylate or 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.

In addition, titanic acid ester can be a chelating.Can be and any suitable sequestrant for example alkyl acetylacetonate, for example chelating of methyl or ethyl Acetyl Acetone thing.Therefore, catalyzer can comprise following mixture or reaction product:

(i) M (OR) ₄Or (ii) M (OR ') _x(Z) _z

Wherein M is titanium or zirconium, each R ' is identical or different and be primary, the second month in a season or uncle's aliphatic hydrocarbyl or-SiR ⁹ ₃, each R wherein ⁹It is alkyl with 1-6 carbon atom; Z is the group of general formula-O-Y-O-, and wherein Y is the alkylidene group that contains the randomly branching of 1-8 carbon atom; With x be 0 or 2, wherein if x be 0, then z be 2 and if x be 2, then z is 1;

With

The compound that (iii) has following general formula:

Wherein

R ¹Be alkylidene group with optional replacement of 1-6 carbon atom,

A ' is selected from:

(i)-(CX ₂) _nC (R ²) ₃, wherein n is 0-5,

(ii) adamantyl and

(iii) adamantyl derivative;

B ' is selected from:

A ")-(CX ₂) _tC (R ²) ₃, wherein the numerical value of t is 0-5,

B ") have 1-6 carbon atom monovalent alkyl and

C ") OR ³, R wherein ³Be selected from (a ") or (b ")

Each X is identical or different and be halogen group or hydrogen;

Each R ²Identical or different, and be X or the alkyl with 1-8 carbon atom.

For example, produce these materials by making above-mentioned alcoholate and α-or beta-diketon or derivatives thereof reaction.The titanium compound that more preferably has those part chelatings that are connected to two alcoholate groups on the titanium.Most preferred organic titanic compound be wherein two alcoholate groups by form greater than 3 carbon atoms those, for example two (diethylidene glycoxy)-titanium-(2,4-diacetylmethane thing).

When Z be-during O-Y-O-, each Sauerstoffatom is bonded directly on the titanium atom, and x is about 2.Preferably, Y is the alkylidene group that contains 1-8 carbon atom.The example of-O-Y-O-base can comprise 1,3-two Ethylene Oxides (O-(CH ₂) ₃-O), 2,4-dimethyl-2,4-dioxolane (O-C ((CH ₃) ₂)-CH ₂-C ((CH ₃) ₂)-O) and 2,3-dimethyl-2,3-dioxy butane (O-C ((CH ₃) ₂)-C-((CH ₃) ₂)-O).

About compound (iii), preferably at least one and most preferably each X be halogen group.Most preferably halogen group is fluorine-based.Similarly, preferably at least one and each R most preferably ²It is halogen group and most preferably it is fluorine-based or each R ²Be alkyl, most preferable or ethyl or butyl.In most preferred prescription, n is 0.R ¹Methylene radical most preferably, but can have the alkyl of 1-5 carbon atom of band or the alkyl of halogen replacement.Adamantyl is diamantane or three rings-3,3,1, the derivative of 1-decane, and it is based on the stiffening ring system of three condensed cyclohexane rings.

Compound example (iii) comprises pentanoyl methyl acetate (MPA) and 4,4,4-trifluoroacetic ethyl acetoacetate (TFA).

Preferably, the component of per relatively 100 weight parts (a), catalyst component (c) is with the amount of 0.3-6 weight part, and the about 0.2-2% that is composition weight exists, and when using sequestrant, component (c) can exist greater than the amount of 6 weight parts.

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, with suitable ratio (for example 1: 1-10: 1) mix.Can in the first part of composition or second section, provide the extra additive of the following stated, but preferably in second section, add.

Single part of the present invention or two portions composition can make in storage stable through preparation, but be exposed to atmospheric moisture curing of following time (being after mixing) under the situation of two portions composition, and can in various application, for example use as coating, seam sealer and encapsulating material.Yet they are particularly suitable for sealing the connection that relatively moves easily, cavity and in goods and intravital other space of structure.Therefore they are particularly suitable for as the glazing sealing agent and are used to seal the wherein important building structure of visual appearance of sealing agent.

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 for example comprises glazing structure or the building unit of the above, and these form further aspect of the present invention.

Composition of the present invention can contain for the silicone elastomer product for example sealing agent and the analogue conventional other composition as optional ingredients.For example composition contains one or more fine reinforcing fillers usually, for example the pyrolysis of high surface area and precipitated silica and on certain degree above-described lime carbonate, perhaps extra non-reinforcing filler, for example quartz of Fen Suiing, diatomite, barium sulfate, ferric oxide, titanium dioxide and carbon black, talcum, wollastonite.Can use separately or other filler except above-described comprises 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.

Silicate in the group that aluminum oxide, next free olivine group, garnet group, silico-aluminate, cyclosilicate, chain silicate and sheet silicate are formed.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].

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 for example asbestos, kaolinite, Al ₄[Si ₄O ₁₀] (OH) ₈And vermiculite.

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.For the sake of clarity, be understood that, be used to handle the lipid acid of filler and/or fatty acid ester with discuss as necessary additive of the present invention those separate and any hydrophobic treatment of common filler will be independent of requisite lipid acid of the present invention and/or fatty acid ester are carried out.

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 150 weight parts usually.

Can be included in other composition in the composition include but not limited to quicken composition solidified promotor for example metal-salt and amine, rheology modifier, adhesion promotor, pigment, thermo-stabilizer, fire retardant, UV stablizer, cured modified dose, chainextender, conduction and/or heat conductive filler, mycocide and/or biocide and the analogue of carboxylic acid (they can be suitably exist with the consumption of 0-0.3wt%), water scavenging agent (typically with as employed those the identical compounds of linking agent, or silazane).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.

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.In some cases, above-mentioned rheologic additive also can play and improve fusible effect.

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, the reaction product of quadrol and silyl acrylate.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.

Thermo-stabilizer can comprise ferric oxide and carbon black, the carboxylate salt of iron, hydration cerium (ceriumhydrate), titanium oxide, barium zirconate, sad cerium and zirconates, and porphyrin.

Fire retardant for example can comprise carbon black, W 4600 and silicate for example wollastonite, platinic compound.

Chainextender can be included in thereby the crosslinked dual functional silane that increases the length of polysiloxane polymer chain before and reduce the elastomeric modulus of stretch of solidified takes place.There are competition in chainextender and linking agent in the reaction of itself and functional polymer's end group.In order to realize significant chain extension, dual functional silane must have the reactivity of the linking agent that is significantly higher than typical trifunctional.The suitable chainextender that is used for condensation cured system comprises and for example is selected from following chainextender:

(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;

The 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.

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.

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.

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; 10 '-the two phenoxy group arsine (trade(brand)names: Vinyzene of 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

The azoles based compound, for example tebuconazole (tebuconazol) is in conjunction with argentiferous zeolite.

Composition is the composition of room temperature vulcanizable preferably, and they at room temperature solidify under the situation that does not have heating.

Can use any suitable mixing equipment, by mixing each composition, the preparation composition.Can optionally add other component.For example can be by polymkeric substance with hydroxyl or hydrolysable group and the employed filler that is mixed together dilution, and mix the pre-composition of it and linking agent and catalyzer, thus prepare preferred one-part moisture gas cured compositions.Can UV stablizer, pigment and other additive be joined in the mixture in any required stage.Optionally, can after polyreaction, other thinner be mixed with other composition component.

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

According to the present invention, provide a kind of preparation can be solidified into elastomeric moisture cured method for compositions, comprising:

(a) in the presence of organic radical diluent materials, appropriate catalyst and optional end-capping reagent, pass through polymerization single polymerization monomer and/or oligopolymer, preparation formula X-A-X ¹The silicon-containing polymer of dilution

Wherein X and X ¹Be independently selected from that but to contain the substituent silyl of one or more condensations and A in each group be number-average molecular weight (Mn) at least 132000 and the polymerization degree be at least 1800 polymer chain; With

B) optionally, quencher polymerization technique; But then with this polymkeric substance with contain at least two and can and choose any one kind of them or multiple filler mixes with suitable crosslinking agent, the suitable condensation catalyst of the group of condensation radical reaction in the polymkeric substance of dilution.

The silicon-containing polymer of dilution preferably has the polymkeric substance that contains organic based polysiloxane of hydroxyl and/or hydrolyzable end group, the present composition can obtain by any suitable polymerization process, as long as described polymkeric substance is diluted in polymerization process in extender and/or the softening agent.The preferred path of silicon-containing polymer for preparing described dilution is as follows:

(i) polycondensation

(ii) open loop/balance

(iii) addition polymerization

(iv) chain extension

Wherein optionally, but the polymkeric substance that end-blocking is obtained by above-mentioned polymerization route, so that desired hydrolyzable end group to be provided.

(i) polycondensation (be the polymerization of multiple monomer and/or oligopolymer, and eliminate low-molecular-weight by product, for example water, ammonia or methyl alcohol etc.).Can use any suitable polycondensation path.Preferred polycondensation depends on the front with regard to the described reaction scheme of condensation reaction, most preferably has the interaction of the compound of hydroxyl and/or hydrolyzable end group.

At A is under the situation of organopolysiloxane chain, and preferred polymerisation process is straight chain and/or side chain organopolysiloxane polyreaction, the wherein R of top formula (2) ⁵With subscript s as previously mentioned.The raw material of polyreaction preferably is the straight chain material basically, and it is terminal with formula R " ₃SiO _1/2The siloxanes end-blocking, each R wherein is " identical or different and be R ⁵But or condensation group.But the combination of the end group of any suitable condensation can be used for polyreaction of the present invention (but being that selected condensation group must stand condensation reaction together so that polymerization).Preferably, " group is hydroxyl or hydrolysable group at least one R.Usually, but as the condensation group of monomer/oligomer end group be the end capped or hydrolyzable substituent silyl of hydroxyl for example-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 ^dP (OR ^b) _3-p, each R wherein ^a, R ^b, R ^d, R ^cWith p as previously described.

Contain parent material that the condensation reaction of the siloxanes of silanol uses and be and have and the hydroxyl of silicon bonding or the hydrolysable group that can the form silanol group on the spot organopolysiloxane oligopolymer of alkoxyl group for example.Preferably, the viscosity of parent material is 10mPa.s to 5000mPa.s.Some parent materials can comprise the end group of non-hydrolysable.

There is catalyzer in many requirements in the above-mentioned technology.Can use any suitable polycondensation catalyst.These comprise above-described any catalyzer, protonic acid, Lewis acid, organic and mineral alkali, metal-salt and the organometallic complex that is used for condensation cured composition of the present invention.Be suitable for polymeric lewis acid catalyst of the present invention (" Lewis acid " is with the absorption electron pair, forms any material of covalent linkage) and comprise for example boron trifluoride, FeCl ₃, AlCl ₃, ZnCl ₂And ZnBr ₂

The special catalyzer of condensation more preferably, for example general formula is R ²⁰SO ₃The acid condensation catalyst of H, wherein R ²⁰The alkyl that representative has a 6-18 carbon atom is hexyl or dodecyl for example, and aryl is phenyl for example, or alkaryl for example dinonyl or two dodecyl naphthyl.Can randomly add water.Preferably, R ²⁰Be alkaryl with alkyl of 6-18 carbon atom, Witco 1298 Soft Acid (DBSA) for example.The special catalyzer of other condensation comprises n-hexyl amine, tetramethyl guanidine, the carboxylate salt of rubidium or caesium, other catalyzer that the oxyhydroxide of magnesium, calcium or strontium and this area are for example mentioned in GB patent application 895091,918823 and EP0382365.Also be preferably based on the catalyzer of phosphonitrilic chloride, for example according to US Patent specification 3839388 and 4564693 or those and general formula of EP application 215470 preparations be [X ³(PX ³ ₂=N) _sPX ³ ₃] ⁺[M ²X ³ _(v-t+1)R ^III _t] ^-Phosphonitrile halogen radical ion catalyzer, as described in the GB2252975, X wherein ³The expression halogen atom, M ²Be to be the element of 1.0-2.0 according to Pauling electronegativity scale's electronegativity, R ^IIIBe the alkyl with maximum 12 carbon atoms, the numerical value of s is 1-6, and v is M ²Valence state or the numerical value of oxidation state and t be to v-1 from 0.

Perhaps, catalyzer can comprise have following general formula contain organic radical silica-based contain oxygen chloro phosphonitrile:

Z ¹-PCl ₂＝N(-PCl ₂＝N) _n-PCl ₂-0

Wherein

Z ¹Representative by oxygen, chlorine atom or hydroxyl bond be incorporated into organic radical on the phosphorus silica-based and

N represents 0 or integer 1-8.Catalyzer can comprise that also above-mentioned condensation product and/or its tautomer (work as Z ¹Catalyzer exists with tautomeric forms when being hydroxyl).

Can be in the present invention as catalyzer can be any suitable compound further for the alternate catalyzer, described compound provide the negative ion source that contains at least one quaternary boron atom that defines among the WO01/79330 and can with the interactional proton of at least one silanol group.

Preferably by using neutralizing agent to come the quencher activity of such catalysts, described neutralizing agent will with catalyst reaction, make it not have activity.Typically, under acids condensation catalyst situation, neutralizing agent is suitable alkali, amine for example, and as list/two and three alkanolamines, for example monoethanolamine (MEA) and trolamine (TEA).Under the situation of the system of using the DBSA catalyzer, can comprise the aluminosilicate zeolite material of finding to absorb DBSA and staying stabilization of polymer for alternate quencher mode.In most of the cases, relict catalyst is retained in the polymer product, perhaps optionally, can remove by filtration or alternate method.Under the catalyst based situation of phosphonitrile, when reaching required viscosity, can be by following operation, make in the method the viscosity of the organic radical silicon compound that obtains keep constant: by adding inhibitor or deactivator suppresses or the employed catalyzer of inactivation or reaction product (are reacted and formed by this catalyzer by carrying out condensation and/or balance and organic radical silicon compound, condensation and/or balance with same promotion organic radical silicon compound), wherein use described inhibitor or deactivator explicitly with phosphonitrile up to now, for example three different nonyl amine, n-Butyl Lithium, lithium silanolate, hexamethyldisilazane and magnesium oxide.

Optionally, can use stop polyreaction and and then any suitable end-capping reagent of restriction molecular-weight average, to introduce as above X ²And X ¹Described silyl-terminated.

(II) balance/open loop

The equilibrium polymerization process for example raw material of ring-opening polymerization is cyclosiloxane (being also referred to as annular siloxane).Useful annular siloxane is known and commercially available acquisition.They have general formula (R ²¹SiO) _m, each R wherein ²¹Be aforesaid R ', m represents the round values of 3-12.R ²¹Can be by for example for example fluorine or chlorine replacement of halogen.Alkyl can be for example methyl, ethyl, n-propyl, trifluoro propyl, normal-butyl, sec-butyl and the tertiary butyl.Alkenyl can be for example vinyl, allyl group, propenyl and butenyl.Aryl and aralkyl can be for example phenyl, tolyl and benzoyl.Preferred group is methyl, ethyl, phenyl, vinyl and trifluoro propyl.Preferred all R ²¹In the group at least 80% is methyl or phenyl, most preferable.The mean value of preferred m is 3-6.The example of suitable cyclosiloxane is octamethylcyclotetrasiloxane, hexamethyl cyclotrisiloxane, decamethylcyclopentasiloxane, ring penta (methyl ethylene) siloxanes, ring four (phenyl methyl) siloxanes, ring pentamethyl-hydrogen siloxane and composition thereof.The material of a specially suitable commercially available acquisition is the mixture that contains octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.Typically, moisture is present in the monomer.The water that exists plays end-capping reagent by form the OH end group on polymkeric substance.

Can use any appropriate catalyst.These comprise alkali metal hydroxide for example lithium hydroxide, sodium hydroxide, potassium hydroxide or cesium hydroxide, the complex compound of alkali metal alcoholates or alkali metal hydroxide and alcohol, the basic metal silanol is silanolate potassium, silanolate caesium, silanolate sodium and lithium silanolate or silanolate trimethylammonium potassium for example.Spendable other catalyzer comprises by tetra-alkyl ammonium hydroxide and siloxanes tetramer reaction deutero-catalyzer and foregoing boryl catalyzer.

Yet being used for balanced class, to react most preferred catalyzer be foregoing halogenation phosphonitrile, phosphonitrile acid and phosphazene base.Optionally, can regulate polymer molecular weight and/or increase the mode end-blocking resulting polymers of functional group.Suitable end-capping reagent comprises the silane of the group with the end group reaction in an energy and the resulting polymers composition for preparing in the polymkeric substance of dilution.Yet for purpose of the present invention, preferred silane is as end-capping reagent.Use them to introduce and above X ²And X ¹Equally described hydroxyl and hydrolysable group.

(iii) addition polymerization

For this specification sheets, " addition polymerization " or (" poly-addition ") technology is a kind of polymerization technique, and is wherein different with condensation reaction, in polymerization process, do not generate by product by monomer and oligopolymer co-reactant, for example water or alcohol.Preferred addition polymerization route is in the presence of appropriate catalyst, at the unsaturated organic group hydrosilylation reactions between alkenyl or alkynyl and the Si-H base for example.

Typically, use the addition polymerization route, with by in the presence of extender and/or softening agent and appropriate catalyst and optional end-capping reagent, by the addition reaction path, make (a) (i) organopolysiloxane or (ii) silane and (b) (i) one or more organopolysiloxane polymkeric substance or (ii) one or more organic polymers reactions; This polymerization technique of quencher optionally, thus segmented copolymer formed.

Organopolysiloxane or silane (a) be selected from contain at least one group that can experience addition class reaction silane (a) (ii) and the organopolysiloxane monomer (a) that contains the group that can experience the reaction of addition class (i).Organopolysiloxane or silane (a) must contain substituting group, so that it can (i) or (ii) experience suitable addition reaction with polymkeric substance (b).Preferred addition reaction is the hydrosilylation reactions between unsaturated group and Si-H base.

Preferred silane (a) (ii) has at least 1 and preferred 2 can experience the group that reacts with (b) (i) or addition class (ii).When this addition reaction was hydrosilylation reactions, silane can contain unsaturated structure, but preferably contained at least one Si-H group.Most preferably each silane contains one or more Si-H groups.Except one or more Si-H groups, preferred silane can comprise for example alkyl, alkoxyl group, acyloxy, ketoxime acid group base (ketoximato), amino, amide group, sour amide group, aminooxy, sulfydryl, alkenyl oxy etc.Wherein, preferred alkoxyl group, acyloxy, ketoxime acid group base, amino, amide group, aminooxy, sulfydryl and alkenyl oxy.The specific examples of silicon hydride has halogenated silanes, trichlorosilane, dimethyl dichlorosilane (DMCS), dimethylchlorosilane and diphenyl dichlorosilane; Organoalkoxysilane, for example Trimethoxy silane, triethoxyl silane, methyldiethoxysilane, methyl dimethoxysilane and phenyl dimethoxy silane; Acyloxy silane, for example methyl diacetoxy silane and diethylamino phenyl acyloxy silane; With ketoxime acid group base silane, for example two (DMKO acid esters)-methyl-monosilanes and two (cyclohexyl ketoxime acid esters) methyl-monosilane.Wherein, preferred halogenated silanes and organoalkoxysilane.Particularly preferred silane comprises for example methyl dimethoxysilane (H-Si (CH ₃) (OCH ₃) ₂).

Should understand, silane (a) (ii) and (b) (i) or (ii) between addition reaction cause the polymer chain propagation process or as mode with predetermined required end group end envelope polymkeric substance, wherein extender can (ii) add with silane (a), promptly before the addition reaction at once or can polymkeric substance (b) (i) and/or (b) exist during (ii) the polyreaction and so silane (a) is (ii) joined in the presence of extender polymeric extender polymer (b) (i) or (b) (ii) in.

Organopolysiloxane monomer (a) is the form of the straight chain chain of formula (1a) and/or side chain organopolysiloxane preferably (i)

R′ _aSiO _4-a/2 (1a)

Wherein each R ' can be identical or different and representative have 1-18 carbon atom alkyl, have the substituted hydrocarbon radical of 1-18 carbon atom or have the-oxyl of maximum 18 carbon atoms, the mean value of a is 1-3, preferably 1.8-2.2.Preferred each R ' is identical or different and enumerate but be not limited to: hydrogen; Alkyl is methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, undecyl and octadecyl for example; Cycloalkyl, for example cyclohexyl; Aryl, for example phenyl, tolyl, xylyl, benzyl and 2-phenylethyl; With the halo alkyl, for example 3,3,3-trifluoro propyl, 3-chloropropyl and dichlorophenyl.Some R ' groups can be the hydrogen bases.Preferably, poly-diorganosiloxane is a polydialkysiloxane, most preferably polydimethylsiloxane.When organic based polysiloxane or silane (a) were the organopolysiloxane monomer, described organopolysiloxane monomer must have at least one can be by addition reaction technology with (b) (i) or the group of at least two groups (typically end group) reaction (ii).Preferably, organopolysiloxane (a) (i) each molecule comprises at least one Si-H base, and preferably each molecule comprises at least two Si-H bases.Preferably, with general formula H (R ") ₂SiO _1/2Siloxanes end-blocking organopolysiloxane (a) (i), wherein each R " is the alkyl of alkyl or replacement, most preferably alkyl.Preferably, the viscosity of organopolysiloxane (a) under 25 ℃ is 10mPa.s to 5000mPa.s.

Organopolysiloxane polymkeric substance (b) is the preferably straight chain of following formula (1b) and/or side chain organopolysiloxane (i):

R

_aSiO _4-a/2 (1b)

Each R wherein

Can be identical or different, and expression has the alkyl of 1-18 carbon atom, has the alkyl of the replacement of 1-18 carbon atom, or have the-oxyl of maximum 18 carbon atoms and the mean value of a is 1-3, preferred 1.8-2.2.Preferably, there is not R Base can be the hydrogen base.Preferably, each R

Identical or different, and exemplify but be not limited to: alkyl, for example methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, undecyl and octadecyl; Cycloalkyl, for example cyclohexyl; Aryl, for example phenyl, tolyl, xylyl, benzyl and 2-styroyl; With the halo alkyl, for example 3,3,3-trifluoro propyl, 3-chloropropyl and dichlorophenyl.

Organopolysiloxane polymkeric substance (b) (i) can comprise any suitable organopolysiloxane main polymer chain, but preferred straight or branched, and comprise at least one, preferably at least two will be by the substituting group of the aforementioned radical reaction in addition reaction path and organopolysiloxane or the silane (a).Preferably, polymkeric substance (b) described or each substituting group in (i) is an end group.When organic based polysiloxane or silane (a) comprise at least one Si-H base, at the preferred substituted (it be designed to and Si-H base interact) of organopolysiloxane polymkeric substance (b) on (i) unsaturated group (for example alkenyl end-blocking, for example (CH of ethenyl blocking, propenyl end-blocking, allyl capped preferably ₂=CHCH ₂-)), or with vinylformic acid or alkyl acrylic CH for example ₂C (CH ₃)-CH ₂-Ji end-blocking.Following structure shows representativeness, the non-limiting example of alkenyl: H ₂C=CH-, H ₂C=CHCH ₂-, H ₂C=C (CH ₃) CH ₂-, H ₂C=CHCH ₂CH ₂-, H ₂C=CHCH ₂CH ₂CH ₂-and H ₂C=CHCH ₂CH ₂CH ₂CH ₂-.Following structure shows representativeness, the non-limiting example of alkynyl: HC ≡ C-, HC ≡ CCH ₂-, HC ≡ CC (CH ₃)-, HC ≡ CC (CH ₃) ₂-, HC ≡ CC (CH ₃) ₂CH ₂-.Perhaps, unsaturated organic group can be the hydrocarbon of organic functional, for example acrylate, methacrylic ester and similar group, for example alkenyl and/or alkynyl.Especially preference chain thiazolinyl.

Organic polymer (b) (ii) can comprise 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), poly-(to trimethyl silyl vinylbenzene) and gather (to trimethyl silyl-alpha-methyl styrene).Under each situation, the (ii) employed monomer of organic polymer (b) comprise with organopolysiloxane or silane (a) at least two substituting groups of reaction-ity group reaction.Typically, organic polymer (b) (ii) comprises at least two unsaturated end groups, preferably can with the interactional alkenyl end group of Si-H in organopolysiloxane or the silane (a) base.Other organic radical monomer (b) (ii) can comprise the end capped low polyphenylene of alkynyl, the end capped aromatic polysulfones oligopolymer of vinyl benzyl.Be suitable for comprising aromatic polyester base monomer and aromatic polyester base monomer as (b) further organic polymer main chain (ii), these two kinds of monomers preferably include the alkenyl end group.

As polymkeric substance (b) most preferred organic radical main polymer chain (ii) may be that the polyoxy alkylidene with unsaturated (for example alkenyl) end group is a polymer based.The number-average molecular weight scope of each polyoxyalkylene polymers (b) can be about 300 to about 10,000.And oxygen base alkylidene unit is not necessarily identical in whole polyoxy alkylidene monomer, but each unit can be different.

Can use among any suitable preparation the application and be used as polymkeric substance (b) polyoxy alkylidene monomer methods (ii).Example comprises those described in EP0397036, US3971751, EP0196565 and the WO2005/103117.Yet for the present invention, the preparation method of polyoxyalkylene polymers (b) is unimportant for the purpose of the present invention.Can use any suitable method for preparing polyoxy alkylidene amide polymer (b) discussed above.Preferable methods comprises and described in WO9906473, WO200306530 and the WO2005103117 its content being incorporated herein by reference.

Therein organopolysiloxane or silane (a) but comprise the group of an only addition reaction and (b) (i) or (ii) comprise with organopolysiloxane or silane (a) but under the situation of the group of two addition reactions of reaction, products therefrom is " ABA " type polymer product, and when organic based polysiloxane or silane (a) but comprise the group of two addition reactions and (b) (i) or (ii) comprise with organopolysiloxane or silane (a) but during the group of two addition reactions of reaction, interaction between these two kinds of components will cause (AB) n segmented copolymer, and wherein the length of polymkeric substance mainly decides by the relative quantity of these two kinds of compositions.

Therefore, can prepare (AB) of straight chain non-hydrolysable of the present invention by using the end capped dialkylsiloxane fluidic of SiH platinum catalytic hydrosilylation alkenyl terminated polyether _nSegmented copolymer.The gained multipolymer is that described capping group is selected from allyl group, propenyl and/or hydrogen (dialkyl group) siloxy-(relative quantity that depends on existing each composition) by the silico-carbo-polyoxy alkylidene block (being inferior propoxy-) of oxygen key connection and the binding substances of capping group.

When selected addition reaction is hydrosilylation reactions, can use any suitable hydrosilylation catalysts.This hydrosilylation catalysts can exemplify promote in the end capped organopolysiloxane of SiH with silicon bonded hydrogen atom and polyoxyethylene on any metallic catalyzer of unsaturated hydrocarbons radical reaction.Metal can exemplify ruthenium, rhodium, palladium, osmium, iridium or platinum.

Hydrosilylation catalysts can exemplify following: Platinic chloride, the Platinic chloride of alcohol modification, the alkene complex of Platinic chloride, the complex compound of Platinic chloride and divinyl tetramethyl disiloxane, be adsorbed on the platinum particulate on the carbon support, be carried on platinum such as Pt (Al on the metal oxide carrier ₂O ₃), platinum black, acetylacetonate platinum, (divinyl tetramethyl disiloxane) platinum is with PtCl ₂Be the inferior platinum of the halogenation of example, PtCl ₄, Pt (CN) ₂, the inferior platinum of halogenation be the complex compound of the unsaturated compound of example with ethene, propylene and organic radical vinylsiloxane, vinylbenzene hexamethyl two platinum.In United States Patent (USP) 3923705, disclose this noble metal catalyst, introduced by reference, to show platinum catalyst at this.A kind of preferred platinum catalyst is a Karstedt ' s catalyzer, and it is disclosed in the United States Patent (USP) 3715334 and 3814730 of Karstedt, is introduced into by reference at this.Karstedt ' s catalyzer is typically to contain at the solvent divinyl tetramethyl disiloxane platinum complex of 1wt% platinum in the toluene for example.Another preferred platinum catalyst is Platinic chloride and the reaction product that contains the organic radical silicon compound of aliphatic unsaturated link(age).It is disclosed in the United States Patent (USP) 3419593, is introduced into by reference at this.Most preferred catalyzer is the neutralized complex of platinous chloride and divinyl tetramethyl disiloxane, for example described in the United States Patent (USP) 5175325.

Perhaps can use for example RhCl of ruthenium catalyst ₃(Bu ₂S) ₃With ruthenium carbonyl compound for example 1,1,1 ,-trifluoroacetyl group acetonization ruthenium, acetylacetonate ruthenium and ten dicarbapentaborane, three rutheniums or 1, (ruthenium 1,3-ketoenolate) for 3-ketone enolization ruthenium.

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 for example Ir (OOCCH of any suitable iridium catalyst ₃) ₃, Ir (C ₅H ₇O ₂) ₃, [Ir (Z ²) (En) ₂] ₂Or [Ir (Z ²) (Dien)] ₂, Z wherein ²Be chlorine, bromine, iodine or alkoxyl group, En is that alkene and Dien are cyclooctadiene.

The additional component of known raising hydrosilylation reactions can be joined in this reaction.These components comprise salt, sodium acetate for example, and it has buffering effect in conjunction with platinum catalyst.

The consumption of hydrosilylation catalyst does not have strict restriction, if its amount enough acceleration have the polyoxyethylene of unsaturated alkyl and the end capped organopolysiloxane of SiH in room temperature or be higher than reaction under the temperature of room temperature in each molecular end.The desired definite consumption of this catalyzer depends on employed special catalyst and is not easy prediction.Yet, for the platiniferous catalyzer, having the polyoxyethylene and the end capped organopolysiloxane of SiH of unsaturated alkyl in each molecular end with respect to per 1,000,000 parts by weight of component, consumption can be low to moderate 1 weight part platinum.The polyoxyethylene and the end capped organopolysiloxane of SiH that have unsaturated organic group in per 1,000,000 parts of components in each molecular end, can be added in an amount of the catalyzer of 10-120 weight part, but typically have the polyoxyethylene and the end capped organopolysiloxane of SiH of unsaturated organic group in each molecular end, be added in an amount of the 10-60 weight part in per 1,000,000 parts of components.Also can replace organo-peroxide solidify and/or crosslinked composition in conjunction with the organic radical hydrogen siloxane as solidifying agent through hydrosilylation reaction catalyst, condition be that each polymer molecule contains at least two and is applicable to and the crosslinked unsaturated group of organic radical hydrogen siloxane.These groups are alkenyl normally, most preferably vinyl.In order to solidify this composition, must contain in each molecule of organohydrogensiloxanes and surpass two silicon bonded hydrogen atoms.Can contain for example about 4-20 Siliciumatom and the about at most 10Pas of the viscosity under 25 ℃ in each molecule of organic radical hydrogen siloxane.Be present in replacement and unsubstituted alkyl that in the organohydrogensiloxanes and the organic group silicon bonding can comprise 1-4 carbon atom, it does not contain olefinic or acetylene series unsaturated link(age) in addition.

When material is when having the organopolysiloxane of at least two Si-H bases, typically use the polysiloxane that contains ≡ Si-H and the material that contains unsaturated link(age) of about 1: 1 mol ratio, carry out this method.Expection also can be carried out this method by the material that adopts the excessive polysiloxane that contains ≡ Si-H or contain unsaturated link(age) and prepare useful material, but this is regarded as not effectively utilizing so this material.Typically, use the excessive slightly material that contains unsaturated link(age), fall at the reaction internal consumption to guarantee all SiH.

Optionally, can be used as the mode end-blocking resulting polymers of regulate polymer molecular weight and/or increase functional group.Suitable end-capping reagent comprises the silane of the group of the addition class reaction with 1 end group in the polymkeric substance that can experience and dilute.When this addition reaction was hydrosilylation reactions, silane can contain unsaturated structure, but preferably contained the Si-H group.Except one or more Si-H groups, preferred silane can comprise for example alkoxyl group, acyloxy, ketoxime acid group (ketoximato) group, amino, amide group, sour amide group, aminooxy, sulfydryl, alkenyl oxy etc.Wherein, preferred alkoxyl group, acyloxy, ketoxime acid group group, amino, amide group, aminooxy, sulfydryl and alkenyl oxy.The specific examples of silicon hydride has halogenated silanes, trichlorosilane, dimethyl dichlorosilane (DMCS), dimethylchlorosilane and diphenyl dichlorosilane; Organoalkoxysilane, for example Trimethoxy silane, triethoxyl silane, methyldiethoxysilane, methyl dimethoxysilane and phenyl dimethoxy silane; Acyloxy silane, for example methyl diacetoxy silane and diethylamino phenyl acyloxy silane; With ketoxime acid group base silane, for example two (DMKO acid esters) methyl-monosilanes and two (cyclohexyl ketoxime acid esters) methyl-monosilane.Wherein, preferred halogenated silanes and organoalkoxysilane.Particularly preferred silane comprises for example methyl dimethoxysilane (H-Si (CH ₃) (OCH ₃) ₂).

Can use end-capping reagent to introduce and optionally comprise-SiOH with the hydrolysable group of afterreaction 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 the monovalence alkyl independently, for example, alkyl particularly has 1-8 carbon atom, (and preferably methyl); Each R ^bAnd R ^dGroup is alkyl or alkoxyl group independently, and alkyl wherein has maximum 6 carbon atoms suitably; R ^cIt is the bivalent hydrocarbon radical that can be separated by one or more siloxanes spacers with maximum 6 Siliciumatoms; Has value 0,1 or 2 with p.

(iv) chain extension

In the case, not to add chainextender in the composition of final pre-preparation, but before being incorporated into other composition in the encapsulant composition, during the chain extension polymerization procedure, chainextender is mixed in the polymkeric substance.Typically, the polymkeric substance parent material is to have the organopolysiloxane that is suitable for the interactional end group of selected chain extension material.Typically, polymer terminal group is hydrolysable group or is suitable for addition reaction (typically hydrosilylation reactions), and will make the suitable reactive group of polymkeric substance chain extension select the chain extension material based on having.The preferred chain extension material that is used to make the polymkeric substance chain extension with hydroxyl and/or hydrolyzable end group as previously mentioned.

For the pre-formation polymkeric substance with alkenyl or Si-H end group that is suitable for being undertaken by the hydrosilylation route addition reaction, chainextender for example comprises:

The silane that contains two alkenyls, two hydrogen silanes, the polymerization degree is 2-25 and has the polydialkysiloxane of at least one Si-alkene base key with respect to each end group,

The polymerization degree be 2-25 and with respect to 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.

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.

By the employed catalyzer of reaction decision catalysis chain extending reaction that will carry out.When the reaction that takes place is condensation reaction, can use foregoing any suitable condensation catalyst.When the reaction that takes place is hydrosilylation reactions, can use foregoing any suitable hydrosilylation catalysts.

Optionally, polymkeric substance contains hydrolyzable end group, can use the above-described end-capping reagent relevant with condensation to obtain suitable end group.Optionally, but when polymkeric substance contains the end group of addition reaction, can use the above-described end-capping reagent relevant to obtain suitable end group with addition polymerization.

Can intermittently or on any suitable mixing roll, carry out this technology continuously.Under the situation of polycondensation, can use for example hydrolyzable silane such as methyltrimethoxy silane or use evaporation, cohesion or centrifugation technique to remove the water that is generated by chemical seasoning by physical sepn.

Chain extension takes place under can be any technology that involves in preferred intermittence or continuous operation mode the suitable temperature and pressure.Therefore, under the catalytic method situation of phosphonitrile, can more preferably under 80 ℃-160 ℃ the temperature polymerization take place at 50 ℃-200 ℃.In addition, in order to promote to remove in condensation course formed by product for example water, HCl or alcohol, the condensation and/or the balance of carrying out the organic radical silicon compound under the pressure of 80kPa can be lower than.The alternative method of removing condensation by-product comprises by chemical seasoning to be used for example hydrolyzable silane such as methyltrimethoxy silane (optionally) or uses evaporation, cohesion or centrifugation technique to remove by physical sepn.

Set forth the present invention by embodiment.For the purpose of comparison, except as otherwise noted, employed extender is HYDROSEAL in all embodiment and Comparative Examples

G250H, the mineral oil fractions (n-paraffin 7%/isoparaffin 51% and alicyclic hydrocarbon 42%) of the hydrotreatment that a kind of TotalFina produces.Except as otherwise noted, measure all viscosity down at 25 ℃.

Embodiment 1

Use the chain extension of dibutyl acetoxysilane

The preparation polymkeric substance

Is 80 with 50g 25 ℃ of following viscosity, and the end capped polydimethylsiloxane of the dimethyl hydroxyl of 000mPas is put into suitable containers.The dibutyltin diacetate catalyzer of 0.2g dibutoxy diacetoxy silane (DBDAc) and 500ppm weight (with respect to the polymkeric substance) water with stoichiometric amount is added, with the acetoxyl group on the hydrolysis DBDAc.When one is measured to initial viscosity and increases, in this reaction mixture, add the extender of 50g immediately and follow the tracks of this viscosity and change, reach maximum value up to the viscosity of product.

Sealant dispensing

With poly-(PO) of the pyrolytic silicon dioxide of 50% mixture of the methyl triacetoxysilane of polymkeric substance, 5% weight of preparation as mentioned above of 86.485% weight and ethyl triacetoxysilane linking agent, 8% weight, 0.5% weight (EO) (rheology modifiers) and 0.015% dibutyltin diacetate catalyzer, prepare the sealing agent (sample 1) of resulting polymers.The sealing agent performance is shown in table 1.

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

Carry 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).

Be cured degree of depth test, how far sealing agent hardens below the surface in 24 hours and 72 hours to be determined at, and method is: fill suitable containers (avoiding introducing gas enclosure), under room temperature (about 23 ℃) and about 50% relative humidity container contained the suitable time period of sealant cures with sealing agent.After appropriate curing time, take out sample from container, and measure the height of solidified sample.

Table 1

Standard performance	Test method	Sample 1
				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
				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
				Hardness	(Shore A) ASTM D2240-97	5
Bond test		7dRT	7H2O
					Glass	2	2

Embodiment 2

Adopt following operation, in having the laboratory batch reactor of mixed pulp, by changing power according to viscosity change, produce the polymkeric substance of increment, described mixed pulp is with identical speed (being 179 rev/mins (RPM) in the following embodiments) blend mixture continuously:

Be incorporated in the mixing roll the end capped polydimethylsiloxane of 0.42kg dimethyl hydroxyl (70mPa.s) and stirring, when under 179RPM, continuing to stir, add 21g DBSA catalyzer and 0.56kg thinner according to the order of sequence.Keep the viscosity that the desired electric current of slurry speed of rotation (mA) of 179RPM is followed the tracks of resulting polymers by measurement.Continue to mix, up at the time point place with amine (for example 0.5-1.0% trolamine) catalyst neutralisation, viscosity begins to descend.The number-average molecular weight of the dilution polydimethylsiloxanepolymer polymer that makes is 170,000, and it is fundamental measurement with ASTMD5296-05 with polystyrene molecular weight equivalent.Table 2 shows the prescription of polymkeric substance.

Table 2

	Sample 2
		25 ℃ of polymer viscosities (mPas) that dilute down	19000
		The wt% of organopolysiloxane	39.3
The wt% of thinner	58.9
		The wt% of DBSA	1.5
The wt% of monoethanolamine	0.3

Use the polymeric constituent of gained dilution organopolysiloxane polymer as the acetoxyl group sealant dispensing, described prescription be polymkeric substance and other component of composition of the dilution that will make above mixed must.The physicals of gained sealing agent (sample 2) is compared with using the physicals at the acetoxyl group diluent formulation (contrasting 1) of the increment that does not exist polymeric polymkeric substance under the diluent materials to make as the routine of 80000mPas 25 ℃ of following viscosity.The acetoxyl group sealant dispensing of being produced has been shown in the table 2.

Table 3

	Sample 2	Contrast 1
			The polymkeric substance of total wt% increment	86.385	?-
Organopolysiloxane (after the polymerization with mixing diluents) wt%	-	?56,385
			Thinner (with mixed with polymers) wt%	-	?30
Triacetoxysilane	5	?5
			Pyrolytic silicon dioxide (surface-area 150m 2/g(BET))wt％	8.6	?8.6
Dibutyltin diacetate	0.015	?0.015

The physicals of sealing agent

Carry out the standard physical performance test to compare the physicals (table 4) of two sealant dispensings after solidifying.As described in top embodiment 1, carry out bonding experiment.

Table 4

	Test method	Sample 1	Contrast 1
				Proportion	ASTM?D1475-98	?0.90	?0.97
Extruded velocity (g/min)	ASTM?D2452-94	?594	?700
				Tensile strength (MPa)	ASTM?D412-98a	?1.16	?2.08
Elongation at break (%)	ASTM?D412-98a	?1098	?480
				100% modulus (MPa)	ASTM?D638-97	?0.13	?0.44
Hardness (Shore A)	ASTM?D2240-97	?2.00	?13
				In bonding (1) on glass		2 (by)	2 (by)
In bonding (2) on glass		2 (by)	2 (by)

Can understand, the acetoxyl group sealing agent that makes according to the present invention is compared with the prescription of prior art has many advantages, for example has higher amount of diluent (50% pair 30%) with regard to similar rheological.Owing to do not need the mixing step of mixed polymer and thinner, so the mixing process during the sealing agent preparation is simplified greatly.Greater than 1000% as can be known, the gained sealing agent shows that elasticity increases from elongation at break.The sealing agent prescription makes under the situation without any significant operational difficulty, can use if having when in polymerization process, not having thinner and can not operate viscosity basically for example the polymkeric substance of 3400000mpas and the fact that the uncured encapsulant composition of gained has significantly low proportion make the processor can fill the sealing agent that more sealing agent tube or other packing/kg are produced.

Embodiment 3

The two kinds of acetoxyl group sealant dispensings of polymer manufacture (sample 3 and 4) that use the present invention to make, and with viscosity that routine makes be that the physicals of the acetoxyl group sealant dispensing (contrast 2) of the increment of 80000 (mPas) compares.

The polymer samples 3 and 4 of dilution is by having formula ((CH ₃) ₂SiO) ₄Ring-type organopolysiloxane and phosphine piperazine catalyst based at Isopar

P hydrocarbon fluid (being sold by ExxonmobilCorporation) exists down as extender (it is that 265 ℃ (ASTM D 86) and viscosity are 3.0mPas (ASTM D 445) with final boiling point that initial boiling point is 235 ℃), and polymerization makes.Using hydroxy-end capped polydimethylsiloxane is selected neutralizing agent as end-capping reagent and silyl phosphoric acid ester.Polymer formulators is shown in Table 5.

Table 5: the polymer formulators of increment

	Sample 3	Sample 4
			Polymerization temperature	100℃	?120℃
(CH 3) 2SiO) 4(wt％)	78.394	?59.795
			25 ℃ of following 70mPas of hydroxy-end capped polydimethylsiloxane (wt%)	1.60	?0.20
Extender (wt%)	20	?40
			Phosphine itrile group catalyzer (wt%)	0.0035	?0.0028
Silyl phosphoric acid ester (wt%)	0.0025	?0.0022

After finishing, sample 3 and sample 4 the two polyreaction that shown table 6 stay the details (ASTM D5296-05) of the molecular weight of residual monomer in the composition and resulting polymers.Because the boiling point of residual monomer significantly is lower than the boiling point of thinner, thus they can be as required from polymkeric substance stripping go out.((CH ₃) ₂SiO) ₄Boiling point be 175 ℃.

Table 6

	Sample 3	Sample 4
Remaining ((CHs) 2SiO) 4(wt％)	7.3	?11.3
			Number-average molecular weight (Mn)	195335	?255394
Weight-average molecular weight (Mw)	429789	?561100

Polymer manufacture organopolysiloxane encapsulant composition by the described gained increment of top table 3.Sample 3 and 4 in the table 7 is respectively to be made by the polymer samples in the table 63 and 4.In this case, the extender of additional quantity is added in the polymkeric substance of increment with further reduction viscosity.The sealing agent that these sealant dispensings all are used for according to the present invention and the comparative example makes.Table 7 provides the details of composition.

Table 7

	Sample 3	Sample 4	Sample 5
				The polymkeric substance of total wt% increment	43.2	43.3	-
25 ℃ of following 80000mPa.s of hydroxy-end capped organopolysiloxane (wt%) (after polymerization with mixing diluents)	-	-	56.4
				Thinner (after the polymerization with mixed with polymers) (wt%)	43.2	43.3	30
Triacetoxysilane (wt%)	5	5	5
				Pyrolytic silicon dioxide (surface-area 150m 2/g(BET))(wt％)	8.585	8.585	8.585
Dibutyltin diacetate (wt%)	0.015	0.015	0.015

The physicals of sealing agent

The standard physical performance test is as described in the top embodiment 1, except as otherwise noted and the result be provided in the table 8.

Table 8: the physicals of sealing agent

	Measuring method	Sample 3	Sample 4	Sample 5
					Proportion	ASTM?D1475-98	?0.92	?0.90	?0.97
Penetration degree (mm/10)	ASTM?D217-97	?152	?180	?300
					Tensile strength (MPa)	ASTM?D412-98a	?4.34	?4.98	?2.08
Elongation at break (%)	ASTM?D412-98a	?＞1000	?＞1000	?480
					100% modulus (MPa)	ASTM?D638-97	?0.12	?0.09	?0.44
Xiao A hardness	ASTM?D2240-97	?4	?1	?13
					At bonding (7H on glass 2O)		2 (by)	2 (by)	2 (by)
At bonding (7dRT) on glass		2 (by)	2 (by)	2 (by)

Can understand, compare with the prescription of prior art, acetoxyl group sealing agent prepared in accordance with the present invention has many advantages.The gained sealing agent demonstrates elasticity to be increased, and this can find out greater than 1000% from elongation at break.This sealant dispensing makes under the situation without any remarkable intractability, can use if having the polymkeric substance that to operate viscosity basically when in the polymerization technique process, not having thinner, and the uncured encapsulant composition of gained has significantly, and lower this fact of proportion makes preparation person can fill the sealing agent that more sealing agent tube or other packing/kg are produced.

Claims (15)

1. one kind can be solidified into elastomeric moisture cured composition, and it comprises:

(a) Xi Shi polymkeric substance, it comprises:

(i) silicon-containing polymer of following formula

X-A-X ¹

Wherein X and X ¹But be independently selected from and contain the substituent silyl of one or more condensations in each group, with A be number-average molecular weight (Mn) at least 132000 and the polymerization degree be at least 1800 siloxane polymer chain or silicone copolymers chain, the viscosity of this polymkeric substance under 25 ℃ is greater than 1000000mPas

(ii) organic extender and/or softening agent,

The polymkeric substance of described dilution is to obtain by polymerization in the presence of described organic extender and/or softening agent;

(b) suitable crosslinking agent, but it comprise at least two can with the group of condensation radical reaction in the polymkeric substance of dilution;

(c) suitable condensation catalyst; With optional

(e) one or more fillers.

2. the composition of claim 1 is characterised in that X ¹Or X is substituent silyl contain hydroxy end groups or hydrolyzable.

3. the composition of claim 2, wherein X ¹Or X is-Si (OH) ₃,-(R ^a) Si (OH) 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 ^aRepresentative has the alkyl of 1-8 carbon atom independently; Each R ^bAnd R ^dGroup is alkyl or alkoxyl group independently, and alkyl wherein has maximum 6 carbon atoms suitably; R ^cIt is the bivalent hydrocarbon radical that can be separated by one or more siloxanes spacers with maximum 6 Siliciumatoms; Has value 0,1 or 2 with p.

4. the composition of aforementioned each claim is characterised in that extender and/or softening agent are selected from one or more in following:

The end capped polydimethylsiloxane of trialkylsilkl

Polyisobutene,

Phosphoric acid ester,

Polyoxyethylene alkylphenyl,

The straight chain of mono carboxylic acid of aliphatic series and/or branched-chain alkyl phenyl ester.

5. each composition of claim 1-4, wherein extender is selected from one or more in following:

Straight or branched list unsaturated hydrocarbons; And/or

Mineral oil fractions comprises straight chain mineral oil, side chain mineral oil and/or ring-type mineral oil and composition thereof.

6. the composition of claim 5, wherein straight or branched list unsaturated hydrocarbons is alkene or its mixture that contains the straight or branched of 12-25 carbon atom.

7. each composition of claim 1-4, wherein linking agent be one or more to contain the silane of acyloxy, ketoxime base or siloxanes and catalyzer be tin catalyst.

8. each composition of claim 1-4, wherein linking agent be one or more to contain the 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.

9. each composition of claim 1-4, wherein composition comprises filler, and described filler comprises one or more fine reinforcing fillers and/or non-reinforcing filler.

10. the composition of claim 9, wherein said reinforcing filler is high surface area pyrolytic silicon dioxide, precipitated silica and lime carbonate.

11. the composition of claim 9, wherein said non-reinforcing filler are quartz, diatomite, barium sulfate, ferric oxide, titanium dioxide, carbon black, talcum or the wollastonites of pulverizing.

12. each composition of claim 1-4, wherein Xi Shi polymkeric substance is by obtaining by the polymerization of one of following path in extender and/or softening agent:

(i) condensation

(ii) open loop/balance

(iii) addition polymerization and

(iv) chain extension

Wherein optionally, but the polymkeric substance that end-blocking is obtained by above-mentioned polymerization route, so that the hydrolyzable end group to be provided.

13. the packing ring that connects sealing agent, tackiness agent, molding, coating and form on the spot, it contains the composition of claim 1.

14. the spatial method between two unit of a sealing, described method comprise apply claim 1-4 as mentioned above each composition and cause or allow said composition curing.

15. each composition of claim 1-4 is as the purposes of sealing agent.