WO2016070434A1 - 含苯并环丁烯基团的有机硅氧烷及其制备和应用 - Google Patents

含苯并环丁烯基团的有机硅氧烷及其制备和应用 Download PDF

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WO2016070434A1
WO2016070434A1 PCT/CN2014/090653 CN2014090653W WO2016070434A1 WO 2016070434 A1 WO2016070434 A1 WO 2016070434A1 CN 2014090653 W CN2014090653 W CN 2014090653W WO 2016070434 A1 WO2016070434 A1 WO 2016070434A1
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group
substituted
alkyl
halogen
organosiloxane
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PCT/CN2014/090653
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English (en)
French (fr)
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房强
金凯凯
王佳佳
朱芝田
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中国科学院上海有机化学研究所
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Priority to PCT/CN2014/090653 priority Critical patent/WO2016070434A1/zh
Publication of WO2016070434A1 publication Critical patent/WO2016070434A1/zh

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    • 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
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • 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
    • 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
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • 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

Definitions

  • the invention belongs to the field of manufacturing high performance polymer monomers, and particularly relates to an organosiloxane containing a benzocyclobutene group, which can be directly thermally cured, and a preparation method thereof.
  • thermosetting resins benzocyclobutene resin molecules have been ring-opened by heat, and the formation of bulk polymers and cured products have been widely used in aerospace regardless of heat resistance and dimensional stability. Aviation, microelectronics, military and civilian applications.
  • silicone resins have high heat resistance, easy processability, and excellent optical properties, and have been widely used in many industrial sectors.
  • silicone resins require cross-linking for application.
  • Commonly used crosslinking methods generally include hydrosilylation and free radical extension, and in most cases, such crosslinking requires either a catalyst (metal platinum) or an initiator.
  • a high temperature resistant material can be obtained. Further, they obtained a polymer having a main chain of siloxane and a side chain containing a thermosetting benzocyclobutene by hydrosilylation (Chinese Patent Application No. 201110367893.X):
  • the above-mentioned silicone monomer containing a benzocyclobutene unit and a silicone resin resin have problems in that the synthesis conditions are severe, the starting materials are difficult to obtain, or the cost is high.
  • the first and second monomers require a palladium-catalyzed HECK reaction for polymerization.
  • the palladium catalyst is expensive, and the metal ligand is used in the reaction; on the other hand, the reaction yield is generally not tall. As a result, the cost of the final silicone is increased, and its application is greatly limited.
  • the benzocyclobutene unit is not directly connected to the siloxane backbone, but is connected through a carbon chain, resulting in Thermal stability cannot be improved. Further, the above reaction also has a problem that the degree of reaction is difficult to control.
  • An object of the present invention is to provide a silicone monomer containing a benzocyclobutene unit and a corresponding silicone resin which are inexpensive to produce and have a mild synthesis condition.
  • an organosiloxane having a siloxane backbone and a benzocyclobutenyl group directly attached to a silicon atom of the siloxane backbone.
  • ⁇ 30% of the silicon atoms on the siloxane backbone have a benzocyclobutene substituent directly attached to Si.
  • ⁇ 50% (preferably 70-100%, more preferably 90-100%) of the silicon atoms on the siloxane backbone have a benzocyclobutenyl group directly attached to Si.
  • the siloxane backbone has the structure of formula A;
  • x is a positive integer of ⁇ 2 (preferably 2 to 200);
  • Each R is independently selected from the group consisting of:
  • substitution means that one or more hydrogen atoms on the group are substituted with a substituent selected from the group consisting of halogen, C1-C4 alkyl, C1-C4 alkyl halide a base, a C2-C4 alkenyl group, a C2-C4 alkynyl group, an unsubstituted phenyl group;
  • At least one R is a benzocyclobutenyl group.
  • benzocyclobutenyl group is
  • each of the silicon atoms on the siloxane backbone has the benzocyclobutenyl group.
  • the organosiloxane is a resin.
  • the organosiloxane has a refractive index of from 1.5 to 1.6.
  • the siloxane backbone comprises a linear backbone and/or a branched backbone, preferably a linear backbone.
  • the organosiloxane has the structure shown in Formula I below:
  • Each R 1 is independently selected from the group consisting of:
  • each of R 1 is independently a group selected from the group consisting of a C1-C4 alkyl group, a C2-C4 alkenyl group, or a substituted or unsubstituted phenyl group.
  • each of R 1 is independently a group selected from the group consisting of methyl, vinyl, and phenyl.
  • each group is a specific group described in each compound of the examples.
  • a process for producing an organosiloxane according to the first aspect of the invention wherein the organosiloxane is hydrolyzed by a silicone monomer represented by the following formula II. Prepared:
  • R 1 is a group selected from the group consisting of:
  • substitution means that one or more hydrogen atoms on the group are substituted with a substituent selected from the group consisting of halogen, C1-C4 alkyl, C1-C4 alkyl halide a base, a C2-C4 alkenyl group, a C2-C4 alkynyl group, an unsubstituted phenyl group;
  • R 2 and R 3 are each independently a group selected from the group consisting of a C1-C4 alkoxy group and a halogen.
  • each of R 2 , R 3 and R 4 is independently a group selected from the group consisting of C 1 -C 2 alkoxy, halogen.
  • the R 1 is a group selected from the group consisting of methyl, vinyl, and phenyl;
  • the polymerization is homopolymerization or copolymerization.
  • the copolymerization is carried out by hydrolysis copolymerization of a monomer of formula II with a bisalkoxysiloxane.
  • the alkoxy group in the bisalkoxysiloxane is independently a substituted or unsubstituted C1-C10 alkoxy group, wherein the substitution refers to one or more hydrogen atoms on the group.
  • a substituent selected from the group consisting of halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, unsubstituted or 1-3 hydrogen atoms on the phenyl ring selected from A phenyl group substituted with a substituent of the lower group: a halogen, a C1-C4 alkyl group.
  • the two alkoxy groups in the bisalkoxysiloxane are the same or different.
  • the hydrolysis polymerization comprises the steps of: using the formula II in the presence of an acid catalyst Hydrolysis of the illustrated silicone monomer and optional bisalkoxysiloxane affords the organosiloxane of the first aspect of the invention.
  • the hydrolysis polymerization is carried out in the presence of water.
  • the molar ratio of the acidic catalyst to the monomer of the formula II used in the hydrolysis polymerization is from 5 to 10: 0.8 to 1.2.
  • the molar ratio of the water, the acidic catalyst and the monomer of the formula II used in the hydrolysis polymerization is 50 to 100:5 to 10:0.8. 1.2.
  • the molar ratio of the acidic catalyst used and the monomer of the formula II to the dialkoxysiloxane is 5 to 10 in the hydrolysis polymerization. :0.8-1.2.
  • the molar ratio of water, acid catalyst and (formula II + double alkoxysiloxane) used in the hydrolysis polymerization is 50. ⁇ 100:5 ⁇ 10:0.8-1.2.
  • the molar ratio of the monomer of the formula II to the dialkoxysiloxane used in the hydrolysis polymerization is from 0.5 to 2: 0.8 to 1.2.
  • the acid catalyst is selected from the group consisting of hydrochloric acid, sulfuric acid, acetic acid, formic acid, or a combination thereof; preferably, the acid catalyst is selected from the group consisting of acetic acid, formic acid, or a combination thereof.
  • the hydrolysis polymerization has one or more conditions selected from the group consisting of:
  • a solvent selected from the group consisting of benzene, toluene, xylene, or a combination thereof;
  • the hydrolysis polymerization is carried out at 10 to 100 ° C; preferably at room temperature to 100 ° C;
  • the hydrolysis polymerization reaction time is 5 to 48 hours.
  • R 1 is a group selected from the group consisting of:
  • substitution means that one or more hydrogen atoms on the group are substituted with a substituent selected from the group consisting of halogen, C1-C4 alkyl, C1-C4 alkyl halide a base, a C2-C4 alkenyl group, a C2-C4 alkynyl group, an unsubstituted phenyl group;
  • R 2 and R 3 are each independently a group selected from the group consisting of a C1-C4 alkoxy group and a halogen.
  • each of R 2 , R 3 and R 4 is independently a group selected from the group consisting of C 1 -C 2 alkoxy, halogen.
  • a fourth aspect of the invention there is provided a method of preparing a monomer according to the third aspect of the invention, the method comprising the steps of:
  • X is a halogen, preferably selected from the group consisting of Cl, Br;
  • R 1 is a group selected from the group consisting of:
  • substitution means that one or more hydrogen atoms on the group are substituted with a substituent selected from the group consisting of halogen, C1-C4 alkyl, C1-C4 alkyl halide a base, a C2-C4 alkenyl group, a C2-C4 alkynyl group, an unsubstituted phenyl group;
  • R 2 , R 3 and R 4 are each independently a group selected from the group consisting of a C1-C4 alkoxy group and a halogen.
  • each of R 2 , R 3 and R 4 is independently a group selected from the group consisting of C 1 -C 2 alkoxy, halogen.
  • the ether solvent is selected from the group consisting of tetrahydrofuran, methyltetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, cyclohexyl methyl ether, cyclopentyl methyl ether, or Its combination.
  • the inert solvent is a mixture of tetrahydrofuran and toluene.
  • reaction is carried out in the presence of a magnesium catalyst; preferably, the magnesium catalyst is magnesium turnings.
  • the reaction comprises: adding in an ether solvent And a magnesium catalyst, and then slowly adding a solution of the halogenated benzocyclobutene in an organic solvent.
  • the organic solvent is a mixture of tetrahydrofuran and toluene (preferably tetrahydrofuran and toluene in a volume ratio of 0.2 to 5:1, Goodland 0.5-3:1).
  • the reaction is carried out at 10 to 50 ° C; preferably at room temperature to 50 ° C.
  • reaction time is 5 to 10 hours.
  • the solvent is removed under normal pressure, and then distilled under reduced pressure to obtain a silicone monomer.
  • the halobenzocyclobutene in the reaction, is from 1:1 to 3: 1-3; preferably from 1:1.5 to 2.5: 1.8 to 2.2.
  • a curing method comprising the step of polymerizing the organosiloxane of the first aspect of the invention to form a cured product.
  • the polymerization is carried out by heating (i.e., heat curing) by heating.
  • the heat curing temperature is 230 to 270 ° C, preferably 240 to 260 ° C.
  • the heat curing comprises pre-curing at 170 to 190 ° C and then curing at 230 to 270 ° C.
  • the heat curing comprises pre-curing at 170 to 190 ° C, and then raising the temperature to 230 to 270 ° C at a rate of temperature increase of 45 to 55 ° C / h, and curing.
  • the heat curing further comprises: slowly heating and/or mechanically vibrating the organosiloxane prior to the pre-cure to remove bubbles to form a dense liquid; preferably, The temperature rise described above is raised from room temperature to 140 to 160 °C.
  • the pre-cure time is 4 to 6 hours.
  • the curing time is 4 to 6 hours.
  • a cured product which is prepared by the method of the fifth aspect of the invention.
  • the cured product has a 5% weight loss temperature in nitrogen of 470 to 530 °C.
  • the cured product has a weight residue of 1000 ° C in nitrogen of ⁇ 60%, preferably ⁇ 65%, more preferably ⁇ 70%, most preferably 73 to 77%.
  • the cured product has a dielectric constant of 2.6 to 3.0 (in the range of 1 to 30 MHz), preferably 2.7 to 2.9.
  • an article comprising the organosiloxane of the formula I according to the first aspect of the invention, the organosilicon monomer of the formula II according to the third aspect of the invention, or As described in the sixth aspect of the invention Cured product; or
  • the article is prepared from an organosiloxane of the formula I according to the first aspect of the invention, a silicone monomer of the formula II according to the third aspect of the invention, or a cured product according to the sixth aspect of the invention. of.
  • the article is a low dielectric constant material or a metal wire overcoated insulating material.
  • the article is a polymeric sheet or film.
  • the article comprises: a substrate, and a film coated on the substrate comprising the cured product of the sixth aspect of the invention.
  • the article is prepared by molding with an organosiloxane of the formula I as described in the first aspect of the invention to obtain a preform, and then the preform. Heat curing is carried out to obtain the article.
  • the molding is carried out by a molding process selected from the group consisting of heat molding, solution spin coating, or solution dispensing.
  • the solution spin coating or solution dispensing comprises the steps of: dissolving the organosiloxane of the formula I according to the first aspect of the invention in an organic solvent to form a solution, followed by spin coating or dripping
  • the solvent is selected from the group consisting of toluene, xylene, trimethylbenzene, diphenyl ether, cyclohexanone, chloroform, acetone, N, N-dimethyl Formamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, or a combination thereof.
  • the degree of polymerization (i.e., n) of the organosiloxane of formula I is from 2 to 20.
  • a crosslinking agent comprising an organosiloxane of the formula I as described in the first aspect of the invention.
  • the crosslinking agent is a crosslinking agent of a high temperature vulcanized silicone rubber (which can be directly added to the silicone resin).
  • a crosslinked silicone rubber wherein the silicone rubber is a high temperature vulcanized silicone rubber, and the silicone rubber comprises a compound of the formula I as described in the first aspect of the invention.
  • the present invention is directed to a method of producing a class of directly siloxane-curable organosiloxanes containing benzocyclobutene groups.
  • Cross-linking polymerization can occur by heating, the cross-linked product has good electrical properties and heat resistance, and the preparation method is simple, and is suitable for packaging materials for insulating coatings and electronic components in the electrical and electronic industry, or as high-temperature silicon sulfide. Rubber crosslinker.
  • siloxane refers to a polymer containing a Si-O-Si bond to form a backbone structure. It is customary to refer to silicone or polysiloxane, which may be linear, cyclic or crosslinked polymers.
  • a preferred organosiloxane has a formula In the structure shown, each R is individually “alkyl I, organic olefinic silicon or alkaryl”.
  • "Formula I polymer” or “organosiloxane of the invention” is used interchangeably and refers to an organosiloxane of formula I.
  • benzocyclobutene substituted or “substituted with benzocyclobutene", “having benzocyclobutenyl” or “having a benzocyclobutene substituent” means the original on each silicon atom in the siloxane a moiety attached to an alkyl group, an alkenyl group or an aryl group (i.e., a moiety originally R) is substituted with a benzocyclobutenyl group; wherein the benzocyclobutenyl group is a benzocyclobutene benzene ring Losing a group formed by a hydrogen atom, for example Or a similar group.
  • halogen means fluoro, chloro, bromo, iodo.
  • halo means that one or more hydrogen atoms on the group are replaced by a halogen.
  • C1-C6 alkyl refers to a straight or branched alkyl group having from 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, or Similar group.
  • C2-C6 alkenyl refers to a straight or branched alkenyl group having 2 to 6 carbon atoms, such as ethenyl, propenyl, allyl, 1-butenyl, 2-butenyl, or the like. Group.
  • C2-C6 alkenyl refers to a straight or branched alkynyl group having 2 to 6 carbon atoms, such as ethynyl, propynyl, allyl, 1-butynyl, 2-butynyl, or Similar group.
  • C1-C4 alkoxy refers to a substituent formed by linking a straight or branched alkyl group having 1 to 4 carbon atoms to oxygen, such as methoxy, ethoxy, n-propoxy, isopropyl. Oxyl, n-butoxy, tert-butoxy, or the like.
  • a relatively simple process is employed to react bromobenzocyclobutene with magnesium metal, and then The obtained benzocyclobutene Grignard reagent is reacted with an organosiloxane to obtain a monomer in which a siloxane is directly linked to a benzocyclobutene unit. Hydrolytic polymerization is carried out using the monomer to obtain a silicone resin having a main chain of siloxane and a side chain of benzocyclobutene.
  • the organosiloxane resins provided herein have a siloxane backbone and a benzocyclobutene substituent on the silicon atom of the siloxane backbone.
  • the benzocyclobutene substituent is directly attached to the silicon atom on the siloxane backbone (ie, via a Si-Ph bond).
  • Each R is independently a substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C2-C6 alkenyl, or substituted or unsubstituted phenyl; said substituent refers to one or more hydrogens on the group
  • the atom is substituted with a substituent selected from the group consisting of halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, unsubstituted or 1-3 hydrogen atoms on the phenyl ring.
  • benzocyclobutene substitution means that one or more R groups in the main chain are replaced by a benzocyclobutene substituent.
  • Each of the siloxane backbones may or may not have a benzocyclobutene substituent, and the silicon atoms on each siloxane backbone may be substituted in any form, such as in a segment Each having a benzocyclobutene substituent, having no benzocyclobutene substituents on other segments, thereby forming a block copolymer; or having a benzocyclobutene at a position separated by one silicon atom Substituent.
  • the substitution mode of the benzocyclobutene substituent can be adjusted by homopolymerization or copolymerization of the monomers, the amount of each monomer, or block copolymerization.
  • ⁇ 30% of the silicon atoms on the siloxane backbone have the benzocyclobutene substituent; preferably, ⁇ 50% of the silicon atoms on the siloxane backbone have The benzocyclobutene substituent; more preferably, ⁇ 70% of the silicon atoms on the siloxane backbone have the benzocyclobutene substituent; optimally, on the siloxane backbone
  • Each of the silicon atoms has the benzocyclobutene substituent.
  • the organosiloxane resin has a refractive index of from 1.5 to 1.6.
  • the siloxane backbone is straight or branched, preferably straight.
  • the organosiloxane has the structure shown in Formula I below:
  • Each of R 1 is independently a group selected from the group consisting of a substituted or unsubstituted C 1 -C 4 alkyl group, a substituted or unsubstituted C 2 -C 4 alkenyl group, or a substituted or unsubstituted phenyl group; wherein the substitution The one or more hydrogen atoms on the group are substituted with a substituent selected from the group consisting of halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, phenyl; The phenyl group is unsubstituted or the phenyl group having 1 to 3 hydrogen atoms on the benzene ring is substituted with a substituent selected from the group consisting of halogen: a C1 to C4 alkyl group; preferably, each of the R 1 groups Independently a group selected from the group consisting of methyl, vinyl, and phenyl.
  • the organosiloxane is prepared by hydrolysis polymerization using a silicone monomer as shown in the following formula II:
  • R 1 is a group selected from the group consisting of a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C2-C6 alkenyl group, or a substituted or unsubstituted phenyl group; wherein the substitution refers to One or more hydrogen atoms on the group are substituted with a substituent selected from the group consisting of halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, phenyl;
  • the phenyl group is unsubstituted or the phenyl group having 1 to 3 hydrogen atoms on the benzene ring is substituted with a substituent selected from the group consisting of halogen: a C1 to C4 alkyl group; preferably, the R 1 is selected Groups from the following groups: methyl, vinyl, phenyl;
  • R 2 and R 3 are each independently a group selected from the group consisting of a C1-C4 alkoxy group and a halogen.
  • the polymerization may be a homopolymerization reaction with a monomer of formula II or a copolymerization reaction of a monomer of formula II with other siloxane monomers.
  • the copolymerization is a hydrolysis copolymerization reaction of a monomer of the formula II with a bisalkoxysiloxane.
  • the hydrolysis polymerization comprises the steps of: hydrolyzing with a silicone monomer as shown in Formula II and optionally a dialkoxysiloxane in the presence of water and an acid catalyst to obtain The organosiloxane described.
  • the molar ratio of water, acid catalyst and monomer of the formula II used in the hydrolysis polymerization is from 50 to 100:5 to 10:1.
  • the preferred acid catalyst is selected from the group consisting of hydrochloric acid, sulfuric acid, acetic acid, formic acid, or a combination thereof; more preferably, the acid catalyst is selected from the group consisting of acetic acid, formic acid, or a combination thereof.
  • the solvent for the hydrolysis polymerization reaction is not particularly limited, and is preferably carried out in a solvent selected from the group consisting of benzene, toluene, xylene, or a combination thereof.
  • the temperature of the hydrolysis polymerization is not particularly limited, but is preferably carried out at 10 to 100 ° C; preferably at room temperature (10 to 40 ° C) to 100 ° C.
  • the hydrolysis polymerization reaction time is not particularly limited, and the end point of the reaction can be determined by a method generally used in the art (e.g., thin layer chromatography, etc.). Preferably, the reaction time is 5 to 20 hours.
  • the invention also provides a silicone monomer as shown in Formula II:
  • R 1 is a group selected from the group consisting of a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C2-C6 alkenyl group, or a substituted or unsubstituted phenyl group; wherein the substitution refers to One or more hydrogen atoms on the group are substituted with a substituent selected from the group consisting of halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, phenyl;
  • the phenyl group is unsubstituted or the phenyl group having 1 to 3 hydrogen atoms on the benzene ring is substituted with a substituent selected from the group consisting of halogen: a C1 to C4 alkyl group; preferably, the R 1 is selected Groups from the following groups: methyl, vinyl, phenyl;
  • R 2 and R 3 are each independently a group selected from the group consisting of a C1-C4 alkoxy group and a halogen.
  • the monomers can be prepared by the following methods:
  • X is a halogen, preferably selected from the group consisting of Cl, Br;
  • R 1 is a group selected from the group consisting of a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C2-C6 alkenyl group, or a substituted or unsubstituted phenyl group; wherein the substituent refers to a group The one or more hydrogen atoms are substituted with a substituent selected from the group consisting of halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, phenyl; wherein the benzene a phenyl group which is unsubstituted or has 1 to 3 hydrogen atoms on the benzene ring substituted with a substituent selected from the group consisting of halogen, C1-C4 alkyl; preferably, R 1 is selected from the group consisting of Group of groups: methyl, vinyl, phenyl;
  • R 2 , R 3 and R 4 are each independently a group selected from the group consisting of a C1-C4 alkoxy group and a halogen.
  • the ether solvent is not particularly limited, and is preferably selected from the group consisting of tetrahydrofuran, methyltetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, cyclohexyl methyl ether, cyclopentyl methyl ether or Its combination.
  • a mixture of tetrahydrofuran and toluene is used.
  • the reaction is carried out in the presence of a magnesium catalyst, and a halogenated benzocyclobutene (preferably bromobenzocyclobutene) is reacted with a magnesium catalyst to form a Grignard reagent, and reaction.
  • a halogenated benzocyclobutene preferably bromobenzocyclobutene
  • the magnesium catalyst is magnesium shavings.
  • the reaction comprises: adding in an ether solvent And a magnesium catalyst, and then slowly adding a solution of the organic solvent of the halogenated benzocyclobutene, preferably, the organic solvent is a mixture of tetrahydrofuran and toluene (2:1, by volume).
  • the reaction is carried out at 10 to 50 ° C; preferably at room temperature to 50 ° C.
  • reaction time is 5 to 10 hours.
  • the solvent is removed under normal pressure, and then distilled under reduced pressure to obtain a silicone monomer.
  • the invention also provides the use of an organosiloxane as shown in Formula I, which can be used in the electrical and electronic industry as an encapsulant for insulating coatings and electronic components, or for preparation
  • an organosiloxane as shown in Formula I which can be used in the electrical and electronic industry as an encapsulant for insulating coatings and electronic components, or for preparation
  • the low dielectric constant material or the metal wire is covered with an insulating material or as a crosslinking agent for the high temperature vulcanized silicone rubber.
  • organosiloxane of the present invention is a cured product for the preparation of an organosiloxane structure prepared by heat curing with an organosiloxane of the formula I as described.
  • the heat curing conditions are not particularly limited, and the performance requirements of the cured product can be adjusted depending on the type of the organosiloxane to be used.
  • the heat curing temperature is set at 230 to 270 ° C, preferably 240 to 260 ° C.
  • the heat curing may also optionally include a pre-cure step, i.e., curing for a period of time at a temperature lower than the heat curing temperature.
  • the heat curing comprises pre-curing at 170 to 190 ° C and then curing at 230 to 270 ° C.
  • the heat curing may be performed under temperature programmed conditions.
  • the heat curing comprises: pre-curing at 170 to 190 ° C, and then heating at a rate of 45 to 55 ° C / h. The temperature was raised to 230 to 270 ° C and cured.
  • the pre-cure time and the curing time are not particularly limited. In a preferred embodiment of the invention, the pre-curing time is 4 to 6 h, and the curing time is 4 to 6 h.
  • n 2 to 20 in the silicone resin of formula I used to prepare the cured product.
  • the cured product has good thermal properties.
  • the cured product has a 5% weight loss temperature in nitrogen of 470 to 530 °C.
  • the cured product has a weight residue of 1000 ° C in nitrogen of ⁇ 60%, preferably ⁇ 65%, more preferably ⁇ 70%, most preferably 73 to 77%.
  • the cured product has good electrical properties.
  • the cured product has a dielectric constant of 2.60 to 3.0 (in the range of 1 to 30 MHz).
  • the silicone resin of the present invention can also be used to prepare an article comprising the organosiloxane of the formula I, a silicone monomer of the formula II, or the cured product; or the article is a use Prepared from the organosiloxane of formula I, the organosilicon monomer of formula II, or the cured product.
  • the article is a low dielectric constant material or a metal wire overcoated insulating material.
  • the article is a polymeric sheet or film.
  • the article comprises: a substrate, and a film comprising the cured product coated on the substrate.
  • the article is prepared by molding with the organosiloxane of the formula I to obtain a preform, and then subjecting the preform to heat curing to obtain The product described.
  • the molding is carried out by a molding process selected from the group consisting of heat molding, solution spin coating, or solution dispensing.
  • a molding process selected from the group consisting of heat molding, solution spin coating, or solution dispensing.
  • the organosiloxane of the formula I has good solubility properties, it is preferred to carry out the treatment by solution spin coating or dripping.
  • the solution spin coating or solution dispensing comprises the steps of: dissolving the organosiloxane of the formula I in an organic solvent to form a solution, followed by spin coating or dispensing; preferably,
  • the solvent is selected from the group consisting of toluene, xylene, trimethylbenzene, diphenyl ether, cyclohexanone, chloroform, acetone, N,N-dimethylformamide, N,N. - dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, or a combination thereof.
  • the degree of polymerization (i.e., n) of the organosiloxane of formula I is from 2 to 20.
  • the organosiloxane of the present invention can also be used as a crosslinking agent for preparing a high temperature vulcanized silicone rubber. In use, the organosiloxane of the present invention is directly added to the silicone resin.
  • the organosiloxane of the present invention can be prepared by hydrolysis polymerization. Compared with the prior art, the preparation of the monomer prepolymer needs to be carried out at a relatively high temperature, the preparation method is simple, the conditions are mild, and the reaction can be carried out. Controlled, and the molecular weight of the obtained prepolymer (i.e., organosiloxane) can be effectively controlled.
  • the organosiloxane of the present invention can be produced without using a noble metal catalyst such as platinum or the like, which greatly reduces the cost of preparation.
  • the preparation method of the invention is simple, the equipment requirements are low, and it is suitable for industrial production.
  • the organosiloxane provided by the present invention can be used for preparing a cured product having excellent electrical properties, heat resistance and mechanical properties, and its thermal stability is remarkably improved.
  • the refractive index of the obtained polymer at room temperature was 1.56 as measured by an Abbe refractometer.
  • the refractive index of the obtained polymer at room temperature was 1.57 as measured by an Abbe refractometer.
  • Example 3 1.5 g of the polymer obtained in Example 3 was placed in a flat-bottom schlenk tube having an inner diameter of 1 cm, and the temperature was raised to 250. °C, and kept at this temperature for 5 hours, then cooled to room temperature, the cured product was removed, ground, and subjected to TGA test. The results showed that the cured product had a 5% weight loss temperature of 496 ° C in nitrogen and a residual weight of 75% at 1000 ° C.
  • Example 3 1.5 g of the polymer obtained in Example 3 was placed in a flat-bottom schlenk tube having an inner diameter of 1 cm, evacuated and slowly heated to 150 ° C under mechanical vibration to remove bubbles to form a dense liquid, warmed to 180 ° C, and kept at this temperature for 5 h. Pre-cured. After cooling to room temperature, it was transferred to a quartz tube furnace and heated to 250 ° C at a rate of 50 ° C / h. After this temperature was maintained for 5 hours, it was taken out and ground into a pellet, and the dielectric constant was measured. The results showed that the frequency range was from 1 MHz to 30 MHz. Its dielectric constant is between 2.75 and 2.85.
  • Example 5 1.5 g of the polymer obtained in Example 5 was placed in a flat-bottom schlenk tube having an inner diameter of 1 cm, heated to 250 ° C, and maintained at this temperature for 5 hours, then cooled to room temperature, the cured product was removed, ground, and subjected to TGA test. The results showed that the cured product had a 5% weight loss temperature of 485 ° C in nitrogen and a residual weight of 73 % at 1000 ° C.
  • Example 3 1.5 g of the polymer obtained in Example 3 was placed in a flat-bottom schlenk tube having an inner diameter of 1 cm, evacuated and slowly heated to 150 ° C under mechanical vibration to remove bubbles to form a dense liquid, warmed to 180 ° C, and kept at this temperature for 5 h. Pre-cured. After cooling to room temperature, it was transferred to a quartz tube furnace and heated to 250 ° C at a rate of 50 ° C / h. After this temperature was maintained for 5 hours, it was taken out and ground into a pellet, and the dielectric constant was measured. The results showed that the frequency range was from 1 MHz to 30 MHz. Its dielectric constant is between 2.72 and 2.83.

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Abstract

本发明提供了一种含苯并环丁烯基团的有机硅氧烷及其制备和应用，具体地，本发明提供了一种含有苯并环丁烯单元的有机硅氧烷，所述有机硅氧烷具有硅氧烷主链，以及具有与硅氧烷主链的硅原子直接相连的苯并环丁烯取代基。本发明的有机硅树脂通过加热即能发生交联聚合，交联产物具有良好的电学性能和耐热性，且制备方法简单，适用于电子电气行业作为绝缘包覆层和电子元器件的封装材料，也可作为高温硫化硅橡胶的交联剂。

Description

含苯并环丁烯基团的有机硅氧烷及其制备和应用 技术领域
本发明属于高性能聚合物单体的制造领域，具体涉及一种含苯并环丁烯基团，可直接热固化的有机硅氧烷，及其制备方法。
背景技术
在已知的热固性树脂中，苯并环丁烯类树脂分子因其受热可开环固化，形成体型高聚物、固化产物无论耐热性还是尺寸稳定性俱佳的特点，已广泛用于航天航空、微电子、军事和民用等领域。
另一方面，有机硅树脂具有高的耐热性、易加工性和优异的光学性能，已被广泛应用许多工业部门。然而，通常情况下，有机硅树脂欲获得应用，需要进行交联。常用的交联方式一般有硅氢加成和自由基扩链方式，而在多数情况下，这样的交联方式或者需要催化剂(金属铂)或者需要引发剂。
将苯并环丁烯和有机硅树脂结合起来，利用苯并环丁烯可直接热固化的特点，可获得能直接热固化的有机硅树脂。许多研究者正是利用这一特点，开发出了多种含硅的苯并环丁烯。陶氏公司开发的含烯烃和硅的苯并环丁烯单体(玻璃钢/复合材料，2005年第4期，16-19.)如下式所示：
Figure PCTCN2014090653-appb-000001
然而，这种单体分子量小，熔点较低，成膜性差，因此在使用时需将其预聚，以形成一定分子量的预聚物：
杨士勇等人报道了下式所示的单体(J.Polym.Sci.Polym.Chem.2009,47,6246-6258)：
Figure PCTCN2014090653-appb-000002
这些单体实际上是对陶氏公司单体的改进，通过引入苯基硅烷以提高聚合物的耐热性。然而，上述单体也同样具有分子量小，熔点较低，成膜性差，使用时需预聚的缺点。
杨军校等报道了下式所示单体(中国发明专利申请号200810044584.7和201110092603.5)：
Figure PCTCN2014090653-appb-000003
这些单体聚合后，可获得高耐温材料。进一步，他们通过硅氢加成得到了主链为硅氧烷、侧链含有热固性苯并环丁烯的聚合物(中国发明专利申请号201110367893.X)：
Figure PCTCN2014090653-appb-000004
然而，上述含苯并环丁烯单元的有机硅单体和有机硅树脂树脂存在合成条件苛刻、起始原料难以获得或成本较高的问题。特别是第一种和第二种单体，聚合时需要使用钯催化的HECK反应，一方面，钯催化剂价格昂贵，反应过程中还要使用金属配体；另一方面，这类反应收率普遍不高。如此，导致最终的硅树脂成本的提高，其应用受到很大程度的限制。
除此之外，由于偶联反应制备得到的含苯并环丁烯的有机硅氧烷中，苯并环丁烯单元不是与硅氧烷主链直接相连，而是通过碳链相连，导致其热稳定性无法提高。另外，上述反应还存在反应程度难以控制的问题。
综上所述，本领域迫切需要开发一种制备成本低，合成条件温和的含苯并环丁烯单元的有机硅单体及相应的硅树脂。
发明内容
本发明的目的是提供一种制备成本低，合成条件温和的含苯并环丁烯单元的有机硅单体及相应的硅树脂。
本发明的第一方面，提供了一种有机硅氧烷，所述有机硅氧烷具有硅氧烷主链，以及具有与硅氧烷主链的硅原子直接相连的苯并环丁烯基。
在另一优选例中，≥30％硅氧烷主链上的硅原子具有与Si直接相连的苯并环丁烯取代基。
在另一优选例中，≥50％(较佳地70-100％，更佳地90-100％)硅氧烷主链上的硅原子具有与Si直接相连的苯并环丁烯基。
在另一优选例中，所述的硅氧烷主链具有式A结构；
Figure PCTCN2014090653-appb-000005
其中，
x为≥2的正整数(较佳地为2～200)；
各R独立地选自下组：
(a)H；
(b)取代或未取代C1～C6的烷基、取代或未取代C2～C6烯基，其中所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代：卤素、C1～C4的烷基、C2～C4的烯基、C2～C4的炔基、未取代的或苯环上的1～3个氢原子被选自下组的取代基取代的苯基：卤素、C1～C4的烷基；
(c)取代或未取代的苯基；所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代：卤素、C1～C4的烷基、C1～C4的卤代烷基、C2～C4的烯基、C2～C4的炔基、未取代的苯基；
(d)苯并环丁烯基；
并且，至少一个R为苯并环丁烯基。
在另一优选例中，所述的苯并环丁烯基为
Figure PCTCN2014090653-appb-000006
在另一优选例中，硅氧烷主链上的每个硅原子都具有所述的苯并环丁烯基。
在另一优选例中，所述的有机硅氧烷为树脂。
在另一优选例，所述有机硅氧烷的折光率为1.5～1.6。
在另一优选例中，所述的硅氧烷主链包括直链主链和/或支链主链，较佳地为直链主链。
在另一优选例中，所述的有机硅氧烷具有如下式I所示结构：
Figure PCTCN2014090653-appb-000007
其中，n为≥2的正整数(较佳地n＝2～100，更佳地n＝2～50，最佳地n＝2～20)；
各R1独立地选自下组：
(a)H；
(b)取代或未取代C1～C6的烷基、取代或未取代C2～C6烯基，其中所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代：卤素、C1～C4的烷基、C2～C4的烯基、C2～C4的炔基、未取代的或苯环上的1～3个氢原子被选自下组的取代基取代的苯基：卤素、C1～C4的烷基；
(c)取代或未取代的苯基；所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代：卤素、C1～C4的烷基、C1～C4的卤代烷基、C2～C4的烯基、C2～C4的炔基、未取代的苯基。
在另一优选例中，各R1各自独立地为选自下组的基团：C1～C4烷基、C2～C4烯基、或取代或未取代的苯基。
在另一优选例，所述的R1各自独立地为选自下组的基团：甲基、乙烯基、苯基。
在另一优选例中，各基团是实施例各化合物中所记载的具体基团。
本发明的第二方面，提供了一种如本发明第一方面所述的有机硅氧烷的制备方法，所述的有机硅氧烷是用如下式II所示的有机硅单体进行水解聚合制备的：
Figure PCTCN2014090653-appb-000008
其中，R1为选自下组的基团：
(a)H；
(b)取代或未取代C1～C6的烷基、取代或未取代C2～C6烯基，其中所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代：卤素、C1～C4的烷基、C2～C4的烯基、C2～C4的炔基、未取代的或苯环上的1～3个氢原子被选自下组的取代基取代的苯基：卤素、C1～C4的烷基；
(c)取代或未取代的苯基；所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代：卤素、C1～C4的烷基、C1～C4的卤代烷基、C2～C4的烯基、C2～C4的炔基、未取代的苯基；
R2、R3各自独立地为选自下组的基团：C1～C4的烷氧基，卤素。
在另一优选例中，R2、R3、R4各自独立地为选自下组的基团：C1～C2烷氧基，卤素。
在另一优选例，所述的R1为选自下组的基团：甲基、乙烯基、苯基；
在另一优选例中，所述的聚合是均聚或共聚。
在另一优选例中，所述的共聚是用式II单体与双烷氧基硅氧烷进行水解共聚。
在另一优选例中，所述的双烷氧基硅氧烷中的烷氧基独立地为取代或未取代的C1～C10烷氧基，其中取代指基团上的一个或多个氢原子被选自下组的取代基取代：卤素、C1～C4的烷基、C2～C4的烯基、C2～C4的炔基、未取代的或苯环上的1～3个氢原子被选自下组的取代基取代的苯基：卤素、C1～C4的烷基。
在另一优选例，所述双烷氧基硅氧烷中的两个烷氧基是相同或不同的。
在另一优选例中，所述的水解聚合包括步骤：在酸催化剂存在下，用如式II 所示的有机硅单体和任选的双烷氧基硅氧烷进行水解，得到如本发明第一方面所述的有机硅氧烷。
在另一优选例中，所述的水解聚合在水存在下进行。
在另一优选例中，当所述的水解聚合为均聚时，所述的水解聚合中，所用的酸性催化剂和式II单体的摩尔比为5～10：0.8～1.2。
在另一优选例中，当所述的水解聚合为均聚时，所述的水解聚合中，所用的水、酸性催化剂和式II单体的摩尔比为50～100：5～10：0.8～1.2。
在另一优选例中，当所述的水解聚合为共聚时，所述的水解聚合中，所用的酸性催化剂和(式II单体+双烷氧基硅氧烷)的摩尔比为5～10:0.8-1.2。
在另一优选例中，当所述的水解聚合为共聚时，所述的水解聚合中，所用的水、酸性催化剂和(式II单体+双烷氧基硅氧烷)的摩尔比为50～100：5～10:0.8-1.2。
在另一优选例中，当所述的水解聚合为共聚时，所述的水解聚合中，所用的式II单体和双烷氧基硅氧烷的摩尔比为0.5-2:0.8-1.2。
在另一优选例中，所述的酸催化剂选自下组：盐酸、硫酸、乙酸、甲酸，或其组合；较佳地，所述的酸催化剂选自下组：乙酸、甲酸，或其组合。
在另一优选例中，所述的水解聚合具有选自下组的一个或多个条件：
在选自下组的溶剂中进行：苯、甲苯、二甲苯，或其组合；
所述的水解聚合在10～100℃下进行；优选在室温～100℃下进行；
所述的水解聚合反应时间为5～48h。
本发明的第三方面，提供了一种如式II所示的有机硅单体：
Figure PCTCN2014090653-appb-000009
其中，R1为选自下组的基团：
(a)H；
(b)取代或未取代C1～C6的烷基、取代或未取代C2～C6烯基，其中所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代：卤素、C1～C4的烷基、C2～C4的烯基、C2～C4的炔基、未取代的或苯环上的1～3个氢原子被选自下组的取代基取代的苯基：卤素、C1～C4的烷基；
(c)取代或未取代的苯基；所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代：卤素、C1～C4的烷基、C1～C4的卤代烷基、C2～C4的烯基、C2～C4的炔基、未取代的苯基；
R2、R3各自独立地为选自下组的基团：C1～C4的烷氧基，卤素。
在另一优选例中，R2、R3、R4各自独立地为选自下组的基团：C1～C2烷氧基，卤素。
本发明的第四方面，提供了一种如本发明第三方面所述的单体的制备方法，所述方法包括步骤：
Figure PCTCN2014090653-appb-000010
在惰性溶剂(如醚类溶剂)中，用卤代苯并环丁烯与
Figure PCTCN2014090653-appb-000011
反应，得到式II所示的有机硅单体；
其中，X为卤素，较佳地选自下组：Cl、Br；
R1为选自下组的基团：
(a)H；
(b)取代或未取代C1～C6的烷基、取代或未取代C2～C6烯基，其中所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代：卤素、C1～C4的烷基、C2～C4的烯基、C2～C4的炔基、未取代的或苯环上的1～3个氢原子被选自下组的取代基取代的苯基：卤素、C1～C4的烷基；
(c)取代或未取代的苯基；所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代：卤素、C1～C4的烷基、C1～C4的卤代烷基、C2～C4的烯基、C2～C4的炔基、未取代的苯基；
R2、R3、R4各自独立地为选自下组的基团：C1～C4烷氧基，卤素。
在另一优选例中，R2、R3、R4各自独立地为选自下组的基团：C1～C2烷氧基，卤素。
在另一优选例中，所述的醚类溶剂选自下组：四氢呋喃、甲基四氢呋喃、乙醚，二氧六环、乙二醇二甲醚、环己基甲醚、环戊基甲醚，或其组合。
在另一优选例中，所述的惰性溶剂为四氢呋喃和甲苯的混合物。
在另一优选例中，所述的惰性溶剂为四氢呋喃和甲苯；优选比例为四氢呋喃：甲苯＝1～10:10(重量比或体积比)的混合物。
在另一优选例中，所述的反应在镁催化剂存在下进行；较佳地，所述的镁催化剂为镁屑。
在另一优选例中，所述的
Figure PCTCN2014090653-appb-000012
选自下组：甲基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、甲基三氯硅烷、乙烯基三氯硅烷，或其组合。
在另一优选例中，所述的反应包括：在醚类溶剂中加入
Figure PCTCN2014090653-appb-000013
和镁催化剂，然后缓慢滴加卤代苯并环丁烯的有机溶剂溶液，较佳地，所述的有机溶剂为四氢呋喃和甲苯的混合液(优选四氢呋喃和甲苯体积比0.2-5:1，较佳地0.5-3:1)。
在另一优选例中，所述的反应在10～50℃下进行；较佳地在室温～50℃下进行。
在另一优选例中，所述的反应时间为5～10h。
在另一优选例中，所述的反应结束后，常压除去溶剂，然后减压蒸馏得到有机硅单体。
在另一优选例中，所述的反应中，所述的卤代苯并环丁烯、
Figure PCTCN2014090653-appb-000014
与镁催化剂的摩尔比为1:1-3:1-3；较佳地为1:1.5-2.5:1.8-2.2。
本发明的第五方面，提供了一种固化方法，所述方法包括步骤：对本发明第一方面所述的有机硅氧烷进行聚合，从而形成固化产物。
在另一优选例中，所述的聚合是通过加热进行聚合固化(即加热固化)。
在另一优选例中，所述的加热固化温度为230～270℃，较佳地为240～260℃。
在另一优选例中，所述的加热固化包括：在170～190℃下进行预固化，然后在230～270℃下进行固化。
在另一优选例中，所述的加热固化包括：在170～190℃下进行预固化，然后以升温速率为45～55℃/h的速率升温至230～270℃，并进行固化。
在另一优选例中，所述的加热固化还包括：在所述预固化之前，对所述有机硅氧烷进行缓慢升温和/或机械振动，从而除去气泡，形成致密液体；优选地，所述的升温为由室温升温至140～160℃。
在另一优选例中，所述预固化时间为4～6h。
在另一优选例中，所述固化时间为4～6h。
本发明的第六方面，提供了一种固化产物，所述的固化产物是用如本发明第五方面所述的方法制备的。
在另一优选例中，所述固化产物在氮气中的5％热失重温度为470～530℃。
在另一优选例中，所述固化产物在氮气中的1000℃重量残余为≥60％，较佳地为≥65％，更佳地为≥70％，最佳地为73～77％。
在另一优选例中，所述固化产物的介电常数为2.6～3.0(1-30MHz范围内)，较佳地为2.7～2.9。
本发明的第七方面，提供了一种制品，所述制品含有如本发明第一方面所述的式I有机硅氧烷、如本发明第三方面所述的式II有机硅单体，或如本发明第六方面所述 的固化产物；或
所述制品是用如本发明第一方面所述的式I有机硅氧烷、如本发明第三方面所述的式II有机硅单体，或如本发明第六方面所述的固化产物制备的。
在另一优选例中，所述的制品为低介电常数材料或金属导线外包覆绝缘材料。
在另一优选例中，所述的制品为聚合物片材或薄膜。
在另一优选例中，所述的制品包括：基材，以及涂覆于基材之上的含有如本发明第六方面所述的固化产物的薄膜。
在另一优选例中，所述的制品是通过以下方法制备的：用如本发明第一方面所述的式I有机硅氧烷进行成型，得到预成型体，然后对所述的预成型体进行加热固化，得到所述的制品。
在另一优选例中，所述的成型是通过选自下组的成型工艺进行的：加热模压，溶液旋涂，或溶液滴涂。
在另一优选例中，所述溶液旋涂或溶液滴涂包括步骤：将如本发明第一方面所述的式I有机硅氧烷溶于有机溶剂中配成溶液，然后进行旋涂或滴涂；较佳地，所述的溶剂选自下组：所述的有机溶剂为甲苯、二甲苯、三甲苯、二苯醚、环己酮、三氯甲烷、丙酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、N-甲基吡咯烷酮，或其组合。
在另一优选例中，所述的式I有机硅氧烷的聚合度(即n)＝2～20。
本发明的第八方面，提供了一种交联剂，所述的交联剂含有如本发明第一方面所述的式I有机硅氧烷。
在另一优选例中，所述的交联剂为高温硫化硅橡胶的交联剂(可直接添加到硅树脂中)。
本发明的第九方面，提供了一种交联的硅橡胶，所述的硅橡胶为高温硫化硅橡胶，且所述的硅橡胶中含有如本发明第一方面所述的式I化合物。
应理解，在本发明范围内中，本发明的上述各技术特征和在下文(如实施例)中具体描述的各技术特征之间都可以互相组合，从而构成新的或优选的技术方案。限于篇幅，在此不再一一累述。
具体实施方式
本发明旨在于提供一类含有苯并环丁烯基团的、可直接热固化的有机硅氧烷的制造方法。通过加热即能发生交联聚合，交联产物具有良好的电学性能和耐热性，且制备方法简单，适用于电子电气行业作为绝缘包覆层和电子元器件的封装材料，或者作为高温硫化硅橡胶的交联剂。
术语
如本文所用，术语“硅氧烷”或“有机硅氧烷”指含Si—O—Si键构成主链结构的聚合物。习惯上称有机硅或聚硅醚，可以是线型、环状或交联的聚合物。本发明中，一种优选的有机硅氧烷具有如式
Figure PCTCN2014090653-appb-000015
所示的结构，其中，各个R各自独术立语地为“烷式I基、有机烯硅基氧或烷芳”基、。“式I聚合物”或“本发明的有机硅氧烷”可互换使用，均指式I所示的有机硅氧烷。
术语“苯并环丁烯取代”或“被苯并环丁烯取代”、“具有苯并环丁烯基”或“具有苯并环丁烯取代基”指硅氧烷中各个硅原子上原本与烷基、烯基或芳基相连的部分(即原本为R的部分)被苯并环丁烯基取代；其中，所述的苯并环丁烯基为苯并环丁烯的苯环上失去一个氢原子形成的基团，例如
Figure PCTCN2014090653-appb-000016
或类似基团。
术语“卤素”指氟、氯、溴、碘。
术语“卤代”指基团上的一个或多个氢原子被卤素所取代。
术语“C1～C6的烷基”指具有1～6个碳原子的直链或支链烷基，如甲基、乙基、正丙基、异丙基、正丁基、叔丁基，或类似基团。
术语“C2～C6烯基”指具有2～6个碳原子的直链或支链烯基，如乙烯基、丙烯基、烯丙基、1-丁烯基、2-丁烯基，或类似基团。
术语“C2～C6烯基”指具有2～6个碳原子的直链或支链炔基，如乙炔基、丙炔基、烯丙基、1-丁炔基、2-丁炔基，或类似基团。
术语“C1～C4的烷氧基”指具有1～4个碳原子的直链或支链烷基与氧相连形成的取代基，如甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、叔丁氧基，或类似基团。
含苯并环丁烯的有机硅氧烷
已知现有的有机硅树脂需要使其形成交联体系才能得到更为广泛的应用。而由于苯并环丁烯单元具有受热后可以使环丁烯单元开环，从而形成具有较高分子量的体系高聚物的特点，适合被引入有机硅树脂中形成交联体系。
然而，现有技术中，均采用了将苯并环丁烯单元与已经进行聚合的有机硅氧烷进行偶联的方法。本领域有过报道的含苯并环丁烯结构单元的有机硅氧烷均需要采用Pt催化的HECK偶联反应，将苯并环丁烯结构单元引入有机硅氧烷中。这样做的缺点在于，当反应结束后，很难将Pt催化剂全部去除，且Pt催化剂属于贵金属，导致现有的含苯并环丁烯的有机硅氧烷成本非常高昂。
本发明中，采用了较为简单的工艺，将溴代苯并环丁烯与金属镁反应，再将 获得的苯并环丁烯格氏试剂与有机硅氧烷作用，制得硅氧烷与苯并环丁烯单元直接相连的单体。用该单体进行水解聚合，即可获得主链为硅氧烷、侧链为苯并环丁烯的有机硅树脂。
具体地，本发明所提供的有机硅氧烷树脂具有硅氧烷主链，以及位于硅氧烷主链的硅原子上的苯并环丁烯取代基。其中，所述的苯并环丁烯取代基为直接与硅氧烷主链上的硅原子相连(即通过Si-Ph键相连)。
所述的硅氧烷主链的种类没有特别限制，在另一优选例中，所述的硅氧烷主链具有形如
Figure PCTCN2014090653-appb-000017
的结构；其中，x＝2～200；
各个R各自独立地为取代或未取代C1～C6的烷基、取代或未取代C2～C6烯基、或取代或未取代的苯基；所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代：卤素、C1～C4的烷基、C2～C4的烯基、C2～C4的炔基、未取代的或苯环上的1～3个氢原子被选自下组的取代基取代的苯基：卤素、C1～C4的烷基；
且所述的苯并环丁烯取代指主链上的一个或多个R基被苯并环丁烯取代基所替换。
每个所述的硅氧烷主链可以任选地具有或不具有苯并环丁烯取代基，各个硅氧烷主链上的硅原子可以以任意的形式被取代，如在某一链段上均具有苯并环丁烯取代基，在其他链段上均不具有苯并环丁烯取代基，从而形成嵌段共聚物的形式；或在间隔一个硅原子的位置具有苯并环丁烯取代基。苯并环丁烯取代基的取代方式可以通过单体的均聚或共聚，不同单体各自的用量，或嵌段共聚等方式进行调节。
在另一优选例中，≥30％位于硅氧烷主链上的硅原子具有所述的苯并环丁烯取代基；较佳地，≥50％位于硅氧烷主链上的硅原子具有所述的苯并环丁烯取代基；更佳地，≥70％位于硅氧烷主链上的硅原子具有所述的苯并环丁烯取代基；最佳地，硅氧烷主链上的每个硅原子都具有所述的苯并环丁烯取代基。
在另一优选例中，所述的有机硅氧烷树脂的折光率为1.5～1.6。
在另一优选例中，所述的硅氧烷主链为直链或支链，较佳地为直链。
在本发明的一种优选实施例中，所述的有机硅氧烷具有如下式I所示结构：
Figure PCTCN2014090653-appb-000018
其中，n＝2～100，较佳地，n＝2～50，更佳地n＝2～20；
各个R1各自独立地为选自下组的基团：取代或未取代C1～C4烷基、取代或未取代C2～C4烯基、或取代或未取代的苯基；其中，所述的取代指基团上的一 个或多个氢原子被选自下组的取代基取代：卤素、C1～C4的烷基、C2～C4的烯基、C2～C4的炔基、苯基；其中，所述的苯基为未取代的或苯环上的1～3个氢原子被选自下组的取代基取代的苯基：卤素、C1～C4的烷基；优选地，所述的R1各自独立地为选自下组的基团：甲基，乙烯基、苯基。
所述的有机硅氧烷是用如下式II所示的有机硅单体进行水解聚合制备的：
Figure PCTCN2014090653-appb-000019
其中，R1为选自下组的基团：取代或未取代C1～C6的烷基、取代或未取代C2～C6烯基、或取代或未取代的苯基；其中，所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代：卤素、C1～C4的烷基、C2～C4的烯基、C2～C4的炔基、苯基；其中，所述的苯基为未取代的或苯环上的1～3个氢原子被选自下组的取代基取代的苯基：卤素、C1～C4的烷基；优选地，所述的R1为选自下组的基团：甲基，乙烯基、苯基；
R2、R3各自独立地为选自下组的基团：C1～C4烷氧基，卤素。
所述的聚合可以是用式II单体进行的均聚反应，也可以是式II单体和其他硅氧烷单体进行的共聚反应。在另一优选例中，所述的共聚是用式II单体与双烷氧基硅氧烷进行的水解共聚反应。
在另一优选例中，所述的水解聚合包括步骤：在水和酸催化剂存在下，用如式II所示的有机硅单体和任选的双烷氧基硅氧烷进行水解，得到所述的有机硅氧烷。在另一优选例中，当所述的水解聚合为均聚时，所述的水解聚合中，所用的水、酸性催化剂和式II单体的摩尔比为50～100：5～10:1。
在所述的水解聚合反应中，由于环丁烯结构单元非常容易开环，因此需选择合适的酸催化剂，方可得到较高的产率。本发明中，优选的所述酸催化剂选自下组：盐酸、硫酸、乙酸、甲酸，或其组合；更优选的所述的酸催化剂选自下组：乙酸、甲酸，或其组合。
所述的水解聚合反应的溶剂没有特别的限制，较佳地在选自下组的溶剂中进行：苯、甲苯、二甲苯，或其组合。
所述的水解聚合的温度没有特别的限制，较佳地在10～100℃下进行；优选在室温(10～40℃)～100℃下进行。
所述的水解聚合反应时间没有特别的限制，可采用本领域通用的方法(如薄层层析等)确定反应的终点，较佳地，所述的反应时间为5～20h。
本发明所采用的所有原料均为市售品，且偶联或聚合时不需要任何过渡金属催化剂。
含苯并环丁烯的有机硅单体
本发明还提供了一种如式II所示的有机硅单体：
Figure PCTCN2014090653-appb-000020
其中，R1为选自下组的基团：取代或未取代C1～C6的烷基、取代或未取代C2～C6烯基、或取代或未取代的苯基；其中，所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代：卤素、C1～C4的烷基、C2～C4的烯基、C2～C4的炔基、苯基；其中，所述的苯基为未取代的或苯环上的1～3个氢原子被选自下组的取代基取代的苯基：卤素、C1～C4的烷基；优选地，所述的R1为选自下组的基团：甲基，乙烯基、苯基；
R2、R3各自独立地为选自下组的基团：C1～C4烷氧基，卤素。
所述的单体可以用下述的方法进行制备：
Figure PCTCN2014090653-appb-000021
在惰性溶剂中，用卤代苯并环丁烯与
Figure PCTCN2014090653-appb-000022
反应，得到式II所示的有机硅单体；
其中，X为卤素，较佳地选自下组：Cl、Br；
R1为选自下组的基团：取代或未取代C1～C6的烷基、取代或未取代C2～C6烯基、或取代或未取代的苯基；其中，所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代：卤素、C1～C4的烷基、C2～C4的烯基、C2～C4的炔基、苯基；其中，所述的苯基为未取代的或苯环上的1～3个氢原子被选自下组的取代基取代的苯基：卤素、C1～C4的烷基；优选地，所述的R1为选自下组的基团：甲基，乙烯基、苯基；
R2、R3、R4各自独立地为选自下组的基团：C1～C4烷氧基，卤素。
所述的醚类溶剂没有特别的限制，较佳地选自下组：四氢呋喃、甲基四氢呋喃、乙醚，二氧六环、乙二醇二甲醚、环己基甲醚、环戊基甲醚或其组合。
在本发明的另一优选例中，为了便于后处理，特别地，使用四氢呋喃和甲苯的混合物。混合物的比例为四氢呋喃：甲苯＝10:1～10(重量比或体积比)。
优选地，所述的反应在镁催化剂存在下进行，用卤代苯并环丁烯(优选为溴代 苯并环丁烯)与镁催化剂进行反应，生成格氏试剂后，与
Figure PCTCN2014090653-appb-000023
反应。较佳地，所述的镁催化剂为镁屑。
在另一优选例中，所述的
Figure PCTCN2014090653-appb-000024
选自下组：甲基三乙氧基硅烷、乙烯基三甲氧基硅烷，或其组合。
在另一优选例中，所述的
Figure PCTCN2014090653-appb-000025
选自下组：甲基三氯硅烷、乙烯基三氯硅烷，或其组合。
在另一优选例中，所述的反应包括：在醚类溶剂中加入
Figure PCTCN2014090653-appb-000026
和镁催化剂，然后缓慢滴加卤代苯并环丁烯的有机溶剂溶液，较佳地，所述的有机溶剂为四氢呋喃和甲苯(2:1，体积比)的混合液。
在另一优选例中，所述的反应在10～50℃下进行；较佳地在室温～50℃下进行。
在另一优选例中，所述的反应时间为5～10h。
在另一优选例中，所述的反应结束后，常压除去溶剂，然后减压蒸馏得到有机硅单体。
有机硅树脂的应用
本发明还提供了一种如式I所示的有机硅氧烷的用途，所述的有机硅氧烷可用于电子电气行业，作为绝缘包覆层和电子元器件的封装材料，或用于制备低介电常数材料或金属导线外包覆绝缘材料，或者作为高温硫化硅橡胶的交联剂。
本发明的有机硅氧烷的一种应用，是用于制备有机硅氧烷结构的固化产物，所述的固化产物是用如所述的式I有机硅氧烷进行加热固化，从而制备的。
其中，所述的加热固化条件没有特别的限制，可根据具体使用的有机硅氧烷种类，对于固化产物的性能要求能具体情况进行调整。在本发明的一种优选实施例中，所述的加热固化温度为在230～270℃，较佳地为240～260℃下进行固化。
所述的加热固化还可以任选地包括预固化步骤，即，在比加热固化温度低的温度下先进行一段时间的固化。在另一优选例中，所述的加热固化包括：在170～190℃下进行预固化，然后在230～270℃下进行固化。
所述的加热固化可以在程序升温的条件下进行，在另一优选例中，所述的加热固化包括：在170～190℃下进行预固化，然后以升温速率为45～55℃/h的速率升温至230～270℃，并进行固化。
所述预固化时间和所述固化的时间没有特别的限制，在本发明的一个优选实施例中，所述预固化的时间为4～6h，所述固化的时间为4～6h。
较佳地，在制备所述的固化产物时，使用链长较短的式I有机硅氧烷，可以更好地调节产物的一系列性质如硬度、玻璃化转变温度等，且加工更为方便。优选的用于制备所述固化产物的式I有机硅树脂中，聚合度(即n)＝2～20。
所述的固化产物具有良好的热学性能。在本发明的一个优选例中，所述固化产物在氮气中的5％热失重温度为470～530℃。在另一优选例中，所述固化产物在氮气中的1000℃重量残余为≥60％，较佳地为≥65％，更佳地为≥70％，最佳地为73～77％。
所述的固化产物具有良好的电学性能。在另一优选例中，所述固化产物的介电常数为2.60～3.0(1-30MHz范围内)。
本发明的有机硅树脂还可以用于制备一种制品，所述制品含有所述的式I有机硅氧烷、式II有机硅单体，或所述的固化产物；或所述制品是用所述的式I有机硅氧烷、式II有机硅单体，或所述的固化产物制备的。
在另一优选例中，所述的制品为低介电常数材料或金属导线外包覆绝缘材料。
在另一优选例中，所述的制品为聚合物片材或薄膜。
在另一优选例中，所述的制品包括：基材，以及涂覆于基材之上的含有所述的固化产物的薄膜。
在另一优选例中，所述的制品是通过以下方法制备的：用所述的式I有机硅氧烷进行成型，得到预成型体，然后对所述的预成型体进行加热固化，得到所述的制品。
在另一优选例中，所述的成型是通过选自下组的成型工艺进行的：加热模压，溶液旋涂，或溶液滴涂。特别地，由于式I有机硅氧烷具有良好的溶解性能，优选可以使用溶液旋涂或滴涂的方式进行加工。
在另一优选例中，所述溶液旋涂或溶液滴涂包括步骤：将所述的式I有机硅氧烷溶于有机溶剂中配成溶液，然后进行旋涂或滴涂；较佳地，所述的溶剂选自下组：所述的有机溶剂为甲苯、二甲苯、三甲苯、二苯醚、环己酮、三氯甲烷、丙酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、N-甲基吡咯烷酮，或其组合。
在另一优选例中，所述的式I有机硅氧烷的聚合度(即n)＝2～20。
本发明的有机硅氧烷还可以用作交联剂，用于制备高温硫化硅橡胶。在使用时，直接将本发明的有机硅氧烷添加到硅树脂中。
本发明的主要优点：
(1)本发明所提供的含有苯并环丁烯的有机硅单体制备过程简单，和现有技 术中所报道的含苯并环丁烯的有机硅氧烷单体相比，合成仅仅采用简单的格氏反应即可完成制备，且所使用的原料烷基烷氧基硅烷和卤代苯并环丁烯均为市售原料，价格低廉，较现有技术中所用的起始原料二乙烯基硅氧烷或含氢硅油相比成本降低显著，使得最终单体的合成成本大大降低。
(2)本发明的有机硅氧烷采用水解聚合就能进行制备，相对于现有技术中，单体的预聚物的制备需要在较高温度下进行，制备方法简单，条件温和，反应可控，且获得的预聚物(即有机硅氧烷)的分子量可以有效地控制。
(3)本发明的有机硅氧烷无需使用贵金属催化剂如铂等进行制备，极大地降低了制备的成本。
(4)本发明的制备方法简单，设备要求低，适合工业化生产。
(5)本发明所提供的有机硅氧烷可用于制备具有很好的电学性能、耐热性能和力学性能的固化产物，其热稳定性得到了显著提高。
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的实验方法，通常按照常规条件，或按照制造厂商所建议的条件。除非另外说明，否则百分比和份数按重量计算。
实施例1 甲基二乙氧基苯并环丁烯基硅烷的制备
Figure PCTCN2014090653-appb-000027
氩气保护下，向500mL干燥三颈瓶中加入镁屑(9.6g,0.4mol)，甲基三乙氧基硅烷(89g,0.5mol)，无水四氢呋喃60mL，室温下慢慢滴加4-溴苯并环丁烯(36.6g,0.2mol)的40mL无水四氢呋喃溶液，滴毕室温搅拌3.5小时后注入100mL无水甲苯，大量的有机盐析出，过滤，旋蒸除去低沸点溶剂后油泵减压蒸馏：收集98-104℃(1.5mmHg)馏分，得无色透明状液体32.75g，收率69％。
氢谱表征1H NMR(CDCl3,400MHz):0.38(s,3H),1.26～1.30(t,6H),3.23(s,4H),3.82～3.88(m,4H),7.11～7.13(d,1H),7.38(s,1H),7.52～7.54(d,2H).
碳谱表征13C NMR(CDCl3,100MHz):3.92,18.44,29.96,30.01,58.53,122.04,127.82,132.46,132.83,145.65,148.27.
实施例2 乙烯基二乙氧基苯并环丁烯基硅烷的制备
Figure PCTCN2014090653-appb-000028
氩气保护下，向500mL干燥三颈瓶中加入镁屑(7.2g,0.3mol)，乙烯基三乙氧基硅烷(45g,0.24mol)，无水四氢呋喃60mL，室温下慢慢滴加4-溴苯并环丁烯(27.2g,0.15mol)的30mL无水四氢呋喃溶液，滴毕，室温搅拌3.5小时后注入100mL无水甲苯，大量的有机盐析出，过滤，旋蒸除去低沸点溶剂后油泵减压蒸馏：收集98-104℃(1.5mmHg)馏分，得无色透明状液体23.4g，收率63％。
1H NMR(CDCl3,400MHz):1.25～1.29(t,6H),3.22(d,4H),3.84～3.89(m,4H),5.92～6.01(m,1H),6.13～6.21(m,2H),7.10～7.12(dd,1H),7.37(s,1H),7.52～7.54(d,2H).
碳谱表征13C NMR(CDCl3,100MHz):18.46,30.02,30.04,58.82,122.05,128.40,131.05,132.53,133.11,136.75,145.67,148.54.
实施例3 预聚体聚甲基苯并环丁烯基硅氧烷的制备
氩气保护下，在反应瓶中加入30克(0.5mol)乙酸，11.8克(0.05mol)由实施例1获得的单体甲基二乙氧基苯并环丁烯基硅烷，回流反应24小时后旋蒸除去低沸点组分，80℃真空干燥5小时获得定量的浅黄色粘稠状产物。GPC表征，数均分子量1000，分子量分布，1.71。
氢谱表征：1H NMR(CDCl3,400MHz):0.22～0.61(m,3H),3.22～3.27(m,4H),6.96～7.58(m,3H).
碳谱表征13C NMR(CDCl3,100MHz):-0.74,29.97,30.01,121.90,127.14,132.00,135.42,145.38,148.03.
通过阿贝折射仪测得，所得聚合物在室温下的折光率为1.56。
实施例4 预聚体聚乙烯基苯并环丁烯基硅氧烷的制备
氩气保护下，在反应瓶中加入30克(0.5mol)乙酸，12.42克(0.05mol)由实施例2获得的单体乙烯基二乙氧基苯并环丁烯基硅烷，回流反应24小时后旋蒸除去低沸点组分，80℃真空干燥5小时获得定量的黄色粘稠状产物。GPC表征，数均分子量1200，分子量分布，1.66。氢谱表征：1H NMR(CDCl3,400MHz):3.13～3.26(m,4H),5.84～6.25(m,3H),6.93～7.63(m,3H),13C NMR(CDCl3,100MHz):30.00,30.02,121.86,127.81,132.56,134.04,135.44,136.54,145.48,148.65。
通过阿贝折射仪测得，所得聚合物在室温下的折光率为1.57。
实施例5 甲基苯并环丁烯基硅氧烷与甲基苯基二甲氧基硅烷共聚物的制备
氩气保护下，在反应瓶中加入6克(0.1mol)乙酸，1.18克(0.005mol)由实施例1获得的单体甲基二乙氧基苯并环丁烯基硅烷，0.91克(0.005mol)甲基苯基二甲氧基硅烷，回流反应24小时后旋蒸除去低沸点组分，80℃真空干燥5小时获得定量的黄色粘稠状产物。GPC表征，数均分子量800，分子量分布，1.5。氢谱表征：1H NMR(CDCl3,400MHz):0.05～0.60(m,6H),3.08～3.27(m,4H),6.88～7.78(m,8H).
实施例6 甲基苯并环丁烯基硅氧烷与二甲基二乙氧基硅烷共聚物的制备
氩气保护下，在反应瓶中加入12克(0.2mol)乙酸，2.36克(0.01mol)由实施例1获得的单体甲基二乙氧基苯并环丁烯基硅烷，1.48克(0.01mol)二甲基二乙氧基硅烷，回流反应24小时后旋蒸除去低沸点组分，80℃真空干燥5小时获得定量的黄色粘稠状产物。GPC表征，数均分子量840，分子量分布，1.53。氢谱表征：1H NMR(CDCl3,400MHz):0.10～0.59(m,9H),3.28～3.30(m,4H),7.08～7.21(m,1H),7.31～7.47(m,1H),7.49～7.68(m,1H).
实施例7 乙烯基苯并环丁烯基硅氧烷与甲基苯基二甲氧基硅烷共聚物的制备
氩气保护下，在反应瓶中加入6克(0.1mol)乙酸，1.24克(0.005mol)由实施例2获得的单体乙烯基二乙氧基苯并环丁烯基硅烷，0.91克(0.005mol)甲基苯基二甲氧基硅烷，回流反应24小时后旋蒸除去低沸点组分，80℃真空干燥5小时获得定量的黄色粘稠状产物。GPC表征，数均分子量780，分子量分布，1.45。氢谱表征：1H NMR(CDCl3,400MHz):0.07～0.62(m,3H),3.08～3.28(m,4H),5.73～6.37(m,3H),6.83～7.78(m,8H).
实施例8 乙烯基苯并环丁烯基硅氧烷与二甲基二乙氧基硅烷共聚物的制备
氩气保护下，在反应瓶中加入12克(0.2mol)乙酸，2.48克(0.01mol)由实施例2获得的单体乙烯基二乙氧基苯并环丁烯基硅烷，1.48克(0.01mol)二甲基二乙氧基硅烷，回流反应24小时后旋蒸除去低沸点组分，80℃真空干燥5小时获得定量的黄色粘稠状产物。GPC表征，数均分子量810，分子量分布，1.48。氢谱表征：1H NMR(CDCl3,400MHz):0.06～0.42(m,6H),3.26～3.29(m,4H),5.84～6.41(m,3H),7.01～7.19(m,1H),7.31～7.47(m,1H),7.48～7.67(m,1H).
实施例9 均聚物的固化及固化产物的耐热性质
将1.5g实施例3所得聚合物置于内径为1cm的平底schlenk管中，升温到250 ℃，并在该温度保持5小时，然后冷至室温，固化物去除，磨细，进行TGA测试。结果表明，固化产物在氮气中5％热失重温度为496℃，1000℃的重量残余为75％。
实施例10 均聚物固化后的介电性质
将1.5g实施例3所得聚合物置于内径为1cm的平底schlenk管中，抽真空并且机械振动下缓慢升温至150℃除去气泡形成致密液体，升温到180℃，并在此温度下保持5h使其预固化。冷至室温后移至石英管式炉以50℃/h速率升温到250℃，并在该温度保持5小时后取出打磨成圆片，测定其介电常数，结果表明，1MHz到30MHz频率范围内，其介电常数介于2.75到2.85之间。
实施例11 共聚物的固化及固化产物的耐热性质
将1.5g实施例5所得聚合物置于内径为1cm的平底schlenk管中，升温到250℃，并在该温度保持5小时，然后冷至室温，固化物去除，磨细，进行TGA测试。结果表明，固化产物在氮气中5％热失重温度为485℃，1000℃的重量残余为73％。
实施例12 共聚物固化后的介电性质
将1.5g实施例3所得聚合物置于内径为1cm的平底schlenk管中，抽真空并且机械振动下缓慢升温至150℃除去气泡形成致密液体，升温到180℃，并在此温度下保持5h使其预固化。冷至室温后移至石英管式炉以50℃/h速率升温到250℃，并在该温度保持5小时后取出打磨成圆片，测定其介电常数，结果表明，1MHz到30MHz频率范围内，其介电常数介于2.72到2.83之间。
在本发明提及的所有文献都在本申请中引用作为参考，就如同每一篇文献被单独引用作为参考那样。此外应理解，在阅读了本发明的上述讲授内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。

Claims (15)

  1. 一种有机硅氧烷，其特征在于，所述有机硅氧烷具有硅氧烷主链，以及具有与硅氧烷主链的硅原子直接相连的苯并环丁烯基。
  2. 如权利要求1所述的有机硅氧烷，其特征在于，所述的硅氧烷主链具有式A结构；
    Figure PCTCN2014090653-appb-100001
    其中，
    x为≥2的正整数(较佳地为2～200)；
    各R独立地选自下组：
    (a)H；
    (b)取代或未取代C1～C6的烷基、取代或未取代C2～C6烯基，其中所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代：卤素、C1～C4的烷基、C2～C4的烯基、C2～C4的炔基、未取代的或苯环上的1～3个氢原子被选自下组的取代基取代的苯基：卤素、C1～C4的烷基；
    (c)取代或未取代的苯基；所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代：卤素、C1～C4的烷基、C1～C4的卤代烷基、C2～C4的烯基、C2～C4的炔基、未取代的苯基；
    (d)苯并环丁烯基；
    并且，至少一个R为苯并环丁烯基。
  3. 如权利要求1所述的有机硅氧烷，其特征在于，所述的有机硅氧烷具有如下式I所示结构：
    Figure PCTCN2014090653-appb-100002
    其中，n为≥2的正整数(较佳地n＝2～100，更佳地n＝2～50，最佳地n＝2～20)；
    各R1独立地选自下组：
    (a)H；
    (b)取代或未取代C1～C6的烷基、取代或未取代C2～C6烯基，其中所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代：卤素、C1～C4的烷基、C2～C4的烯基、C2～C4的炔基、未取代的或苯环上的1～3个氢原子被选自下组的取代基取代的苯基：卤素、C1～C4的烷基；
    (c)取代或未取代的苯基；所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代：卤素、C1～C4的烷基、C1～C4的卤代烷基、C2～C4的烯基、C2～C4的炔基、未取代的苯基。
  4. 如权利要求1所述的有机硅氧烷的制备方法，其特征在于，所述的有机硅氧烷是用如下式II所示的有机硅单体进行水解聚合制备的：
    Figure PCTCN2014090653-appb-100003
    其中，R1为选自下组的基团：
    (a)H；
    (b)取代或未取代C1～C6的烷基、取代或未取代C2～C6烯基，其中所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代：卤素、C1～C4的烷基、C2～C4的烯基、C2～C4的炔基、未取代的或苯环上的1～3个氢原子被选自下组的取代基取代的苯基：卤素、C1～C4的烷基；
    (c)取代或未取代的苯基；所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代：卤素、C1～C4的烷基、C1～C4的卤代烷基、C2～C4的烯基、C2～C4的炔基、未取代的苯基；
    R2、R3各自独立地为选自下组的基团：C1～C4的烷氧基，卤素。
  5. 如权利要求4所述的方法，其特征在于，所述的水解聚合包括步骤：在酸催化剂存在下，用如式II所示的有机硅单体和任选的双烷氧基硅氧烷进行水解，得到如权利要求1所述的有机硅氧烷。
  6. 如权利要求5所述的方法，其特征在于，所述的酸催化剂选自下组：盐酸、硫酸、乙酸、甲酸，或其组合；较佳地，所述的酸催化剂选自下组：乙酸、甲酸，或其组合。
  7. 如权利要求5所述的方法，其特征在于，所述的水解聚合具有选自下组的一个或多个条件：
    在选自下组的溶剂中进行：苯、甲苯、二甲苯，或其组合；
    所述的水解聚合在10～100℃下进行；优选在室温～100℃下进行；
    所述的水解聚合反应时间为5～48h。
  8. 一种如式II所示的有机硅单体：
    Figure PCTCN2014090653-appb-100004
    其中，R1为选自下组的基团：
    (a)H；
    (b)取代或未取代C1～C6的烷基、取代或未取代C2～C6烯基，其中所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代：卤素、C1～C4的烷基、C2～C4的烯基、C2～C4的炔基、未取代的或苯环上的1～3个氢原子被选自下组的取代基取代的苯基：卤素、C1～C4的烷基；
    (c)取代或未取代的苯基；所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代：卤素、C1～C4的烷基、C1～C4的卤代烷基、C2～C4的烯基、C2～C4的炔基、未取代的苯基；
    R2、R3各自独立地为选自下组的基团：C1～C4的烷氧基，卤素。
  9. 如权利要求8所述的单体的制备方法，其特征在于，包括步骤：
    Figure PCTCN2014090653-appb-100005
    在惰性溶剂(如醚类溶剂)中，用卤代苯并环丁烯与
    Figure PCTCN2014090653-appb-100006
    反应，得到式II所示的有机硅单体；
    其中，X为卤素，较佳地选自下组：Cl、Br；
    R1为选自下组的基团：
    (a)H；
    (b)取代或未取代C1～C6的烷基、取代或未取代C2～C6烯基，其中所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代：卤素、C1～C4的烷基、C2～C4的烯基、C2～C4的炔基、未取代的或苯环上的1～3个氢原子被选自下组的取代基取代的苯基：卤素、C1～C4的烷基；
    (c)取代或未取代的苯基；所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代：卤素、C1～C4的烷基、C1～C4的卤代烷基、C2～C4的烯基、C2～C4的炔基、未取代的苯基；
    R2、R3、R4各自独立地为选自下组的基团：C1～C4烷氧基，卤素。
  10. 一种固化方法，其特征在于，包括步骤：对权利要求1所述的有机硅氧烷进行聚合，从而形成固化产物。
  11. 一种固化产物，其特征在于，所述的固化产物是用如权利要求10所述的方法制备的。
  12. 一种制品，其特征在于，所述制品含有如权利要求1所述的式I有机硅氧烷、如权利要求8所述的式II有机硅单体，或如权利要求11所述的固化产物；或
    所述制品是用如权利要求1所述的式I有机硅氧烷、如权利要求8所述的式II有机硅单体，或如权利要求11所述的固化产物制备的。
  13. 如权利要求12所述的制品的制备方法，其特征在于，包括：用如权利要求1所述的式I有机硅氧烷进行成型，得到预成型体，然后对所述的预成型体进行加热固化，得到所述的制品。
  14. 一种交联剂，其特征在于，所述的交联剂含有如权利要求1所述的式I有机硅氧烷。
  15. 一种交联的硅橡胶，其特征在于，所述的硅橡胶为高温硫化硅橡胶，且所述的硅橡胶中含有如权利要求1所述的式I化合物。
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