CN1894311A - Organic elastomer silicone vulcanizates - Google Patents
Organic elastomer silicone vulcanizates Download PDFInfo
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- CN1894311A CN1894311A CN 200480037414 CN200480037414A CN1894311A CN 1894311 A CN1894311 A CN 1894311A CN 200480037414 CN200480037414 CN 200480037414 CN 200480037414 A CN200480037414 A CN 200480037414A CN 1894311 A CN1894311 A CN 1894311A
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- organopolysiloxane
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Abstract
A method for making an organic elastomeric base composition comprising an organic elastomer and silicone, the product prepared by the method, and the cured organic rubber obtained therefrom is disclosed. The method comprises; (I) mixing (A) an organic elastomer with (B) an optional compatibilizer, (C) an optional catalyst, (D) a silicone base comprising a curable organopolysiloxane, (E) an optional crosslinking agent, (F) a cure agent in an amount sufficient to cure said organopolysiloxane; and (II) dynamically vulcanizing the organopolysiloxane, wherein the weight ratio of organic elastomer (A) to silicone base (D) in the elastomeric base composition ranges from 95:5 to 30:70.
Description
[0001] the present invention relates to prepare the method for the organic elastomer base composition that contains organic elastomerics and siloxanes, by the product and the thus obtained solidified organo-silicone rubber of this method preparation.
[0002] still need be with the organic elastomer of efficient manner improvement its performance under ultimate temperature.Especially, still need to be provided at the organic elastomer composition that uses in the various application that wherein require height and/or low-temperature performance.Also need improve the organic elastomer of its processing with efficient manner.
[0003]] exist less relatively successful trial by the interpolation silica alkyl polymer or with it in conjunction with the organic elastomer that modification is provided.Because the uncompatibility of organic elastomer and silica alkyl polymer causes being difficult to obtain stable uniform mixture.In addition, but blend must co-crosslinking.Provide some representative example of organic elastomer and silicone elastomer composition to comprise United States Patent (USP) 4942202,5171787 and 5350804.
[0004] U.S.4942202 has instructed a kind of rubber combination and sulfurized rubber product of hydrocarbon compoud containing fluorine.By make organo-peroxide under shearing strain with (I) silicon rubber, (II) when independent use not with the saturated elastomerics of organo-peroxide reaction, (III) when having organo-peroxide, can react with another elastomerics of silicon rubber co-crosslinking, thus the composition of preparation ' 202.Other elastomerics (III) also can with component (II) co-crosslinking or highly miscible.
[0005] U.S.5171787 has instructed and has contained organic silicone elastomers base compounded rubber composition, and uses thereof.Comprise the polymkeric substance of the formation rubber of organopolysiloxane and organic rubber by compounding (A), (B) each molecule has the silicon compound of at least two hydrolysable group and (C) heavy metal compound, amine or the quaternary ammonium salt of catalytic hydrolysis and condensation reaction; And make experience hydrolysis of gained prescription and condensation reaction, keep prescription to avoid simultaneously by shearing strain; Add linking agent subsequently, follow crosslinked described organic rubber, thus the composition of preparation ' 787.
[0006] U.S.5350804 has instructed a kind of compounded rubber composition, it comprise (a) 100 ℃ of following mooney viscosities at least 70, form the organic rubber shape elastic composition of the matrix phase of compounded rubber composition; (b) as the cure silicone rubber of the disperse phase of matrix in mutually.
[0007] the invention provides the use dynamic vulcanization method, based on the organic elastomer base composition that mixes siloxanes and organic elastomer.These organic elastomer base compositions come from novel hybrid technique of the present invention.These novel hybrid techniques provide a large amount of silicone rubber based compositions and are incorporated into the interior composition of fluorocarbon elastomer.Yet, keep the physicals feature of many required organic elastomers by the gained solidified organic rubber composition of organic elastomer base composition of the present invention preparation.
[0008] the invention provides the method that preparation contains the organic elastomer base composition of organic elastomer and siloxanes simultaneously, wherein silicone base is mixed with organic elastomer, and in this organic elastomer the dynamic vulcanization silicone base.Therefore, the present invention relates to prepare the method for elastomeric base composition, this method comprises:
(I) mix
(A) organic elastomer,
(B) Ren Xuan expanding material,
(C) Ren Xuan catalyzer,
(D) comprise the silicone base of curable organic polysiloxane,
(E) Ren Xuan linking agent,
(F) consumption is enough to solidify the solidifying agent of described organopolysiloxane; With
(II) this organopolysiloxane of dynamic vulcanization,
Wherein the weight ratio scope of organic elastomer (A) and silicone base (D) is 95: 5 to 30: 70 in elastomeric base composition.
[0009] preferably, mix by expressing technique.The order of blending ingredients (A)-(F) is not crucial.Can form the order of blending ingredients (A)-(F) by two embodiment preferred of instructing herein.In first embodiment, at first blending ingredients (A), (B) and (C) form " organic elastomer of modification ", subsequently it are mixed with component (D), (E) with (F).In second embodiment, at first blending ingredients (D), (E) and (F) form " siloxane glue material ", subsequently it are mixed with component (A), (B) with (C).
[0010] the invention further relates to elastomeric base composition and the solidified organic elastomer composition and the goods that prepare thus that obtains by method of the present invention.
(A) organic elastomer
[0011] component (A) is that second-order transition temperature (Tg) is lower than room temperature, perhaps is lower than 23 ℃, perhaps is lower than 15 ℃, perhaps is lower than 0 ℃ organic elastomer." second-order transition temperature " is meant the temperature of polymkeric substance when glassy transition is rubbery state.Can pass through ordinary method, for example dynamic mechanical analysis (DMA) and dsc (DSC) are measured second-order transition temperature." organic elastomer " as used herein do not comprise fluorohydrocarbon and based elastomer.Organic elastomer component (A) can be selected from any in organic elastomer known in the art main group and the rubber (showing the ASTM term in bracket), for example natural rubber (NR), polyisoprene rubber (IR); styrene-butadiene rubber(SBR) (SBR); divinyl rubber (BR); chloroprene rubber (CR); chlorinatedpolyethylene (CPE); isoprene-isobutylene rubber; paracril (NBR); chlorosulfonated polyethylene (CSM); acrylic rubber (ACM); epichloro hydrin rubber (ECO); ethylene-vinyl acetate rubber (EVM); ethylene-propylene acids rubber; ethene-alpha-olefin copolymer rubber; ethene-alpha-olefin-diolefine binary polymerization rubber (EPDM) and hydrogenated nitrile-butadiene rubber (HNBR).
[0012] or, organic elastomer is a high performance elastomer, and it is selected from chlorosulfonated polyethylene (CSM), chlorinatedpolyethylene (CPE/CM), ethylene-vinyl acetate rubber (EVM), epichloro hydrin rubber (ECO), hydrogenated nitrile-butadiene rubber (HNBR) and acrylic rubber (ACM).Perhaps, organic elastomer is ethene-alpha-olefin-diolefine binary polymerization rubber (EPDM).
[0013] in the organic elastomer embodiment of the chemical modification of the following stated, (A) be selected from the organic elastomer that contains organic polymer, described organic polymer can with expanding material (B) reaction to produce the organic elastomer of modification.Think that organic elastomer component (A) can be the mixture of organic polymer.Yet, in the embodiment of the organic elastomer of chemical modification, 2wt% at least, perhaps 5wt% at least, perhaps at least 10% organic elastomer composition should contain have can with the organic polymer of the reactive group of expanding material (B) reaction.
(B) expanding material
[0014] expanding material (B) can be selected from any hydrocarbon, organo-siloxane, fluorohydrocarbon or its combination, think that they to improve silicone base (D) and organic elastomer (A) blended mode modification organic elastomer or silicone base, have successive organic phase and discontinuous (promptly inner) siloxanes mixture mutually with generation.Typically, expanding material can be a kind of in two types.In first embodiment, (be called physical compatibilizer herein), expanding material is selected from any hydrocarbon, organo-siloxane, fluorohydrocarbon or its combination, think they with the reaction of organic elastomer (A) or silicone base (D), still improve mixing of organic elastomer and silicone base simultaneously.(be called chemical expanding material herein) in second embodiment, expanding material is selected from any hydrocarbon, organo-siloxane, fluorohydrocarbon or its combination, think they can with organic elastomer or silicone base chemical reaction.Yet in any one embodiment, expanding material necessarily can not hinder the dynamical cure of the organopolysiloxane component of the following stated.
[0015] in organic embodiment of physically modified, expanding material (B) can be selected from and improve silicone base and organic elastomer blended any expanding material known in the art.Typically, this expanding material is the reaction product of organopolysiloxane and organic polymer.
[0016] in organic embodiment of chemical modification, typically, expanding material (B) can be selected from (B ') contains organic (being non-silicone) compounds of two or more ethylenic groups, (B ") contains the organopolysiloxane of at least two alkenyls; (B ) also contains at least one hydrolysable group that is connected on its Siliciumatom or the functional silane of alkene of at least one hydroxyl; (B " ") has the amine of being selected from; acid amides; isocyanuric acid ester; phenol, acrylate, the organopolysiloxane of at least one organo-functional group of epoxy and thiol group, and (B '), any combination of (B "); (B ) and (B " ").
[0017] organic expanding material (B ') can especially exemplify such as diallyl phthalate, cyanacrylate, 2,4,6-triallyl Oxy-1,3,5-triazine, triallyl 1,3,5-benzenetricarboxylic acid ester, 1,5-hexadiene, low-molecular-weight polyhutadiene, 1,7-octadiene, 2,2 '-diallyl bisphenol, N, the compound of N '-diallyl tartrate diamide, diallyl urea, diallyl succinate and divinylsulfone and so on.
[0018] (the optional comfortable intramolecularly of B ") has straight chain, side chain or the ring-type organopolysiloxane of at least two alkenyls to expanding material.The example of this organopolysiloxane comprises divinyl tetramethyl disiloxane, ring trimethylammonium trivinyl trisiloxanes, ring tetramethyl-tetrem thiazolinyl tetrasiloxane, hydroxy-end capped poly-ethylene methacrylic radical siloxane, hydroxy-end capped poly-ethylene methacrylic radical siloxane-common-polydimethylsiloxane, the end capped polydimethylsiloxane of dimethylvinylsiloxy, four (dimethylvinylsiloxy) silane and three (dimethylvinylsiloxy) phenyl silane.Perhaps, (B ") is that viscosity is about 25-100mPa.s to expanding material, contains the hydroxy-end capped poly-ethylene methacrylic radical siloxane [HO (MeViSiO) of the hydroxyl of 20-35% vinyl and 2-4% and silicon bonding
xH] oligopolymer.
[0019] expanding material (B ) is to contain at least one alkylene group, and it is unsaturated typically to contain vinyl, and the silane of part that is selected from least one and silicon bonding of hydrolysable group or hydroxyl.Suitable hydrolysable group comprises alkoxyl group, aryloxy, acyloxy or amide group.The example of this silane is vinyltriethoxysilane, vinyltrimethoxy silane, hexenyl triethoxyl silane, hexenyl Trimethoxy silane, methyl ethylene disilane alcohol, octenyl triethoxyl silane, vinyltriacetoxy silane, vinyl three (2-ethoxy ethoxy) silane, two (the N-methylacetamide base) silane of methyl ethylene, methyl ethylene disilane alcohol.
[0020] be organopolysiloxane expanding material (B " ") with at least one organo-functional group that is selected from amine, acid amides, isocyanuric acid ester, phenol, acrylate, epoxy and thiol group.Possible situation is that a part of curable organic polysiloxane in the silicone base component (D) of the following stated also can serve as expanding material.For example, can use catalyzer (C), a part of curable organic polysiloxane in the silicone base (D) is at first reacted with organic elastomer (A), produce the organic elastomer of modification.Then, further mixed and modified organic elastomer and the silicone base (D) that all the other contain the curable organic polysiloxane, and dynamic vulcanization organopolysiloxane as described below.
[0021] in another chemical modification embodiment, can select any organic elastomer as component (A), condition be this organic elastomer contain can with at least one group of at least a portion siloxane glue material reaction.In other words, this organic elastomer should be by reacting for selected operation curing mechanism of organopolysiloxane and silicone base.Add solidifying agent (F) to organopolysiloxane component (D) with randomly in the linking agent component (E), so that pass through dynamic vulcanization technology curing organopolysiloxane.Typically, in the dynamic vulcanization technological process, promptly in the step (II), the curing chemistry that takes place in the siloxane glue material surface also can with the organic elastomer precursor reactant, this further is dispersed in siloxanes in the organic elastomer.The representative limiting examples of the reactive group on organic elastomer comprises methyl, methylene radical, vinyl and halogen.For example, methyl on organic elastomer or methylene radical can with the peroxide reactions of selecting with solidifying agent as siloxane glue material, so between organopolysiloxane and organic elastomer, form chemical bond.As another example, the vinyl on organic elastomer can be by addition curing mechanism or the reaction of radically curing mechanism.
[0022] in " siloxane glue material " embodiment, depend on the type of modification, typically, expanding material (B) can be joined in the siloxane glue material.
[0023] can determine by normal experiment in the consumption of per 100 parts of employed expanding materials of organic elastomer, typically,, use the 0.05-15 weight part, perhaps 0.05-10 weight part, perhaps 0.1-5 weight part expanding material for per 100 parts of organic elastomers.
(C) catalyzer
[0024] Ren Xuan component (C) is a catalyzer.Typically, in organic embodiment of chemical modification, use catalyzer.Just because of this, it typically is radical initiator, and described radical initiator is selected from the known in the art any organic compound that generates free radical under heating up.Do not limit initiator particularly; it can be any known azo or diazonium compound; for example 2; 2 '-Diisopropyl azodicarboxylate; but be preferably selected from organo-peroxide, for example hydroperoxide, peroxidation diacyl, ketone peroxide, peroxy esters, dialkyl, peroxide two carbonic ethers, peroxy ketal, peroxy acid, acyl group alkyl sulphonyl superoxide and alkyl list peroxide two carbonic ethers.Yet crucial requirement is should enough lack the transformation period of initiator, so that promote the reaction of expanding material (B) and organic elastomer (A) in time for preparing and temperature limitation.Modification temperature itself depends on the type of selected organic elastomer and expanding material again, and typically is low to moderate actual consistent with uniform mixing component (A)-(C).The specific examples of the spendable suitable superoxide of the method according to this invention especially comprises: 2, and 5-dimethyl-2,5-two (t-butylperoxy) hexane; Benzoyl peroxide; Dicumyl peroxide; The O-toluic acid peroxide tert-butyl ester; The ring-type peroxy ketal; T-butyl hydroperoxide; Cross the oxy pentanoic acid tert-butyl ester; Lauroyl peroxide; 2 ethyl hexanoic acid peroxide tert-pentyl ester; Vinyl three (t-butylperoxy) silane; Peroxide di-t-butyl, 1, two (t-butyl peroxy sec.-propyl) benzene of 3-; 2,2,4-tri-methyl-amyl-2-hydroperoxide; 2, two (t-butylperoxy)-2 of 5-, 5-dimethyl hexin-3, t-butylperoxy-3,5,5 Trimethylhexanoic acid ester; Cumene hydroperoxide; T-butyl per(oxy)benzoate; With diisopropyl benzene list hydroperoxide.In per 100 parts of organic elastomers, typically use less than 2 weight part superoxide, perhaps also can use 0.05-1 part and 0.2-0.7 part.
(D) silicone base, (E) optional linking agent and (F) solidifying agent
[0025] component (D) is to contain curable organic polysiloxane (D ') and the filler (silicone base of D ") randomly.The curable organic polysiloxane is defined as at any organopolysiloxane of its molecular memory at least two curable groups herein.Organopolysiloxane is well known in the art, and usually is expressed as and contains any amount of M unit (R
3SiO
0.5), D unit (R
2SiO), T unit (RSiO
1.5) or Q unit (SiO
2), wherein R is any univalence hydrocarbyl independently.Perhaps, organopolysiloxane usually is described to have following general formula: [R
mSi (O)
4-m/2]
n, wherein R is any univalence hydrocarbyl independently, and m=1-3, and n is at least 2.
[0026] organopolysiloxane in silicone base (D) must have at least two curable groups at its intramolecularly." curable groups " as used herein is defined as and can reacts with self or with another organic group, perhaps with any organic or siloxane groups of linking agent reaction with cross-lined organic polyorganosiloxane.This crosslinked solidified organopolysiloxane that causes.In case produce the organopolysiloxane known in the art of silicon rubber when the representative of the curable organic polysiloxane type that can use is curing in silicone base.At " the Encyclopedia of Chemical Technology " of Kirk-Othmer, the 4th edition, Vol.22, p.82-142, John Wiley﹠amp; Sons discloses the limiting examples of the representative of this organopolysiloxane among the NY, at this by with reference to being introduced into.Typically, can pass through many mechanism of crosslinkings, use various curing groups, solidifying agent and optional linking agent on organopolysiloxane, come curing organopolysiloxane.Although there are many mechanism of crosslinkings, preparing the employed more common mechanism of crosslinking of silicon rubber by the curable organic polysiloxane in the art is crosslinked, hydrosilylation or the addition curing and condensation cured that free radical causes.Therefore, the curable organic polysiloxane can be selected from but be not limited to experience any any organopolysiloxane of these aforementioned mechanism of crosslinkings.Select component (D), (E) consistent with curing or mechanism of crosslinking with (F).For example, if select hydrosilylation or addition curing (being called " hydrosilylation cure embodiment " herein), the silicone base that then contains the organopolysiloxane with at least two vinyl (curable groups) will be as component (D '), the organic hydride silicon compound is used as component (F) as component (E) and platinum catalyst.For condensation cured (condensation cured embodiment), selection contains and has at least two silicone base with the organopolysiloxane of the hydrolysable precursors (being that silanol or organoalkoxysilane are regarded as curable groups) of the hydroxyl or the hydroxyl of silicon bonding as component (D), and select condensation cure catalyst known in the art, for example tin catalyst is as component (F).Crosslinked (" radically curing embodiment ") for the free radical initiation, if mixture solidified in time of dynamic vulcanization step (II) and temperature range is talked about, then can select any organopolysiloxane as component (D), and select radical initiator as component (F).Depend on the selection of the crosslinked interior component (F) that this free radical causes, any alkyl for example methyl can be regarded as curable groups, and this is because their can be crosslinked under the condition that this free radical causes.
[0027] employed siloxanes phase, promptly defined herein component (D), (E) and combination (F), consumption can change with the consumption of employed organic elastomer (A).
[0028] be the weight ratio of report organic elastomer (A) and silicone base (D) easily, its scope typically is 95: 5 to 30: 70, and perhaps 90: 10 to 40: 60, perhaps 80: 20 to 40: 60.
[0029] in hydrosilylation cure embodiment of the present invention, can select component (D), (E) and (F), so that in sulfuration process, produce silicon rubber by the hydrosilylation cure technology.Therefore, in the hydrosilylation cure embodiment, (D ') is selected from and contains at least two diorganopolysiloxanecompositions uncompounded rubber and optional (D ") reinforcing fillers with alkenyl of 2-20 carbon atom.Alkenyl is exemplified by vinyl, allyl group, butenyl, pentenyl, hexenyl and decene base, preferred vinyl or hexenyl particularly.The position of alkenyl functionality is not crucial and it can be at molecule chain end, at the non-terminal position place of molecular chain, perhaps at these two position bondings.Typically, alkenyl be vinyl or hexenyl and this group with 0.0001-3 mole %, perhaps the content of 0.0005-1 mole % is present in the diorganopolysiloxanecompositions.The organic group with the silicon bonding of all the other (being non-alkenyl) is independently selected from and does not contain aliphatic undersaturated hydrocarbon or halogenated hydrocarbon group in the diorganopolysiloxanecompositions.These can exemplify the alkyl with 1-20 carbon atom, for example methyl, ethyl, propyl group, butyl, amyl group and hexyl particularly; Cycloalkyl, for example cyclohexyl and suberyl; Aryl with 6-12 carbon atom, for example phenyl, tolyl and xylyl; Aralkyl with 7-20 carbon atom, for example benzyl and styroyl; With haloalkyl with 1-20 carbon atom, for example 3,3,3-trifluoro propyl and chloro methyl.Certainly be appreciated that and select these groups, make the second-order transition temperature of diorganopolysiloxanecompositions be lower than room temperature, so cured polymer is an elastomerics.Typically, the organic group with the silicon bonding of non-alkenyl accounts at least 85 of organic group in the diorganopolysiloxanecompositions in diorganopolysiloxanecompositions, perhaps 90mol% at least.
[0030] therefore, polydiorganosiloxane (D ') can be homopolymer, copolymer or the terpolymer that contains this organic group.Example especially comprises and contains the unitary homopolymer of dimethylsilane oxygen base, contain 3,3, the unitary homopolymer of 3-trifluoro propyl methyl-silicane oxygen base, the multipolymer that contains dimethylsilane oxygen base unit and phenyl methyl siloxy units, contain dimethylsilane oxygen base unit and 3,3, the unitary multipolymer of 3-trifluoro propyl methyl-silicane oxygen base, the multipolymer of dimethylsilane oxygen base unit and the unitary multipolymer of phenylbenzene siloxy-and dimethylsilane oxygen base unit, phenylbenzene siloxy units and phenyl methyl siloxy units.Molecular structure neither be crucial, can exemplify the linear chain structure of straight chain and part branching, and wherein the straight chain system is the most typical.
[0031] specifically exemplifying of diorganopolysiloxanecompositions (D ') comprises: the end capped dimethyl siloxane of trimethylsiloxy-methyl ethylene silicone copolymers; End capped methylphenyl siloxane-the dimethyl siloxane of trimethylsiloxy-methyl ethylene silicone copolymers; Trimethylsiloxy is end capped 3,3,3-trifluoro propyl methylsiloxane multipolymer; Trimethylsiloxy is end capped 3,3,3-trifluoro propyl methyl-methyl ethylene silicone copolymers; The end capped dimethyl polysiloxane of dimethylvinylsiloxy; The end capped dimethyl siloxane of dimethylvinylsiloxy-methyl ethylene silicone copolymers; The end capped methyl phenyl silicone of dimethylvinylsiloxy; End capped methylphenyl siloxane-the dimethyl siloxane of dimethylvinylsiloxy-methyl ethylene silicone copolymers; Wherein at least one end group is the similar multipolymer of present as dimethylhydroxysilox(.The typical system that is used for lower temperature application comprises methylphenyl siloxane-dimethyl siloxane-methyl ethylene silicone copolymers and diphenyl siloxane-dimethyl siloxane-methyl ethylene silicone copolymers, and especially wherein the molar content of dimethyl siloxane units is about 85-95%.
[0032] organopolysiloxane also can be made up of the mixture of two or more organopolysiloxanes.Perhaps, diorganopolysiloxanecompositions (D ') is straight chain polydimethylsiloxane homopolymer and preferably all uses ethenyl blocking at each end of its molecule that perhaps it is this homopolymer that also contains at least one vinyl along its main chain.
[0033] for purpose of the present invention, preferred diorganopolysiloxanecompositions is that molecular weight is enough to obtain the diorganopolysiloxanecompositions uncompounded rubber at least about 30 Williams plasticity value, wherein measures described plasticity value by the test method 926 of ASTM (American society for testing materials) (ASTM).Although there is not any absolute upper limit in the plasticity value of component (D '), the actual consideration of the processibility in the mixing equipment of routine limits this numerical value usually.Typically, plasticity value should be 40-200, perhaps 50-150.
[0034] diorganopolysiloxanecompositions that contains unsaturated group of preparation high-consistency is known and they do not require in this manual and go through.
[0035] (D ") is any filler of known enhancing diorganopolysiloxanecompositions (D ') and is preferably selected from specific surface area and is at least about 50m Ren Xuan component
2The thermally-stabilised mineral of the particulate of/g, for example silicon oxide of pyrolysis and precipitation forms, silicon oxide aerosol and titanium dioxide.The silicon oxide of pyrolysis form is based on the typical reinforcing filler of its high surface area, and its surface-area is 450m at most
2/ g.Perhaps, can use surface-area to be 50-400m
2/ g, perhaps 90-380m
2The pyrolysis method silicon oxide of/g.For per 100 weight part diorganopolysiloxanecompositions (D '), with about 150 weight parts of about 5-, perhaps the content of 10-100 or 15-70 weight part adds filler.
[0036] typically handle filler and make its surface hydrophobicity, this is a typical way in the silicon rubber field.This can realize by silicon oxide is reacted with the liquid silicone compound that contains the hydrolysable precursors of silanol group or silanol group.The compound (being also referred to as anti-crape agent or softening agent in the silicon rubber field) that can be used as filler treatment agent comprises the composition of lower molecular weight liquid hydroxyl or alkoxy end-capped poly-diorganopolysiloxanecompositions, six organic sily oxide, ring dimethyl-silicon azane and six organic disilazanes and so on.
[0037] component (D) also can contain in silicone rubber formulations other material commonly used, comprising but be not limited to other additive known in the art that does not disturb step (II) of oxidation inhibitor, crosslinking coagent, machining agent, pigment and the following stated.
[0038] in hydrosilylation cure embodiment of the present invention, interpolation component (E) and it are the organic hydride silicon compounds (E ') crosslinked with diorganopolysiloxanecompositions (D ').The organic hydride silicon compound is to contain at least two organopolysiloxanes with the silicon bonded hydrogen atom at each intramolecularly, described and the reaction of the alkenyl functionality with (D ') in dynamic vulcanization step (II) process of the inventive method of silicon bonded hydrogen atom.Further (molecular weight) restriction is that component (E ') must have the hydrogen at least about 0.1 weight %, perhaps 0.2-2%, and perhaps the hydrogen bond of 0.5-1.7% is incorporated on the silicon.Those skilled in the art will appreciate that certainly diorganopolysiloxanecompositions (D ') or component (E ') or these two must have the functionality greater than 2, to solidify diorganopolysiloxanecompositions (be these functionality sums on average must greater than 4).In component (E '), or not crucial and it can be at the end of molecular chain, along the non-terminal position of molecular chain, perhaps at these two position bondings with the position of the hydrogen of silicon bonding.Organic group with the silicon bonding in the component (E ') is independently selected from above for described any stable hydrocarbon of diorganopolysiloxanecompositions (D ') or halo alkyl, comprising its embodiment preferred.The molecular structure of component (E ') neither be crucial, can exemplify straight chain, branching, ring-type and the reticulated structure of straight chain, part branching, and wherein straight-chain polymer or multipolymer are typical.Certainly to recognize that this component must be compatible with D ' (that is, solidifying aspect the diorganopolysiloxanecompositions, it is effective).
[0039] component (E ') can exemplify following: low-molecular-weight siloxanes, for example PhSi (OSiMe
2H)
3The end capped hydrogenated methyl polysiloxane of trimethylsiloxy; The end capped dimethyl siloxane of trimethylsiloxy-hydrogenated methyl silicone copolymers; The end capped dimethyl polysiloxane of dimethyl hydrogenation siloxy-; The end capped methylhydrogenpolysi,oxane of dimethyl hydrogen siloxy-; The end capped dimethyl siloxane of dimethyl hydrogen siloxy--hydrogenated methyl silicone copolymers; The ring-type methylhydrogenpolysi,oxane; Ring-type dimethyl siloxane-hydrogenated methyl silicone copolymers; Four (dimethyl hydrogen siloxy-) silane; Contain SiO
4/2The end capped hydrogenated methyl siloxane polymer of unitary trimethylsiloxy; By (CH
3)
2HSiO
1/2And SiO
4/2The silicone resin that the unit is formed; By (CH
3)
2HSiO
1/2, (CH
3)
3SiO
1/2And SiO
4/2The silicone resin that the unit is formed; By (CH
3)
2HSiO
1/2And CF
3CH
2CH
3SiO
3/2The silicone resin of forming; With by (CH
3)
2HSiO
1/2, (CH
3)
3SiO
1/2, CH
3SiO
3/2, Ph
3SiO
3/2And SiO
4/2The silicone resin that the unit is formed, wherein Ph represents phenyl.
[0040] typical organic hydride silicon compound is to contain to use R
3SiO
1/2Or HR
2SiO
1/2Unitary polymkeric substance of unit terminated RHSiO or multipolymer, wherein R is independently selected from the alkyl with 1-20 carbon atom, and phenyl or trifluoro propyl typically are methyl.In addition, the viscosity of component (E ') typically is about 0.5-3,000mPa.s, perhaps 1-2000mPa.s under 25 ℃.Component (E ') typically has 0.5-1.7% weight and is bonded to hydrogen on the silicon.Perhaps, to be selected from basically the polymkeric substance be made up of the hydrogenated methyl siloxane unit or to form, have hydrogen and the viscosity under 25 ℃ that 0.5-1.7% weight is bonded on the silicon by dimethyl siloxane units and hydrogenated methyl siloxane unit basically be the multipolymer of 1-2000mPa.s to component (E ').This typical system has the end group in trimethylsiloxy of being selected from or the dimethyl hydrogenation siloxy-.Perhaps, component (E ') is selected from resinous unitary multipolymer or reticulated structure.Multipolymer or reticulated structure unit comprise RSiO
3/2Unit or SiO
4/2The unit, and also can contain R
3SiO
1/2, R
2SiO
2/2And/or RSiO
3/2The unit, wherein R is independently selected from hydrogen or has the alkyl of 1-20 carbon atom, phenyl or trifluoro propyl, typically methyl.Be appreciated that and select competent R to be bonded to hydrogen on the silicon so that component (E ') typically has 0.5-1.7% weight as hydrogen.In addition, typically, the viscosity of component (E ') under 25 ℃ is about 0.5-3,000mPa.s, perhaps 1-2000mPa.s.Component (E ') also can be two or more combination of above-described system.
[0041], is enough to solidify the content use organic hydride silicon compound (E ') of diorganopolysiloxanecompositions (D ') with in the presence of the component (F) of the following stated.Typically, regulate its content, make the mol ratio of within it SiH and Si-alkenyl in (D ') greater than 1.Typically, it is about 50 that the ratio of this SiH/ alkenyl is lower than, perhaps 1-20, perhaps 1-12.The functional material of these SiH-be well known in the art and many be commercially available.
[0042] in hydrosilylation cure embodiment of the present invention, component (F) is a kind of hydrosilylation catalysts (F '), and it promotes the curing of diorganopolysiloxanecompositions.Can exemplify platinum catalyst, for example platinum black, be carried on platinum on the silicon oxide, be carried on platinum, Platinic chloride, the alcoholic solution of Platinic chloride, platinum/alkene complex, platinum/alkenyl siloxanes complex compound, platinum/beta-diketon complex compound, platinum/phosphine complex compound and analogue on the carbon; Rhodium catalyst, for example rhodium chloride and rhodium chloride/two (normal-butyl) sulfide complex compound and analogue; And palladium catalyst, for example palladium on carbon, Palladous chloride and analogue.Component (F ') typically is platinum based catalyst, for example Platinic chloride; Platinum dichloride, Tetrachloroplatinum; By the platinum complex catalyst (it dilutes with the end capped polydimethylsiloxane of dimethylvinylsiloxy) that the reaction of Platinic chloride and divinyl tetramethyl disiloxane is produced, it is according to the U.S. Patent No. 3419593 described preparations of Willing; And the neutralized complex of platinous chloride and divinyl tetramethyl disiloxane, it is according to people's such as Brown U.S. Patent No. 5175325 described preparations; These patents are introduced by reference at this.Perhaps, catalyzer (F) is the neutralized complex of platinous chloride and divinyl tetramethyl disiloxane.
[0043] will be enough to promote the component (F ') of the catalytic amount of reaction between organopolysiloxane (D ') and the component (E ') to join in the composition of the present invention, so as in time of dynamic vulcanization step (II) and temperature limitation curing organopolysiloxane.Typically, add hydrosilylation catalysts,, provide the atoms metal of about 0.1-500ppm, perhaps 0.25-50ppm so that based on the gross weight of elastomeric base composition.
[0044] in another embodiment, select component (D), (E) and (F), so that the condensation cured of organopolysiloxane to be provided.For condensation cured, selection has at least two organopolysiloxanes with the hydrolysable precursors (being that silanol or organoalkoxysilane are regarded as curable groups) of the hydroxyl or the hydroxyl of silicon bonding as component (D), with selection condensation cure catalyst known in the art, tin catalyst for example is as component (F).The organopolysiloxane that can be used as the organopolysiloxane of condensation curable be its intramolecularly contain at least two with the hydroxyl of silicon bonding or be hydrolyzed into silanol group (SiOH)) one or more organopolysiloxanes of group.Typically, if extra at least two SiOH bases or the SiOH precursor group of existing, then in the addition curing embodiment the following stated can be used as organopolysiloxane in the condensation cured embodiment as any organopolysiloxane of component (D), but alkenyl is not necessarily in condensation cured embodiment.As the organic hydride silicon compound of optional linking agent (E) and following identical for component (E) description.Yet more typically, linking agent is selected from alkoxyl group or the end capped organopolysiloxane of acyloxy, and they are known in the art in carrying out organopolysiloxane condensation cured.The condensation catalyst that can be used as solidifying agent in this embodiment is to promote to react between the SiOH base and organic hydride silicon compound (E) the SiH base of (if existence) in condensation reaction between the SiOH base in the diorganopolysiloxanecompositions (D) and the diorganopolysiloxanecompositions (D) so that solidify the former any compound by formation-Si-O-Si-key.The example of appropriate catalyst comprises metal carboxylate, for example dibutyltin diacetate, dibutyl tin laurate, acetate tripropyl tin, stannous octoate, stannous oxalate, naphthoic acid (naphthanate) Ya Xi; Amine, for example triethylamine, ethylidene triamine; And quaternary ammonium compound, for example benzyltrimethylammonium hydroxide, beta-hydroxyethyl trimethylammonium-2 ethyl hexanoic acid ammonium and beta-hydroxyethyl benzyl trimethyl dimethyl butyrate ammonium oxide (referring to, U.S.3024210 for example).
[0045] in an embodiment again, can select component (D), (E) and (F), so that the radically curing of organopolysiloxane to be provided.In this embodiment, organopolysiloxane can be any organopolysiloxane, but typically, organopolysiloxane has at least two alkenyls.Therefore, describing any organopolysiloxane that is suitable as (D ') more than in the addition curing embodiment also can be used for do not require linking agent (E), but it can assisting the radically curing embodiment in the free radical embodiment of the present invention.Can be from for selecting component (C), selecting solidifying agent (F) any radical initiator described above.
(G) Ren Xuan additive
[0046] except above-mentioned main ingredient (A)-(F), also one or more optional additives (G) of (promptly less than all 50 weight % of compositions) in a small amount can be incorporated in organic basic elastic composition of the present invention.Can enumerate these optional additives by following limiting examples: increment filler, for example quartz, lime carbonate and diatomite; Pigment, for example ferric oxide and titanium oxide; Filler, for example carbon black and finely-divided metal; Thermo-stabilizer, for example hydrous ceria, calcium hydroxide, magnesium oxide; And fire retardant, for example halohydrocarbon, hibbsite, magnesium hydroxide, wollastonite, organo phosphorous compounds and other fire-retardant (FR) material.Typically after dynamical cure, these additives are joined in the final composition, but also can add them at any some place of preparation, condition is their not interfere with dynamic sulfuration mechanism.The additional component of adding as preparation the following stated solidified elastic composition, these additives can be identical or different.
Mix
[0047] can be by any method of processing known in the art and mixed elastomer material, carry out the mixing of in step (I) component (A)-(F) and optional (G).Typical hybrid technology includes but not limited to mixing roll, forcing machine, Banbury, kneader or roller.Perhaps, can use expressing technique.Perhaps, can realize the mixing step (I) and the dynamic vulcanization step (II) of the inventive method by using twin screw extruder.Typically, in 100-350 ℃ temperature range, perhaps 125-300 ℃, perhaps extrude hybrid technique under 150-250 ℃.In an embodiment preferred of the inventive method, in twin screw extruder, less than 3 minutes, perhaps less than mixing in 2 minutes time period.
[0048] the present invention the widest aspect in, the order of blending ingredients (A)-(F) is not crucial.Typically, add (G) afterwards at (F), but this is not crucial, if (G) do not disturb organopolysiloxane curing (for example, (G) can with (A) organic elastomer and/or with the pre-mixing of (D) silicone base).Yet, in two embodiments of the following stated, can stipulate order by merging.
First mixes embodiment comprises:
(I) mix
(A) organic elastomer
(B) expanding material,
(C) Ren Xuan catalyzer,
Form the organic elastomer of modification; The organic elastomer that mixes this modification then with
(D) comprise the silicone base of curable organic polysiloxane,
(E) Ren Xuan linking agent,
(F) consumption is enough to solidify the solidifying agent of described organopolysiloxane.
[0049] the first step in this mixing embodiment produces product, is called " organic elastomer of modification " herein.Term as used herein " organic elastomer of modification " in case be meant further produce when mixing with siloxanes basis composition have continuous organic elastomer mutually with the organic elastomer of the organic/mixture of siloxanes of discontinuous (inside) siloxanes phase.The organic elastomer of modification can be regarded as chemical modification or physically modified, and this depends on the selection of component (A), (B) and optional (C), and below the employed subsidiary conditions in this mixing step that further describes.In the embodiment of the present invention of the organic elastomer for preparing chemical modification, select and blending ingredients (A), (B) and optional (C) reaction product of its mode feasible generation organic elastomer and expanding material.In the embodiment of the present invention of the organic elastomer for preparing physically modified, select and blending ingredients (A), (B) and optional (C) the physical mixture product of its mode feasible generation organic elastomer and expanding material.In either case, when the product of step (I) produces the organic elastomer of modification, organic elastomer (A) is modified, its mode make to produce organic/mixture of siloxanes, in case it has successive organic phase and discontinuous (inside) siloxanes mixture mutually with generation when further mixing with siloxanes basis composition.
[0050] then according to any hybrid technology described herein, blending ingredients (D), (E) and (F) and " organic elastomer of modification ".
Second mixes embodiment comprises:
(I) mix
(D) comprise the silicone base of curable organic polysiloxane,
(E) Ren Xuan linking agent,
(F) solidifying agent,
Form siloxane glue material, mix then this siloxane glue material with
(A) organic elastomer,
(B) Ren Xuan expanding material and
(C) Ren Xuan catalyzer.
[0051] second mixes embodiment is characterised in that at first mixed curing agent (F) and silicone base (D), forms siloxane glue material, mixes with organic elastomer (A) afterwards.Therefore, typically and (C) by hybrid silicone sizing material and organic elastomer (A) and the component of choosing wantonly (B), the organopolysiloxane in the dynamic vulcanization siloxane glue material then, thus prepare the organic elastomer base composition.
Dynamic vulcanization
[0052] second of the inventive method step (II) was the dynamic vulcanization organopolysiloxane.The dynamic vulcanization step is solidified organopolysiloxane.Step (II) can take place simultaneously with mixing step (I), perhaps carries out afterwards at mixing step (I).Typically, step (II) takes place simultaneously with mixing step (I), and by carrying out with described identical temperature range of step (I) and mixed processes.
Elastic composition
[0053] the invention still further relates to according to the organic elastomer composition of method described herein preparation and further relate to the solidified elastic composition of preparation thus.The contriver thinks, technology of the present invention provides unique and useful organic elastomer composition, this is by comparing with the organic elastomer for preparing with other method or technology and the similar bonded composition of silicone base, and the inherent physicals of this organic basic elastic composition proves.In addition, the solidified organic elastomer composition hereinafter described by organic basic elastic composition preparation of the present invention also has unique and useful performance.For example, the solidified organic elastomer by organic basic elastic composition preparation of the present invention has good astoundingly low temperature and high-temperature behavior and improved workability.
[0054] can by solidifying the organic elastomer component in the organic elastomer base composition of the present invention, prepare solidified organic elastomer base composition of the present invention by known curing technology.The curing of the organic elastomer and the additional component of adding before solidifying is well-known in the art.Can use any and additive in these known technologies, solidify organic elastomer base composition of the present invention, and by its preparation solidified organic elastomer.
[0055] extra component can be joined in the organic elastomer base composition, solidify organic elastomeric component afterwards.These comprise that other organic elastomer of blend or other organic elastomer base composition are in organic elastomer base composition of the present invention.These extra components also can be typically to join any component or composition in organic elastomer or the organic elastomer glue for preparation solidified organic elastomer composition.Typically, the optional self filler of these components, processing aid and solidifying agent.Many commercially available organic elastomers may comprise the component that these are extra.Organic elastomer with these additional component can be used as aforesaid component (A), and condition is the dynamic vulcanization that they do not hinder the silicone base in the inventive method step (II).Perhaps, can before final curing organic elastomer, this extra component be joined in the organic elastomer base composition.
[0056] solidified organic elastomer composition also can comprise filler.The example of filler comprises carbon black, coal ash particle, silicon oxide, metal oxide, for example ferric oxide and zinc oxide, zinc sulphide, lime carbonate, wollastonite, Calucium Silicate powder, barium sulfate and other filler known in the art.
[0057] solidified organic elastomer composition can be used in the various application, for example be used to prepare various manufacturing goods, wherein can exemplify but be not limited to O shape ring, packing ring, sealing member, lining, flexible pipe, pipeline, barrier film, sleeve pipe, valve, band, tectum (blanket), coating, roller, moulded parts, extrusion sheet, seam sealer and extruded product, be used for comprising but be not limited to the transportation, comprising motor vehicle, water craft and aviation; Chemistry and petroleum installation; Electric wire and cable; Food processing plant; Nuclear power plant; Space flight; Medical use; With oil/gas drilling industry with typically use high performance elastomer, during for example other of ECO, FKM, HNBR, acrylic rubber and silicone elastomer used.
Embodiment
[0058] lists following embodiment and further set forth composition of the present invention and method.All umbers and percentage ratio obtain down at about 23 ℃ based on weight and all measuring results among the embodiment, except as otherwise noted.
Material
CATALYST1 be 1.5% 1,3-divinyl-1,1,3, the platinum complex of 3-tetramethyl disiloxane; 6% tetramethyl divinyl disiloxane; The polydimethylsiloxane of 92% dimethyl ethenyl blocking and 0.5% has the dimethyl cyclopolysiloxane more than or equal to 6 dimethyl siloxane units.
DI-CUP R is by Hercules, and Inc. is with the dicumyl peroxide (CSA#80-43-3) of the commercially available 98-100% of DI-CUP R form.
DI-CUP 40C is by Hercules, and Inc. is with the dicumyl peroxide (CSA#80-43-3) on the precipitated chalk of loading on of the commercially available 39.5-41.5% of DI-CUP 40C form.
EPDM1 is by Dupont Dow Elastomers, and LLC is with the commercially available ethylene-propylene terpolymer (EPDM) that contains low diolefine of Nordel IP NDR3640.00 form.
GP-50 is with the commercially available silicon rubber base-material of Silastic GP-50 form by Dow Corning Corporation.
LCS-755 is with the commercially available silicon rubber base-material of Silastic LCS-755 form by Dow Corning Corporation.
TRIG 145PD is by Akzo Nobel Chemicals, Inc. with TRIGONOX 145B-45PD form commercially available 2,5-dimethyl-2,5-two (t-butylperoxy) hexin (CAS#78-63-7).
VAROX is by R.T.Vanderbilt, Company, Inc. with VAROX DBPH-50 form commercially available on inert filler 2,5-dimethyl-2,5-two (t-butylperoxy) hexane.
Luperox F is by Atofina Chemicals, and Inc. is with two-(2-t-butyl peroxy sec.-propyl) commercially available benzene of LUPEROX F form.
N774 is with the commercially available carbon black of Sterling NS form by Cabot Corporation.
Austin Black is with the commercially available comminuted coal of AustinBlack 325 forms by Coal Fillers Incorporated.
Ricon 150 is polyhutadiene (CAS#9003-17-2) and commercially available with Ricon 150 forms by Startomer Company.
X-LINKER1 is Dow Corning 6-3570, the end capped dimethyl methyl of trimethylsiloxy hydrogen siloxane, and its viscosity is 5cSt, and has the hydrogen of 0.76wt% on silicon.
Test
[0059] by measures stretching, elongation and 100% modulus properties of solidified elastomeric base composition based on the operation of ASTM D 412.Measure Xiao A hardness by operation based on ASSTM D 2240.
Embodiment 1
[0060] in end runner mill, mixes GP-50 (60g) and Luperox F (0.2g), form siloxane glue material.150 ℃ and 125rpm (rev/min) under, this siloxane glue material and EPDM (140g) are joined in the 379ml Haake mixing roll of being furnished with the Banbury rotor.After about 8 minutes and moment of torsion increased, material temperature was about 200 ℃.In the time of 12 minutes, take out elastomeric base composition.
In case cooling, then compounding gained elastomeric base composition (50g) and Dicup R (1g) and N774 (17.5g) in end runner mill, and mix each component are up to evenly.
Embodiment 2
[0062] in end runner mill, mixes GP-50 (60g), Luperox F (0.2g) and Ricon 150 (0.3g), form siloxane glue material.150 ℃ and 125rpm (rev/min) under, this siloxane glue material and EPDM (140g) are joined in the 379mlHaake mixing roll of being furnished with the Banbury rotor.After about 8 minutes and moment of torsion increased, material temperature was about 200 ℃.In the time of 12 minutes, take out elastomeric base composition.
[0063] in case cooling, then compounding gained elastomeric base composition (50g) and Dicup R (1g) and N774 (17.5g) in end runner mill, and mix each component are up to evenly.
Embodiment 3
[0064] in end runner mill, mixes LCS-755 (100 parts), Catalyst 1 (0.22 part), ETCH (0.23 part) and X-LINKER 1 (1.5 parts), form siloxane glue material.150 ℃ and 125rpm (rev/min) under, this siloxane glue material (60g) and EPDM (140g) are joined in the 379ml Haake mixing roll of being furnished with the Banbury rotor.After about 8 minutes and moment of torsion increased, material temperature was about 200 ℃.In the time of 12 minutes, take out elastomeric base composition.
[0065] in case cooling, then compounding gained elastomeric base composition (50g) and Dicup R (1g) and N774 (17.5g) in end runner mill, and mix each component are up to evenly.
[0066] under 177 ℃, dull and stereotyped curing embodiment 1-3 totally 10 minutes.Summarized the physicals of gained solidified elastomeric base composition in the table 1.
Table 1
| Embodiment # | 1 | 2 | 3 |
| Xiao A hardness | 59 | 61 | 63 |
| Tensile strength, MPa | 12.6 | 11.2 | 9.4 |
| Elongation, % | 228 | 201 | 246 |
Embodiment 4
[0067] 120 ℃ and 125rpm (rev/min) under, BPDM (140g), DI-CUP40C (0.3g) and Ricon 150 (0.3g) are joined in the 379ml Haake mixing roll of being furnished with the Banbury rotor.After about 3 minutes, material temperature is about 160 ℃.Add GP-50 (60g), add Luperox F (0.2g) then.After about 11 minutes and moment of torsion increased, temperature was above 200 ℃.In the time of 15 minutes, take out elastomeric base composition.
[0068] in case cooling, then compounding gained elastomeric base composition (50g) and Dicup R (1g) and N774 (17.5g) in end runner mill, and mix each component are up to evenly.The Xiao A hardness of solidified elastomeric base composition is 60, and tensile strength is 11.7MPa, and elongation is 202%.
Embodiment 5
[0069] adopts the 25mm Werner and Pfleiderer twin screw extruder of screw speed, the basic elastic composition of preparation fluorohydrocarbon with the processing sections that is heated to 150 ℃ and 180 ℃ and 500rpm.At first mix LCS-755 (100 parts), ZnO (5 parts) and Varox (0.5 part), form siloxane glue material.For sample A, the feeding speed of forcing machine is 174g/min for organic elastomer EPDM1, and is 160g/min for siloxane glue material.For sample B, speed separately is 106g/min and 225g/min.For sample C, speed separately is 72g/min and 147g/min.In per 100 parts of EPDM1, the gained organic elastomer composition that compounding obtains from this forcing machine and 7 parts of DI-CUP 40C and 15 parts of AustinBlack.Dull and stereotyped solidified sample is 10 minutes under 177 ℃.The Xiao A hardness of sample A is 54, and tensile strength is that 5.3MPa and elongation are 229%.The Xiao A hardness of sample B is 53, and tensile strength is that 5.7MPa and elongation are 209%.The Xiao A hardness of sample C is 52, and tensile strength is that 5.3MPa and elongation are 205%.
Claims (11)
1. the method for preparing elastomeric base composition, this method comprises:
(I) mix
(A) organic elastomer, with
(B) Ren Xuan expanding material,
(C) Ren Xuan catalyzer,
(D) comprise the silicone base of curable organic polysiloxane,
(E) Ren Xuan linking agent,
(F) consumption is enough to solidify the solidifying agent of described organopolysiloxane;
With
(II) this organopolysiloxane of dynamic vulcanization,
Wherein the weight ratio scope of organic elastomer (A) and silicone base (D) is 95: 5 to 30: 70 in elastomeric base composition.
2. the process of claim 1 wherein and mix by expressing technique.
3. the process of claim 1 wherein and at first mix:
(A) organic elastomer,
(B) expanding material,
(C) Ren Xuan catalyzer,
Form the organic elastomer of modification; The organic elastomer that mixes this modification then with
(D) comprise the silicone base of curable organic polysiloxane,
(E) Ren Xuan linking agent,
(F) consumption is enough to solidify the solidifying agent of described organopolysiloxane.
4. the process of claim 1 wherein and at first mix:
(D) comprise the silicone base of curable organic polysiloxane,
(E) Ren Xuan linking agent,
(F) solidifying agent,
Form siloxane glue material; Mix then this siloxane glue material with
(A) organic elastomer,
(B) Ren Xuan expanding material and
(C) Ren Xuan catalyzer.
5. any one method of claim 1-4, wherein organic elastomer is selected from natural rubber (NR), polyisoprene rubber (IR); styrene-butadiene rubber(SBR) (SBR); divinyl rubber (BR); chloroprene rubber (CR); chlorinatedpolyethylene (CPE); isoprene-isobutylene rubber; paracril (NBR); chlorosulfonated polyethylene (CSM); acrylic rubber (ACM); epichloro hydrin rubber (ECO); ethylene-vinyl acetate rubber (EVM); ethylene-propylene acids rubber; ethene-alpha-olefin copolymer rubber; ethene-alpha-olefin-diene binary polymerization rubber (EPDM) or hydrogenated nitrile rubber (HNBR).
6. wherein there is catalyzer (C) in any one method of claim 1-4 and for being selected from the organo-peroxide in hydroperoxide, peroxidation diacyl, ketone peroxide, peroxy esters, dialkyl, peroxide two carbonic ethers, peroxy ketal, peroxy acid, acyl group alkyl sulphonyl superoxide and alkyl list peroxide two carbonic ethers.
7. any one method of claim 1-4, wherein silicone base is that the Williams plasticity value is at least about 30 diorganopolysiloxanecompositions uncompounded rubber, wherein said plasticity value is measured by the test method 926 of ASTM (American society for testing materials) (ASTM).
8. wherein there is solidifying agent (F) in any one method of claim 1-4 and is the organo-peroxide that is selected from hydroperoxide, peroxidation diacyl, ketone peroxide, peroxy esters, dialkyl, peroxide two carbonic ethers, peroxy ketal, peroxy acid, acyl group alkyl sulphonyl superoxide and alkyl list peroxide two carbonic ethers.
9. the product of producing by any one method of claim 1-8.
10. the solidified elastic composition that contains the product of right requirement 9.
11. contain the manufacturing goods of the product of right requirement 9 or 10.
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|---|---|---|---|
| US52952703P | 2003-12-15 | 2003-12-15 | |
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| US60/529,518 | 2003-12-15 | ||
| US60/529,527 | 2003-12-15 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102516558A (en) * | 2011-12-16 | 2012-06-27 | 山东大学 | Polysiloxane modified nitrile rubber, synthesis method and preparation of vulcanized rubber |
| CN102666710A (en) * | 2009-09-22 | 2012-09-12 | 联合碳化化学及塑料技术有限责任公司 | Flexible, molded or extruded articles and semiconductive compounds for their manufacture |
| CN103904530A (en) * | 2014-03-06 | 2014-07-02 | 佛山市高明毅力温控器有限公司 | Manufacturing process for sealing structure of electric junction box |
| CN105906950A (en) * | 2016-05-30 | 2016-08-31 | 成都硅宝科技股份有限公司 | High temperature resistant ethylene propylene rubber/silicon rubber blend and preparation method thereof |
| CN108559270A (en) * | 2014-04-15 | 2018-09-21 | 3M创新有限公司 | Curable organosilicon composition |
| CN110982281A (en) * | 2019-12-19 | 2020-04-10 | 福建拓烯新材料科技有限公司 | Blended fluorosilicone rubber composition and preparation method thereof |
| WO2022204935A1 (en) * | 2021-03-30 | 2022-10-06 | Dow Global Technologies Llc | Curable polyolefin composition and cured product |
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2004
- 2004-12-13 CN CN 200480037414 patent/CN1894311A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102666710A (en) * | 2009-09-22 | 2012-09-12 | 联合碳化化学及塑料技术有限责任公司 | Flexible, molded or extruded articles and semiconductive compounds for their manufacture |
| CN102666710B (en) * | 2009-09-22 | 2016-08-31 | 联合碳化化学及塑料技术有限责任公司 | Flexible molding or the goods of extrusion and for preparing their quasiconductor mixed thing |
| CN102516558A (en) * | 2011-12-16 | 2012-06-27 | 山东大学 | Polysiloxane modified nitrile rubber, synthesis method and preparation of vulcanized rubber |
| CN102516558B (en) * | 2011-12-16 | 2013-12-04 | 山东大学 | Polysiloxane modified nitrile rubber, synthesis method and preparation of vulcanized rubber |
| CN103904530A (en) * | 2014-03-06 | 2014-07-02 | 佛山市高明毅力温控器有限公司 | Manufacturing process for sealing structure of electric junction box |
| CN108559270A (en) * | 2014-04-15 | 2018-09-21 | 3M创新有限公司 | Curable organosilicon composition |
| CN108559270B (en) * | 2014-04-15 | 2021-06-08 | 3M创新有限公司 | Curable silicone composition |
| CN105906950A (en) * | 2016-05-30 | 2016-08-31 | 成都硅宝科技股份有限公司 | High temperature resistant ethylene propylene rubber/silicon rubber blend and preparation method thereof |
| CN110982281A (en) * | 2019-12-19 | 2020-04-10 | 福建拓烯新材料科技有限公司 | Blended fluorosilicone rubber composition and preparation method thereof |
| WO2022204935A1 (en) * | 2021-03-30 | 2022-10-06 | Dow Global Technologies Llc | Curable polyolefin composition and cured product |
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