CN108299645A - Can directly heat cure organosiloxane preparation and application - Google Patents

Can directly heat cure organosiloxane preparation and application Download PDF

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CN108299645A
CN108299645A CN201810114109.6A CN201810114109A CN108299645A CN 108299645 A CN108299645 A CN 108299645A CN 201810114109 A CN201810114109 A CN 201810114109A CN 108299645 A CN108299645 A CN 108299645A
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substitution
unsubstituted
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organosiloxane
alkyl
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CN108299645B (en
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房强
王佳佳
金凯凯
孙晶
周俊峰
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Shanghai Institute of Organic Chemistry of CAS
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Shanghai Institute of Organic Chemistry of CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
    • C07F7/083—Syntheses without formation of a Si-C bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Silicon Polymers (AREA)

Abstract

The present invention provides it is a kind of can the direct organosiloxane of heat cure preparation and application, specifically, the present invention provides organosiloxane of the one kind containing heat curable group, aryl substituent containing thermosetting property group is attached by the organosiloxane by Si O Si keys with siloxanyl monomers or polysiloxanes, obtains the functionalization siloxanes or polysiloxanes matrix resin of a series of new.The organosiloxane of the present invention can crosslink polymerization by heating, and preparation method is simple and efficient, and be suitable for encapsulating material of the electric industry as insulating coating and electronic component, also can be used as the crosslinking agent of silicon rubber or silicones.

Description

Can directly heat cure organosiloxane preparation and application
Technical field
The invention belongs to the manufacturing fields of high-performance polymer monomer, and in particular to a kind of novel containing thermosetting property group Organosiloxane, and preparation method thereof.
Background technology
Organic siloxane polymer is extensive due to its resistant of high or low temperature, workability, insulation performance, optical property etc. Applied to fields such as electric, Electronic Packagings.Under normal conditions, organic siloxane polymer is made in the following way It is standby：First, condensation is hydrolyzed in organosiloxane monomer under acid or alkaline conditions；Second is that being added by the Pt silicon hydrogen being catalyzed At reaction；Third, being obtained by the chain reaction that some other initiator causes.Such as：The Sylgard 184 of Dow Corning Corporation is just It is the silicon rubber obtained by hydrosilylation；Also, typical poly dimethyl linear siloxane is obtained by hydrolytic condensation .These preparation methods need that initiator or catalyst is added, and the residual of catalyst to a certain extent can be to finally obtaining The performance of polymer material have adverse effect on.
In recent years, in order to avoid this disadvantage, researchers develop some can directly heat cure organosiloxane, lead to It crosses and thermosetting property group is introduced into organosiloxane, obtain a series of organosiloxane monomers containing thermosetting property group or poly- Close object.Then, cause polymerization under heating conditions, obtain organic siloxane polymer material.Typical heat curable group has： Benzocyclobutene, Trifluorovinyl Aryl Ethers, alkynyl, alkenyl, maleimide etc..Such as：The benzo ring of the Dow Chemical Company's exploitation The siloxanyl monomers (fiberglass/composite material, the 4th phase in 2005,16-19.) of butylene functionalization are shown below：
However, this monomer is Heck between halogenated benzocyclobutene and vinyl double seal head by palladium chtalyst anti- It should obtain, on the one hand, palladium catalyst is expensive, needed in reaction process using metal ligand, alkali etc., for reactant Be is more demanding；On the other hand, this kind of reaction yield is not generally high, and the separating-purifying of product is more difficult.Therefore, it leads The raising of final silicones cost, application is caused significantly to be limited.
Poplar scholar is brave et al. to report monomer (J.Polym.Sci.Polym.Chem.2009,47,6246- shown in following formula 6258)：
These monomers are actually the improvement to the Dow Chemical Company's monomer, by introducing phenyl silane to improve the resistance to of polymer It is hot.However, the preparation of above-mentioned monomer is equally more not easy with purification.
Poplar military school etc. has obtained the polymerization that main chain contains thermosetting property benzocyclobutene for siloxanes, side chain by Si―H addition reaction The preparation of object (Chinese invention patent application number 201110367893.X), more above-mentioned two classes siloxanyl monomers is more simple, knot Structure is as follows：
Room waits improved above-mentioned several siloxanyl monomers or polymer by force, obtains side chain as follows containing heat The organic siloxane polymer (Polym.Chem.2015,6,5984) of solidity benzocyclobutane alkenyl group：
It, can be greatly by the way that benzocyclobutane alkenyl group to be directly attached with the silicon atom on organosiloxane backbones Improve the thermal stability of polymer.
Other than benzocyclobutane alkenyl group, Trifluorovinyl Aryl Ethers are another kind of widely used thermosetting bases Group.Room is equal by force to be connected to Trifluorovinyl Aryl Ethers in the side chain of organosiloxane, obtains as follows fluorine-containing organic linear And annular siloxanes (Macromolecules, 2014,47,6311. Polym.Chem.2016,7,3378.)：
The introducing of fluorine atom can improve the hydrophobicity and insulation performance of material, for organosilicon to a certain extent Application of the oxygen alkane polymer material in microelectronic industry provides help.
However, the preparation of these above-mentioned siloxanyl monomers or polymer still has deficiency：Reaction process is not efficient enough, and silicon hydrogen adds It can be unfavorable to the raising of hot property at company's methylene of generation.
In conclusion can be direct there is an urgent need in the art to develop that a kind of preparation process is efficiently simple, reaction condition is mild The organosiloxane of heat cure and corresponding silicones or silicon rubber etc..
Invention content
That the object of the present invention is to provide a kind of preparation process is efficiently simple, synthesis condition is mild directly heat cure to have Organic siloxane and corresponding silicones or silicon rubber etc..
The first aspect of the present invention, provide it is a kind of can direct heat cure organosiloxane, the organosiloxane is logical It crosses-Si-O-Si- keys to be attached silicone backbone and the aryl substituent containing thermosetting property group, and the siloxanes With Formulas I structure；
Wherein, the integer (the preferably integer of 1-20, the more preferably integer of 1-10) that n is 1-1000；
Wherein, each RaIt is each independently selected from following substituent group：Substitution or unsubstituted C1~C6 alkyl, substitution or not Replace alkoxy, substitution or unsubstituted C2~C6 alkenyls, substitution or unsubstituted C2~C6 alkynyls, the substitution of C1~C6 or does not take The phenyl in generation or
Each RbIt is each independently selected from following substituent group：The alkyl, substituted or unsubstituted of nothing, substitution or unsubstituted C1~C6 It is the alkoxy of C1~C6, substituted or unsubstituted C2~C6 alkenyls, substituted or unsubstituted C2~C6 alkynyls, substituted or unsubstituted Phenyl, substituted or unsubstituted C1-C6 silylation, substituted or unsubstituted C1-C6 siloxies,
The substitution refers to one or more hydrogen atoms on group and is replaced by substituent group selected from the group below：Halogen, C1~ The alkyl of C6, the alkenyl of C2~C6, the alkynyl of C2~C6, unsubstituted phenyl；
The RbWhen being no, the organosiloxane is cyclic structure；
Each R is independently selected from the following group：
(1)H；
(2) alkyl, substitution or the unsubstituted C2~C12 alkenyls of substitution or unsubstituted C1~C12, wherein the substitution refers to One or more hydrogen atoms on group are replaced by substituent group selected from the group below：Halogen, the alkyl of C1~C12, C2~C12 What 1~3 hydrogen atom on alkenyl, the alkynyl of C2~C12, unsubstituted phenyl ring or phenyl ring was replaced by substituent group selected from the group below Phenyl：The alkynyl of the alkyl of C1~C12, the alkenyl of C2~C12, C2~C12；
(3) substituted or unsubstituted phenyl, the substitution refer to one or more hydrogen atoms on group and are selected from the group Substituent group substitution：Halogen, the alkyl of C1~C12, the alkenyl of C2~C12, the alkynyl of C2~C12, unsubstituted phenyl；
(4) thermosetting property aryl group；
The thermosetting property aryl group includes：Benzocyclobutane alkenylThe virtue of trifluoro vinyl ether substitution BaseThe phenyl of vinyl substitutionThe phenyl of acetenyl substitution
And at least one R is thermosetting property aryl group.
In another preferred example, the polysiloxanes is annular siloxanes or linear polysiloxane.
In another preferred example, the polysiloxanes is selected from the group (b1) or (b2)：
(b1)Wherein, n=3~8；R3Selected from following substituent group：The alkane of substitution or unsubstituted C1~C6 Base, substitution or unsubstituted C2~C6 alkenyls, substitution or unsubstituted C2~C6 alkynyls, substituted or unsubstituted phenyl, described takes One or more hydrogen atoms on acute pyogenic infection of finger tip group are replaced by substituent group selected from the group below：Halogen, alkyl, the C2~C6 of C1~C6 Alkenyl, C2~C6 alkynyl, unsubstituted phenyl；Or
(b2)Wherein, n=2~1000；Each R4Independently selected from：H, SiMe3；Each R5Independently selected from Following substituent group：H, the substitution or alkyl of unsubstituted C1~C6, substitution or unsubstituted C2~C6 alkenyls, substitution or unsubstituted C2~ C6 alkynyls, substituted or unsubstituted phenyl, the substitution refer to one or more hydrogen atoms on group and are taken by selected from the group below Replace for base：Halogen, the alkyl of C1~C6, the alkenyl of C2~C6, the alkynyl of C2~C6, unsubstituted phenyl；
In another preferred example, the organosiloxane includes organosiloxane monomer and/or organosiloxane polymerization Object.
In another preferred example, the silicone polymer backbone includes linear backbone and/or branch main chain, preferably For linear backbone.
In another preferred example, the index of refraction of the organosiloxane is 1.5~1.6.
In another preferred example, the organosiloxane has such as Formula Il structure：
Wherein
In another preferred example, each R is each independently group selected from the group below：C1~C4 alkyl, C2~C4 alkenyls, Or substituted or unsubstituted phenyl.
In another preference, the R is each independently group selected from the group below：Methyl, vinyl, phenyl, or heat Solidity group.
In another preferred example, each group is specific group recorded in each compound of embodiment.
In another preferred example, each R is independently selected from the following group：
(1)H；
(2) alkyl, substitution or the unsubstituted C2~C4 alkenyls of substitution or unsubstituted C1~C4, wherein the substitution refers to base One or more hydrogen atoms in group are replaced by substituent group selected from the group below：Halogen, the alkyl of C1~C4, the alkenyl of C2~C6, The phenyl that 1~3 hydrogen atom on the alkynyl of C2~C6, unsubstituted phenyl ring or phenyl ring is replaced by substituent group selected from the group below： The alkynyl of the alkyl of C1~C6, the alkenyl of C2~C6, C2~C6；
(3) thermosetting property aryl group, the thermosetting property aryl group are group selected from the group below：
And at least one R is thermosetting property aryl group.
In another preferred example, the organosiloxane has structure selected from the group below：
The second aspect of the present invention provides a kind of preparation side of organosiloxane as described in the first aspect of the invention Method, the organosiloxane are by prepared by condensation reaction as follows：
Wherein, X and Y is selected from following (1) or (2)：
(1) X=H, Y=OH, OMe, OEt；
(2) X=OH, OMe, OEt, Y=H.
In another preferred example, X=H, Y=OEt.
In another preferred example, X=OEt, Y=H.
In another preferred example, X=OH, Y=H.
In another preferred example, the silane I-a is selected from the group：
(1) alkoxy silaneWherein, R2For H, Me or Et；Each R1It is taken independently selected from following Dai Ji：Alkyl, substitution or the unsubstituted C2~C12 alkenyls of substitution or unsubstituted C1~C12, substitution or unsubstituted C2~C12 alkynes Base, substituted or unsubstituted phenyl, the substitution refer to one or more hydrogen atoms on group by substituent group selected from the group below Substitution：Halogen, the alkyl of C1~C12, the alkenyl of C2~C12, the alkynyl of C2~C12, unsubstituted phenyl；
(2) annular siloxanesWherein, n=3~8；R3Selected from following substituent group：Substitution or unsubstituted C1 The alkyl of~C6, the alkoxy of substitution or unsubstituted C1~C6, substitution or unsubstituted C2~C6 alkenyls, substitution or unsubstituted C2~ C6 alkynyls, substituted or unsubstituted phenyl, the substitution refer to one or more hydrogen atoms on group and are taken by selected from the group below Replace for base：Halogen, the alkyl of C1~C6, the alkenyl of C2~C6, the alkynyl of C2~C6, unsubstituted phenyl；
(3) linear polysiloxaneWherein, n=2~1000；Each R4Independently selected from：H, SiMe3；Each R5 Independently selected from following substituent group：H, substitution or the alkyl of unsubstituted C1~C6, substitution or unsubstituted C1~C6 alkoxy, Substitution or unsubstituted C2~C6 alkenyls, substitution or unsubstituted C2~C6 alkynyls, substituted or unsubstituted phenyl, the substitution refer to One or more hydrogen atoms on group are replaced by substituent group selected from the group below：Halogen, the alkyl of C1~C6, the alkene of C2~C6 Base, the alkynyl of C2~C6, unsubstituted phenyl.
In another preferred example, the condensation reaction includes the following steps：In catalyst (C6F5)3In the presence of, with such as formula Silane I-a shown in I and monomer I-b carries out condensation reaction in atent solvent, obtains as described in the first aspect of the invention Organosiloxane；
In another preferred example, the condensation reaction carries out in atent solvent selected from the group below：N-hexane, benzene, first Benzene, dimethylbenzene or combinations thereof；Preferably, the condensation reaction carries out in toluene；
In another preferred example, catalyst B (C in the condensation reaction6F5)3Dosage be 0.1mol%~1 Mol%；
In another preferred example, the condensation reaction has one or more conditions selected from the group below：
The condensation reaction carries out at -20~80 DEG C；It is preferred that being carried out at 0~60 DEG C；
The condensation reaction time be 0.5~for 24 hours.
In another preferred example, the condensation reaction also has following one or more features：
The condensation reaction is in strong lewis acid B (C6F5)3Catalysis is lower to be carried out
The condensation reaction carries out in atent solvent selected from the group below：N-hexane, benzene,toluene,xylene or its group It closes；
The condensation reaction carries out at -20~80 DEG C；
The condensation reaction time be 0.5~for 24 hours.
In another preferred example, the catalyst B (C6F5)3Dosage be 0.1%~1%.
In another preferred example, the condensation reaction includes the following steps：In catalyst (C6F5)3In the presence of, with such as formula Silane A shown in I carries out condensation reaction with B monomer in atent solvent, obtains the organosiloxane as shown in formula (I).
The third aspect of the present invention, provides a kind of cross-linked silicone oxygen alkane cured product, and the cured product is to use Prepared by method as described below：The organosiloxane is polymerize to the first aspect of the present invention, is crosslinked with to be formed Organic siloxane.
In another preferred example, the polymerization is to carry out polymerizing curable (being heating and curing) by heating.
In another preferred example, the temperature that is heating and curing is 130~270 DEG C, preferably 150~260 DEG C.
In another preferred example, it is described be heating and curing including：Precuring is carried out at 150~190 DEG C, then 230 Cure after being carried out at~270 DEG C.
In another preferred example, it is described be heating and curing including：Precuring is carried out at 150~190 DEG C, then with heating Rate is that the rate of 15~55 DEG C/h is warming up to 230~270 DEG C, and cures after carrying out.
In another preferred example, described be heating and curing further includes：Before the precuring, to the organosiloxane Slowly heating and/or mechanical oscillation are carried out, to remove bubble, form dense liquids；Preferably, the heating is by room temperature It is warming up to 100~140 DEG C.
In another preferred example, the pre-cure time is 4~8h.
In another preferred example, the hardening time is 4~8h.
The fourth aspect of the present invention, provides a kind of product, and the product contains Formulas I as described in the first aspect of the invention Organosiloxane or the cured product as described in third aspect present invention；Or：
The product be with as described in the first aspect of the invention Formulas I organosiloxane or such as third aspect present invention institute Prepared by the cured product stated.
In another preferred example, the product is selected from the group：Crosslinking agent, crosslinked silicon rubber, crosslinked silicones.
In another preferred example, the product is advanced low-k materials or plain conductor outer cladding insulating materials.
In another preferred example, the product is polymer sheet or film.
In another preferred example, the product includes：Base material, and coated on base material containing such as the present invention the The film of cured product described in six aspects.
In another preferred example, the product is prepared by the following method：With as described in the first aspect of the invention Formula A organosiloxanes be molded, obtain preform, be then heating and curing to the preform, obtain institute The product stated.
In another preferred example, the molding is carried out by moulding process selected from the group below：Heating and mould pressing, solution Spin coating or solution drop coating.
In another preferred example, the solution spin coating or solution drop coating include step：It will as described in the first aspect of the invention Formula A organosiloxanes be dissolved in wiring solution-forming in organic solvent, then carry out spin coating or drop coating；Preferably, the solvent choosing From the following group：The organic solvent is toluene, dimethylbenzene, trimethylbenzene, diphenyl ether, cyclohexanone, chloroform, acetone, N, N- bis- Methylformamide, n,N-dimethylacetamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, or combinations thereof.
The seventh aspect of the present invention, provides a kind of crosslinking agent, and the crosslinking agent contains such as first aspect present invention institute The formula A organosiloxanes stated.
In another preferred example, the crosslinking agent, which is the crosslinking agent of high-temperature silicon disulfide rubber, (can be directly appended to silicon tree In fat).
The eighth aspect of the present invention provides a kind of crosslinked silicon rubber, and the silicon rubber is high-temperature silicon disulfide rubber, And contain formula A organosiloxanes as described in the first aspect of the invention in the silicon rubber.
In the scope of the invention, above-mentioned each technical characteristic of the invention and each specifically described in below (e.g. embodiment) It can be combined with each other between technical characteristic, to form a new or preferred technical solution.As space is limited, herein no longer one by one It is tired to state.
Specific implementation mode
The present invention intends to provide it is a kind of it is novel can the direct organosiloxane of heat cure preparation method.It is by heating Polymerization can be crosslinked, cross-linking products have good insulation performance, heat resistance, the transparency and mechanical property etc., and preparation side Method is simple, is suitable for encapsulating material of the electric industry as insulating coating and electronic component, or as high temperature sulphur The crosslinking agent of SiClx rubber.
Term
As used herein, term " siloxanes " or " organosiloxane " refer to the compound of the composition of bond structure containing Si-O-Si.This In invention, a kind of preferred organosiloxane has such as formulaShown in structure, wherein each R is each independently For alkyl, alkenyl or aryl,For organic silicon monomer, cyclic organic siloxane or linear polysiloxane.
Term " formula A organosiloxanes " or " organosiloxane of the invention " are used interchangeably, and are referred both to shown in formula A organic Siloxanes；
It is former that term " organosilicon containing thermosetting property group " or the organosilicon of heat cure " can directly " refer to each silicon in silane The part (part for being originally used for R) being connected originally with alkyl, alkenyl or aryl on son is replaced by thermosetting property group；
Term " thermosetting property group " refers specifically to benzocyclobutane alkenyl in the present inventionTrifluoro vinyl ether takes The aryl in generationThe phenyl of vinyl substitutionThe phenyl of acetenyl substitution
Term " halogen " refers to fluorine, chlorine, bromine, iodine.
Term " halogenated " refers to one or more hydrogen atoms on group and is replaced by halogen.
Term " alkyl of C1~C12 " refers to the linear or branched alkyl group with 1~6 carbon atom, such as methyl, ethyl, just Propyl, isopropyl, normal-butyl, tertiary butyl, or similar group.
Term " alkenyl of C2~C12 " refers to the linear chain or branched chain alkenyl with 2~12 carbon atoms, such as vinyl, propylene Base, allyl, 1- cyclobutenyls, 2- cyclobutenyls, or similar group.
Term " alkynyl of C2~C12 " refers to the linear chain or branched chain alkynyl with 2~12 carbon atoms, such as acetenyl, propine Base, allyl, 1- butynyls, 2- butynyls, or similar group.
Organosiloxane containing thermosetting property group
Organosiloxane is needed to form it into cross-linking system in general and could preferably be applied.In recent years, in order to The adverse effect for avoiding the catalyst used in conventional crosslinking method or initiator from generating material property, researchers are constantly Thermosetting property group is introduced in organosiloxane monomer or polymer, is obtained by its heat polymerization at a certain temperature Required cross-linked silicone resin or silicon rubber etc..Wherein, typical thermosetting property group has benzocyclobutane alkenylThe aryl of trifluoro vinyl ether substitutionThe phenyl of vinyl substitutionSecond The phenyl of alkynyl substitutedDeng.However, in the prior art, generally by the siloxanes containing thermosetting property group Hydrolytic condensation is obtained required by the hydrosilylation between silane and organosiloxane containing thermosetting property group Organosiloxane monomer or polymer.There are still certain defects for both methods：First, the hydrolytic condensation of organosiloxane A certain amount of silanol is inevitably resulted from, the process is more difficult to control, and the presence of silicone hydroxyl can be organic to being formed by The performance (especially electric property) of siloxane polymer material has adverse effect on；Second is that hydrosilylation can be formed it is soft - the Si-CH of property2-CH2Key, wherein even the presence of methylene is unfavorable to the raising of siloxanes thermal stability.
Present invention employs the techniques being simple and efficient, using silicon hydrogen monomer and alkoxy silane containing thermosetting property group (or hydroxy silicon oil) or siloxanes (or silanol) containing thermosetting property group are with silicon hydrogen monomer (or containing hydrogen silicone oil) in B (C6F5)3 Catalytic action under carry out condensation reaction, obtain with the organosiloxane of-Si-O-Si- novel groups containing thermosetting property being keyed Monomer or polymer.
Specifically, organosiloxane provided by the present invention by silicone backbone and contains thermosetting by-Si-O-Si- keys Property group aryl substituent be attached, be it is a kind of it is novel can direct heat cure organosiloxane.The siloxanes With shaped likeStructure.Wherein,For organic silicon monomer, cyclic organic siloxane or linear polysiloxane；Respectively A R is each independently alkyl, substitution or the unsubstituted C2~C12 alkenyls of substitution or unsubstituted C1~C12, replaces or do not take For C2~C12 alkynyls, substituted or unsubstituted phenyl；The substitution refers to one or more hydrogen atoms on group by under The substituent group substitution of group：Halogen, the alkyl of C1~C12, the alkenyl of C2~C12, the alkynyl of C2~C12, unsubstituted or phenyl ring On the phenyl that is replaced by substituent group selected from the group below of 1~4 hydrogen atom：The alkyl of halogen, C1~C12；Also, at least one R is thermosetting property aryl group (benzocyclobutane alkenylThe aryl of trifluoro vinyl ether substitution The phenyl of vinyl substitutionThe phenyl of acetenyl substitution)。
In another preferred example, the organosiloxane includes organosiloxane monomer and/or organosiloxane polymerization Object.
In another preferred example, the silicone polymer backbone includes linear backbone and/or branch main chain, preferably For linear backbone.
In another preferred example, the index of refraction of the organosiloxane is 1.5~1.6.
In another preferred example, the organosiloxane has such as Formula Il structure：
Wherein
Each R is each independently alkyl, substitution or the unsubstituted C2~C12 alkenyls of substitution or unsubstituted C1~C12, takes Generation or unsubstituted C2~C12 alkynyls, substituted or unsubstituted phenyl；The substitution refers to one or more hydrogen atoms on group Replaced by substituent group selected from the group below：The alkynyl, unsubstituted of halogen, the alkyl of C1~C12, the alkenyl of C2~C12, C2~C12 Or phenyl that 1~4 hydrogen atom on phenyl ring is replaced by substituent group selected from the group below：The alkyl of halogen, C1~C12；
The organosiloxane is by prepared by the condensation reaction between silane A and silane B as shown in following formula I 's：
Wherein, X and Y is selected from following：
X=H, and Y=OH, OMe, OEt；Or X=OH, OMe, OEt, and Y=H.
In another preferred example, the condensation reaction includes the following steps：In catalyst (C6F5)3In the presence of, with such as formula Silane A shown in I carries out condensation reaction with B monomer in atent solvent, obtains the organosiloxane；
The atent solvent of the condensation reaction is not particularly limited, preferably, the condensation reaction is in toluene It carries out；
Catalyst B (C in the condensation reaction6F5)3Dosage be 0.1mol%~1mol%；
The temperature of the condensation reaction is not particularly limited, and is preferably carried out at -20~80 DEG C；It is preferred that 0~ 60 DEG C of progress；
The condensation reaction time is not particularly limited, preferably 0.5~for 24 hours.
All raw materials of the present invention are commercially available product.
The application of organosiloxane
The present invention also provides a kind of purposes such as organosiloxane shown in formula A, the organosiloxane can be used for Electric industry, as the encapsulating material of insulating coating and electronic component, or be used to prepare advanced low-k materials or Plain conductor outer cladding insulating materials, or the crosslinking agent as high-temperature silicon disulfide rubber.
A kind of application of the organosiloxane of the present invention, is the cured product for being used to prepare organosiloxane structural, described Cured product be to be heating and curing with formula A organosiloxanes as mentioned, to prepare.
Wherein, the condition of being heating and curing is not particularly limited, can according to specifically used organosiloxane type, The performance requirement energy concrete condition of cured product is adjusted.In one preferred embodiment of the invention, described plus Heat curing temperature is to be cured at preferably 240~260 DEG C at 230~270 DEG C.
Described being heating and curing can also optionally include pre-cure step, that is, in the temperature lower than the temperature that is heating and curing The lower solidification for first carrying out a period of time.In another preferred example, it is described be heating and curing including：It is carried out at 150~190 DEG C Then precuring is cured at 230~270 DEG C.
Described being heating and curing can carry out under conditions of temperature programming, and in another preferred example, the heating is solid Change includes：Precuring is carried out at 150~190 DEG C, then 230 are warming up to the rate that heating rate is 15~55 DEG C/h~ 270 DEG C, and cured.
The pre-cure time and the cured time are not particularly limited, in a preferred embodiment of the present invention In, the time of the precuring is 4~8h, and the cured time is 4~8h.
The cured product has good thermal property.In the preference of the present invention, the cured product The 5% thermal weight loss temperature in nitrogen is 430~550 DEG C；
In another preferred example, weight remnants of the cured product in nitrogen at 1000 DEG C are >=20%；
The cured product has good insulation performance.In the preference of the present invention, the cured product Dielectric constant be 2.4~2.8 (within the scope of 1-30MHz)；
In another preferred example, the dielectric constant of the cured product is preferably 2.4~2.6.
The organosiloxane of the present invention can be also used for preparing a kind of product, and the product contains the formula A organosilicons Oxygen alkane, Formula II organic silicon monomer or the cured product；Or the product is that have with the formula A organosiloxanes, Formula II Prepared by machine silicon monomer or the cured product.
In another preferred example, the product is advanced low-k materials or plain conductor outer cladding insulating materials.
In another preferred example, the product is polymer sheet or film.
In another preferred example, the product includes：Base material, and coated on base material contain the solidification The film of product.
In another preferred example, the product is prepared by the following method：With the formula A organosiloxanes into Row molding, obtains preform, is then heating and curing to the preform, obtains the product.
In another preferred example, the molding is carried out by moulding process selected from the group below：Heating and mould pressing, solution Spin coating or solution drop coating.
In another preferred example, the solution spin coating or solution drop coating include step：In another preferred example, the solution Spin coating or solution drop coating include step：Formula A organosiloxanes as described in the first aspect of the invention are dissolved in organic solvent and are matched At solution, spin coating or drop coating are then carried out；Preferably, the solvent is selected from the group：The organic solvent is toluene, diformazan Benzene, trimethylbenzene, diphenyl ether, cyclohexanone, chloroform, acetone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, diformazan Base sulfoxide, N-Methyl pyrrolidone, or combinations thereof.
The organosiloxane of the present invention is also used as crosslinking agent, is used to prepare high-temperature silicon disulfide rubber.When in use, directly It connects and the organosiloxane of the present invention is added in silicones.
Main advantages of the present invention：
(1) prepared by the organosiloxane provided by the present invention containing thermosetting property group and purification process is simple and existing The preparation method reported in technology is compared, and by-product is released in gaseous form, and product system monomer is conducive to purifying.
(2) organosiloxane of the invention avoids silanol caused by conventional hydrolysis method, consolidates for what is finally obtained Change the raising of the heat resistance, insulation performance of product advantageously.
(3) organosiloxane of the invention is to avoid traditional silicon hydrogen by condensation reaction generation-Si-O-Si- structures Addition reaction is formed by the adverse effect that even methylene flexible chain brings the raising of organosiloxane thermal stability.
(4) preparation method of the invention is simple, and equipment requirement is low, is suitble to industrialized production.
(5) organosiloxane provided by the present invention, which can be used for preparing, has good electric property, heat resistance and power The cured product of performance is learned, thermal stability is significantly improved.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip Part, or according to the normal condition proposed by manufacturer.Unless otherwise stated, otherwise percentage and number be for calculation in the molar ratio.
The preparation of the organosiloxane of 1 four aryl trifluoro vinyl ether of embodiment substitution
Under argon gas protection, to equipped with B (C6F5)3(102mg, 0.2mmol) and tetraethoxysilane (2.02g, 4- trifluoro-ethylene phenyl dimethylsilanes (8.99g, 38.76mmol) are added dropwise in 10mL toluene solutions 9.69mmol), Stop reaction after dripping complete be stirred at room temperature 8 hours, after rotating removing low boiling point solvent, crude product progress silica gel column chromatography obtains colourless Transparency liquid 7.20g, yield 73%.
The preparation of the organosiloxane of 2 triaryl trifluoro vinyl ether of embodiment substitution
Under argon gas protection, to equipped with B (C6F5)3(67mg, 0.13mmol) and perfluoro capryl triethoxysilane (5.32g, 4- trifluoro-ethylene phenyl dimethylsilanes (6.06g, 26.1mmol), drop are added dropwise in 10mL toluene solutions 8.7mmol) Finish be stirred at room temperature 8 hours after stop reaction, revolving remove low boiling point solvent after, crude product carry out silica gel column chromatography obtain it is colourless Prescribed liquid 6.50g, yield 61.4%.
The preparation of the organosiloxane of 3 tetravinyl phenyl of embodiment substitution
Under argon gas protection, to equipped with B (C6F5)3(61mg, 0.12mmol) and tetraethoxysilane (1.25g, 6 mmol) In 10mL toluene solutions be added dropwise 4- ethenylphenyls dimethylsilane (3.89g, 24mmol), drop finish be stirred at room temperature 6 hours after stop It only reacts, after revolving removes low boiling point solvent, crude product carries out silica gel column chromatography and obtains colourless transparent liquid 3.35g, and yield is 76%.
The preparation of organic annular siloxane of 4 tetravinyl phenyl of embodiment substitution
Under argon gas protection, to equipped with B (C6F5)3(82mg, 0.16mmol) and 4- ethenylphenyl dimethylethoxysilanes Tetramethyl-ring tetrasiloxane (1.93g, 8 mmol) is added dropwise in the 12mL toluene solutions of (6.6g, 32mmol), drop, which finishes, is stirred at room temperature 6 Stop reaction after hour, after revolving removes low boiling point solvent, crude product carries out silica gel column chromatography and obtains colourless transparent liquid 5.08g, yield 67%.
The preparation of organic annular siloxane of 5 four aryl trifluoro vinyl ether of embodiment substitution
Under argon gas protection, to equipped with B (C6F5)3(51mg, 0.1mmol) and 4- trifluoro-ethylene phenyl dimethylethoxies Tetramethyl-ring tetrasiloxane (1.2 g, 5mmol) is added dropwise in the 15mL toluene solutions of base silane (5.53g, 20mmol), drips and finishes room Temperature stirring stops reaction after 6 hours, after revolving removes low boiling point solvent, crude product carries out silica gel column chromatography and obtains water white transparency liquid Body 4.86g, yield 79%.
The preparation of the organopolysiloxane of 6 ethenylphenyl of embodiment substitution
Under argon gas protection, to equipped with B (C6F5)3(95mg, 0.185mmol) and 4- ethenylphenyl dimethylethyloxy silicon Containing hydrogen silicone oil (2.2g) is added dropwise in the 15mL toluene solutions of alkane (7.64g, 37mmol), stops instead after dripping complete be stirred at room temperature 6 hours It answers, is settled in absolute methanol, obtain colourless viscous liquid 8.34g.
The preparation of the organopolysiloxane of 7 aryl trifluoro vinyl ether of embodiment substitution
Under argon gas protection, to equipped with B (C6F5)3(61mg, 0.12mmol) and 4- trifluoro-ethylene phenyl dimethylethoxies In the 10mL toluene solutions of base silane (6.64g, 24mmol) be added dropwise containing hydrogen silicone oil (1.4g), drop finish be stirred at room temperature 6 hours after stop It only reacts, is settled in absolute methanol, obtain colourless viscous liquid 6.94g.
The solidification of the organosiloxane of 8 four aryl trifluoro vinyl ether of embodiment substitution and the heat-resisting property of cured product
1 resulting polymers of 0.8g embodiments are placed in the flat bottom glass pipe that internal diameter is 1cm, 160 DEG C are warming up to, at this Temperature is kept for 2 hours, is then warming up to 240 DEG C, and kept for 5 hours in the temperature, is cooled to room temperature, solidfied material is taken out, levigate, Carry out TGA tests.The result shows that cured product 5% thermal weight loss temperature in nitrogen is 476 DEG C, 1000 DEG C of weight remnants are 27%.
The dielectric property of the organosiloxane cured product of 9 four aryl trifluoro vinyl ether of embodiment substitution
1 resulting polymers of 0.8g embodiments are placed in the flat bottom glass pipe that internal diameter is 1cm, are vacuumized and mechanical oscillation Under be to slowly warm up to 150 DEG C of removing bubble formation dense liquids, be warming up to 160 DEG C, and keep 5h to keep its pre- solid at this temperature Change.It is cooled to after room temperature and moves to quartz tube furnace and be warming up to 250 DEG C with 50 DEG C/h rates, and is taken out after the temperature is kept for 5 hours It is polished into disk, measures its dielectric constant, the results showed that, in 1 MHz to 30MHz frequency ranges, dielectric constant is between 2.50 To between 2.58.
The solidification of the organosiloxane of 10 triaryl trifluoro vinyl ether of embodiment substitution and the heat-resisting property of cured product
2 resulting polymers of 0.6g embodiments are placed in the flat bottom glass pipe that internal diameter is 1cm, 160 DEG C are warming up to, at this Temperature is kept for 2 hours, is then warming up to 240 DEG C, and kept for 5 hours in the temperature, is cooled to room temperature, solidfied material is taken out, levigate, Carry out TGA tests.The result shows that cured product 5% thermal weight loss temperature in nitrogen is 440 DEG C, 1000 DEG C of weight remnants are 21%.
The dielectric property of the organosiloxane cured product of 11 triaryl trifluoro vinyl ether of embodiment substitution
2 resulting polymers of 0.9g embodiments are placed in the flat bottom glass pipe that internal diameter is 1cm, are vacuumized and mechanical oscillation Under be to slowly warm up to 150 DEG C of removing bubble formation dense liquids, be warming up to 160 DEG C, and keep 5h to keep its pre- solid at this temperature Change.It is cooled to after room temperature and moves to quartz tube furnace and be warming up to 250 DEG C with 50 DEG C/h rates, and is taken out after the temperature is kept for 5 hours It is polished into disk, measures its dielectric constant, the results showed that, in 1 MHz to 30MHz frequency ranges, dielectric constant is between 2.30 To between 2.45.
The solidification of the organosiloxane of 12 tetravinyl phenyl of embodiment substitution and the heat-resisting property of cured product
3 resulting polymers of 0.6g embodiments are placed in the flat bottom glass pipe that internal diameter is 1cm, 100 DEG C are warming up to, at this Temperature is kept for 2 hours, is then warming up to 160 DEG C, and kept for 6 hours in the temperature, is cooled to room temperature, solidfied material is taken out, levigate, Carry out TGA tests.The result shows that cured product 5% thermal weight loss temperature in nitrogen is 453 DEG C, 1000 DEG C of weight remnants are 34%.
The dielectric property of the organosiloxane cured product of 13 tetravinyl phenyl of embodiment substitution
3 resulting polymers of 0.6g embodiments are placed in the flat bottom glass pipe that internal diameter is 1cm, are vacuumized and mechanical oscillation Under be to slowly warm up to 60 DEG C of removing bubble formation dense liquids, be warming up to 100 DEG C, and keep 5h to keep its pre- solid at this temperature Change.It is cooled to after room temperature and moves to quartz tube furnace and be warming up to 160 DEG C with 30 DEG C/h rates, and is taken out after the temperature is kept for 5 hours It is polished into disk, measures its dielectric constant, the results showed that, in 1 MHz to 30MHz frequency ranges, dielectric constant is between 2.62 To between 2.68.
The solidification of organic annular siloxane of 14 tetravinyl phenyl of embodiment substitution and the heat-resisting property of cured product
4 resulting polymers of 0.6g embodiments are placed in the flat bottom glass pipe that internal diameter is 1cm, 100 DEG C are warming up to, at this Temperature is kept for 2 hours, is then warming up to 160 DEG C, and kept for 6 hours in the temperature, is cooled to room temperature, solidfied material is taken out, levigate, Carry out TGA tests.The result shows that cured product 5% thermal weight loss temperature in nitrogen is 456 DEG C, 1000 DEG C of weight remnants are 34%.
The dielectric property of organic annular siloxane cured product of 15 tetravinyl phenyl of embodiment substitution
4 resulting polymers of 0.6g embodiments are placed in the flat bottom glass pipe that internal diameter is 1cm, are vacuumized and mechanical oscillation Under be to slowly warm up to 60 DEG C of removing bubble formation dense liquids, be warming up to 100 DEG C, and keep 5h to keep its pre- solid at this temperature Change.It is cooled to after room temperature and moves to quartz tube furnace and be warming up to 160 DEG C with 30 DEG C/h rates, and is taken out after the temperature is kept for 5 hours It is polished into disk, measures its dielectric constant, the results showed that, in 1 MHz to 30MHz frequency ranges, dielectric constant is between 2.60 To between 2.69.
16 4 aryl trifluoro vinyl ether of embodiment substitution organic annular siloxane solidification and cured product it is heat-resisting Property
5 resulting polymers of 0.7g embodiments are placed in the flat bottom glass pipe that internal diameter is 1cm, 160 DEG C are warming up to, at this Temperature is kept for 2 hours, is then warming up to 240 DEG C, and kept for 6 hours in the temperature, is cooled to room temperature, solidfied material is taken out, levigate, Carry out TGA tests.The result shows that cured product 5% thermal weight loss temperature in nitrogen is 469 DEG C, 1000 DEG C of weight remnants are 28%.
The dielectric property of organic annular siloxane cured product of 17 4 aryl trifluoro vinyl ether of embodiment substitution
5 resulting polymers of 0.7g embodiments are placed in the flat bottom glass pipe that internal diameter is 1cm, are vacuumized and mechanical oscillation Under be to slowly warm up to 150 DEG C of removing bubble formation dense liquids, be warming up to 160 DEG C, and keep 5h to keep its pre- solid at this temperature Change.It is cooled to after room temperature and moves to quartz tube furnace and be warming up to 250 DEG C with 50 DEG C/h rates, and is taken out after the temperature is kept for 5 hours It is polished into disk, measures its dielectric constant, the results showed that, in 1 MHz to 30MHz frequency ranges, dielectric constant is between 2.50 To between 2.56.
The solidification of the organopolysiloxane of 18 ethenylphenyl of embodiment substitution and the heat-resisting property of cured product
6 resulting polymers of 0.7g embodiments are placed in the flat bottom glass pipe that internal diameter is 1cm, 100 DEG C are warming up to, at this Temperature is kept for 2 hours, is then warming up to 160 DEG C, and kept for 6 hours in the temperature, is cooled to room temperature, solidfied material is taken out, levigate, Carry out TGA tests.The result shows that cured product 5% thermal weight loss temperature in nitrogen is 457 DEG C, 1000 DEG C of weight remnants are 38%.
The dielectric property of the organopolysiloxane cured product of 19 ethenylphenyl of embodiment substitution
6 resulting polymers of 0.7g embodiments are placed in the flat bottom glass pipe that internal diameter is 1cm, are vacuumized and mechanical oscillation Under be to slowly warm up to 60 DEG C of removing bubble formation dense liquids, be warming up to 100 DEG C, and keep 5h to keep its pre- solid at this temperature Change.It is cooled to after room temperature and moves to quartz tube furnace and be warming up to 160 DEG C with 30 DEG C/h rates, and is taken out after the temperature is kept for 5 hours It is polished into disk, measures its dielectric constant, the results showed that, in 1 MHz to 30MHz frequency ranges, dielectric constant is between 2.62 To between 2.69.
The solidification of the organopolysiloxane of 20 aryl trifluoro vinyl ether of embodiment substitution and the heat-resisting property of cured product
7 resulting polymers of 0.8g embodiments are placed in the flat bottom glass pipe that internal diameter is 1cm, 160 DEG C are warming up to, at this Temperature is kept for 2 hours, is then warming up to 240 DEG C, and kept for 6 hours in the temperature, is cooled to room temperature, solidfied material is taken out, levigate, Carry out TGA tests.The result shows that cured product 5% thermal weight loss temperature in nitrogen is 478 DEG C, 1000 DEG C of weight remnants are 31%.
The dielectric property of the organopolysiloxane cured product of 21 aryl trifluoro vinyl ether of embodiment substitution
7 resulting polymers of 0.8g embodiments are placed in the flat bottom glass pipe that internal diameter is 1cm, are vacuumized and mechanical oscillation Under be to slowly warm up to 150 DEG C of removing bubble formation dense liquids, be warming up to 160 DEG C, and keep 5h to keep its pre- solid at this temperature Change.It is cooled to after room temperature and moves to quartz tube furnace and be warming up to 240 DEG C with 50 DEG C/h rates, and is taken out after the temperature is kept for 5 hours It is polished into disk, measures its dielectric constant, the results showed that, in 1 MHz to 30MHz frequency ranges, dielectric constant is between 2.49 To between 2.56.
All references mentioned in the present invention is incorporated herein by reference, independent just as each document It is incorporated as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art can To be made various changes or modifications to the present invention, such equivalent forms equally fall within model defined by the application the appended claims It encloses.

Claims (10)

1. one kind can directly heat cure organosiloxane, which is characterized in that the organosiloxane pass through-Si-O-Si- keys will Silicone backbone is attached with the aryl substituent containing thermosetting property group, and the siloxanes has Formulas I structure；
Wherein, n is the integer of 1-1000；
Wherein, each RaIt is each independently selected from following substituent group：Substitution or alkyl, the substitution or unsubstituted of unsubstituted C1~C6 Alkoxy, substitution or the unsubstituted C2~C6 alkenyls of C1~C6, substitution or unsubstituted C2~C6 alkynyls, substituted or unsubstituted benzene Base or
Each RbIt is each independently selected from following substituent group：The alkyl, substituted or unsubstituted of nothing, substitution or unsubstituted C1~C6 The alkoxy of C1~C6, substituted or unsubstituted C2~C6 alkenyls, substituted or unsubstituted C2~C6 alkynyls, substitution or unsubstituted Phenyl, substituted or unsubstituted C1-C6 silylation, substituted or unsubstituted C1-C6 siloxies,
The substitution refers to one or more hydrogen atoms on group and is replaced by substituent group selected from the group below：Halogen, C1~C6's Alkyl, the alkenyl of C2~C6, the alkynyl of C2~C6, unsubstituted phenyl；
The RbWhen being no, the organosiloxane is cyclic structure；
Each R is independently selected from the following group：
(1)H；
(2) alkyl, substitution or the unsubstituted C2~C12 alkenyls of substitution or unsubstituted C1~C12, wherein the substitution refers to group On one or more hydrogen atoms replaced by substituent group selected from the group below：Halogen, the alkyl of C1~C12, the alkenyl of C2~C12, The phenyl that 1~3 hydrogen atom on the alkynyl of C2~C12, unsubstituted phenyl ring or phenyl ring is replaced by substituent group selected from the group below： The alkynyl of the alkyl of C1~C12, the alkenyl of C2~C12, C2~C12；
(3) substituted or unsubstituted phenyl, the substitution refer to one or more hydrogen atoms on group and are taken by selected from the group below Replace for base：Halogen, the alkyl of C1~C12, the alkenyl of C2~C12, the alkynyl of C2~C12, unsubstituted phenyl；
(4) thermosetting property aryl group；
The thermosetting property aryl group includes：Benzocyclobutane alkenylThe aryl of trifluoro vinyl ether substitutionThe phenyl of vinyl substitutionThe phenyl of acetenyl substitutionAnd at least It is thermosetting property aryl group there are one R.
2. organosiloxane as described in claim 1, which is characterized in that the organosiloxane has such as Formula Il knot Structure：
Wherein
3. organosiloxane as described in claim 1, which is characterized in that each R is independently selected from the following group：
(1)H；
(2) alkyl, substitution or the unsubstituted C2~C4 alkenyls of substitution or unsubstituted C1~C4, wherein the substitution refers on group One or more hydrogen atoms replaced by substituent group selected from the group below：Halogen, the alkyl of C1~C4, the alkenyl of C2~C6, C2~ The phenyl that 1~3 hydrogen atom on the alkynyl of C6, unsubstituted phenyl ring or phenyl ring is replaced by substituent group selected from the group below：C1~ The alkynyl of the alkyl of C6, the alkenyl of C2~C6, C2~C6；
(3) thermosetting property aryl group, the thermosetting property aryl group are group selected from the group below：
And at least one R is thermosetting property aryl group.
4. organosiloxane as described in claim 1, which is characterized in that the organosiloxane has knot selected from the group below Structure：
5. the preparation method of organosiloxane as described in claim 1, which is characterized in that the organosiloxane is to pass through Prepared by condensation reaction as follows：
Wherein, X and Y is selected from following (1) or (2)：
(1) X=H, Y=OH, OMe, OEt；
(2) X=OH, OMe, OEt, Y=H.
6. method as claimed in claim 5, which is characterized in that the silane I-a is selected from the group：
(1) alkoxy silaneWherein, R2For H, Me or Et；Each R1Independently selected from following substitution Base：Alkyl, substitution or the unsubstituted C2~C12 alkenyls of substitution or unsubstituted C1~C12, substitution or unsubstituted C2~C12 alkynyls, Substituted or unsubstituted phenyl, the substitution refer to one or more hydrogen atoms on group and are taken by substituent group selected from the group below Generation：Halogen, the alkyl of C1~C12, the alkenyl of C2~C12, the alkynyl of C2~C12, unsubstituted phenyl；
(2) annular siloxanesWherein, n=3~8；R3Selected from following substituent group：Substitution or unsubstituted C1~C6 Alkyl, alkoxy, substitution or the unsubstituted C2~C6 alkenyls of substitution or unsubstituted C1~C6, substitution or unsubstituted C2~C6 alkynes Base, substituted or unsubstituted phenyl, the substitution refer to one or more hydrogen atoms on group by substituent group selected from the group below Substitution：Halogen, the alkyl of C1~C6, the alkenyl of C2~C6, the alkynyl of C2~C6, unsubstituted phenyl；
(3) linear polysiloxaneWherein, n=2~1000；Each R4Independently selected from：H, SiMe3；Each R5It is independent Ground is selected from following substituent group：H, substitution or the alkyl of unsubstituted C1~C6, the alkoxy of substitution or unsubstituted C1~C6, substitution or Unsubstituted C2~C6 alkenyls, substitution or unsubstituted C2~C6 alkynyls, substituted or unsubstituted phenyl, the substitution refer on group One or more hydrogen atoms replaced by substituent group selected from the group below：Halogen, the alkyl of C1~C6, the alkenyl of C2~C6, C2~ The alkynyl of C6, unsubstituted phenyl.
7. method as claimed in claim 6, which is characterized in that the condensation reaction includes the following steps：In catalyst (C6F5)3In the presence of, condensation reaction is carried out in atent solvent with the silane I-a as shown in Formulas I and monomer I-b, is obtained such as this Organosiloxane described in invention first aspect.
8. method as claimed in claim 6, which is characterized in that the condensation reaction also has following one or more special Sign：
The condensation reaction is in strong lewis acid B (C6F5)3Catalysis is lower to be carried out
The condensation reaction carries out in atent solvent selected from the group below：N-hexane, benzene,toluene,xylene or combinations thereof；
The condensation reaction carries out at -20~80 DEG C；
The condensation reaction time be 0.5~for 24 hours.
9. a kind of cross-linked silicone oxygen alkane cured product, which is characterized in that the cured product is with method as described below It prepares：Organosiloxane described in claim 1 is polymerize, to form cross-linked silicone oxygen alkane.
10. a kind of product, which is characterized in that the product contains Formulas I organosiloxane as described in claim 1 or as weighed Profit requires the cured product described in 9；Or：
The product is with Formulas I organosiloxane as described in claim 1 or cured product system as claimed in claim 9 Standby.
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