WO2017107589A1 - 一种有机硅改性的聚苯醚树脂、制备方法及用途 - Google Patents

一种有机硅改性的聚苯醚树脂、制备方法及用途 Download PDF

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WO2017107589A1
WO2017107589A1 PCT/CN2016/099134 CN2016099134W WO2017107589A1 WO 2017107589 A1 WO2017107589 A1 WO 2017107589A1 CN 2016099134 W CN2016099134 W CN 2016099134W WO 2017107589 A1 WO2017107589 A1 WO 2017107589A1
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substituted
resin
unsubstituted
polyphenylene ether
group
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PCT/CN2016/099134
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English (en)
French (fr)
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袁婵娥
罗鸿运
林伟
范华勇
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广东生益科技股份有限公司
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Priority to US16/066,272 priority Critical patent/US20200283575A1/en
Publication of WO2017107589A1 publication Critical patent/WO2017107589A1/zh

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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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • C08G65/485—Polyphenylene oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
    • C—CHEMISTRY; METALLURGY
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    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/246—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using polymer based synthetic fibres
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/308—Heat stability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • 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
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0162—Silicon containing polymer, e.g. silicone
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles

Definitions

  • the invention belongs to the technical field of copper clad laminates, relates to a silicone modified polyphenylene ether resin, a preparation method and application thereof, and further relates to a polyphenylene ether resin containing unsaturated double bond silicone modified, preparation method and use thereof , a preparation method, and a thermosetting resin composition, prepreg, and laminate containing the same.
  • the polyphenylene ether resin has a large amount of benzene ring structure and no strong polar groups, which gives the polyphenylene ether resin excellent properties, such as high glass transition temperature, good dimensional stability, small linear expansion coefficient, and water absorption.
  • the cured product of polyphenylene ether resin with double bond structure has become a preferred resin material for substrates of high-frequency printed circuit boards due to its good mechanical properties and excellent dielectric properties, and it relies on end groups.
  • the double bond and other resins containing double bonds are prepared by free radical reaction or self-curing to prepare a laminate having high glass transition temperature, high heat resistance and high heat and humidity resistance.
  • Silicone has excellent heat resistance, weather resistance, flame retardancy, dielectric properties and low water absorption. Simultaneous introduction of unsaturated double bonds and siloxy groups in the polyphenylene ether resin will further ensure the curing of the resin. Heat resistance, dielectric properties and hydrophobicity of the material.
  • Polyphenylene ether resin having an unsaturated double bond structure has become a preferred resin material for substrates of high frequency printed circuit boards due to its good mechanical properties and excellent dielectric properties.
  • the reactant is washed successively with an aqueous alkali metal hydroxide solution and hydrochloric acid
  • an object of the present invention is to provide a silicone-modified polyphenylene ether resin, a resin composition containing the same, a resin glue liquid, a resin cured product, a prepreg, a copper clad laminate, and a laminate. And printed circuit boards.
  • R 1 is selected or R 2 is H, allyl or isoallyl;
  • R 3 , R 4 and R 5 are each independently selected from a C 1 -C 8 substituted or unsubstituted linear or branched alkyl group, a C 2 -C 8 substituted or unsubstituted linear or branched alkenyl group, a C 5 -C 12 substituted or unsubstituted alicyclic group, a C 6 -C 20 substituted or unsubstituted aryl group or a C 6 -C 20 substituted or unsubstituted aryloxy group, preferably selected from or And at least one of R 3 , R 4 and R 5 is an unsaturated group; R 14 is selected from H, C 1 -C 14 substituted or unsubstituted straight or branched alkyl, C 5 -C 12 substituted or Unsubstituted alicyclic group or C 1 -C 14 alkoxy group.
  • n 1 and n 2 are each independently a positive integer and satisfy 4 ⁇ n 1 + n 2 ⁇ 25, for example, n 1 + n 2 may be 5, 6, 7, 8, 9, 10, 11, 12, 13 14, 15, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, etc.
  • the n 1 , n 2 satisfy 6 ⁇ n 1 +n 2 ⁇ 20, preferably 8 ⁇ n 1 +n 2 ⁇ 15;
  • the polyphenylene ether resin is selected from the group consisting of compounds or n 1 and n 2 in the compound are each independently a positive integer and satisfy 4 ⁇ n 1 + n 2 ⁇ 25, preferably 6 ⁇ n 1 + n 2 ⁇ 20, further preferably 8 ⁇ n 1 + n 2 ⁇ 15.
  • a method for preparing a silicone-modified polyphenylene ether resin according to the present invention wherein R 3 and R 4 are each independently selected from a C 1 -C 8 substituted or unsubstituted linear or branched alkyl group, a C 2 -C 8 substituted or unsubstituted linear or branched alkenyl group, a C 5 -C 12 substituted or unsubstituted alicyclic group or a C 6 -C 20 substituted or unsubstituted aryl group, and R 5 is C When 6 to C 20 are substituted or unsubstituted aryloxy groups, and at least one of R 3 , R 4 and R 5 is an unsaturated group, the method comprises the steps of:
  • R 1 and n have the same meaning as in claim 1 or 2;
  • R 3 , R 4 and R 5 are each independently selected from a C 1 -C 8 substituted or unsubstituted linear or branched alkyl group, a C 2 -C 8 substituted or unsubstituted straight or branched chain
  • the method includes the following steps:
  • R 1 and n have the same meaning as in claim 1 or 2;
  • R 3 and R 4 are each independently selected from -CH 3 , or And R 5 is The method includes the following steps:
  • R 1 , R 14 and n have the same meanings as in claim 1 or 2;
  • R 3 , R 4 and R 5 are each independently selected from -CH 3 , or And when at least one of R 3 , R 4 and R 5 is an unsaturated group, the method comprises the following steps:
  • R 1 and n have the same meaning as in claim 1 or 2;
  • the anhydrous solvent is selected from any one or a mixture of any two of tetrahydrofuran, dichloromethane, acetone or methyl ethyl ketone; the mixture such as a mixture of tetrahydrofuran and dichloromethane, dichloromethane and methyl ethyl ketone a mixture of tetrahydrofuran and methyl ethyl ketone, a mixture of acetone, tetrahydrofuran and methyl ethyl ketone.
  • the first temperature and the second temperature are each independently selected from 0 to 60 ° C; the first reaction time and the second reaction time are each independently preferably from 2 to 24 h, further preferably from 3 to 22 h, particularly preferably. 4 to 20h;
  • the third temperature is selected from 0 to 60 ° C; for example, 2 ° C, 5 ° C, 10 ° C, 15 ° C, 20 ° C, 25 ° C, 30 ° C, 35 ° C, 40 ° C, 45 ° C, 50 ° C, 55 ° C, 58°C, etc.
  • the third reaction time is preferably from 2 to 24 hours, for example, 2h, 3h, 5h, 6h, 7h, 9h, 11h, 13h, 15h, 16h, 17h, 19h, 20h, 22h, 24h, etc., further preferably 3 ⁇ 22h, particularly preferably 4 to 20h.
  • a resin composition containing the silicone-modified polyphenylene ether resin of the present invention is a resin composition containing the silicone-modified polyphenylene ether resin of the present invention.
  • the resin composition may further include a resin having a double bond other than the silicone-modified polyphenylene ether resin of the formula (I) and an initiator, and the reaction is a radical reaction, and the silicone resin in the resin composition
  • the modified polyphenylene ether resin is preferably added in an amount of 10 to 90 parts by weight, and the other resin having a double bond is preferably added in an amount of 10 to 90 parts by weight.
  • the initiator can be added according to actual needs by those skilled in the art.
  • the "resin with double bond other than the silicone-modified polyphenylene ether resin of the formula (I) structure" of the present invention is preferably a polyolefin resin or a silicone resin.
  • the polyolefin resin is preferably any one or a mixture of at least two of a styrene-butadiene copolymer, a polybutadiene or a styrene-butadiene-divinylbenzene copolymer; the styrene - Butadiene copolymer, polybutadiene, styrene-butadiene-divinylbenzene copolymer can be independently modified by amino group, maleic anhydride, epoxy modified, acrylate modified Sex, hydroxyl modified or carboxyl modified.
  • the "resin with double bond other than the silicone-modified polyphenylene ether resin of the formula (I) structure” is selected from Sartomer's styrene-butadiene copolymer R100, Japan's Soda Polybutadiene B-1000 or Sartomer styrene-butadiene-divinylbenzene copolymer R250.
  • the silicone resin is selected from any one of the following organosilicon compound structures containing an unsaturated double bond:
  • the silicone resin is selected from any one of the following organosilicon compound structures containing an unsaturated double bond:
  • R 9 is selected from a substituted or unsubstituted C 1 -C 12 linear alkyl group or a substituted or unsubstituted C 1 -C 12 branched alkyl group; 2 ⁇ p ⁇ 10, and p is a natural number.
  • the initiator free radical initiator is selected from the group consisting of organic peroxide initiators.
  • the organic peroxide of the present invention is selected from the group consisting of di-tert-butyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, cumene peroxy neodecanoate, and tertiary oxidized neodecanoate.
  • the resin composition may further comprise a hydrosilycol resin and a hydrosilylation catalyst, and the reaction is a hydrosilylation reaction, and the amount of the silicone-modified polyphenylene ether resin in the resin composition and the amount of the hydrosilycol resin are added according to Calculated by the equivalent of the silicon hydrogen bond and the double bond, the hydrosilylation catalyst can be added according to actual needs by those skilled in the art.
  • the silicon hydride resin of the present invention is selected from any one selected from the group consisting of the following silicon compound structures containing silicon hydrogen bonds:
  • R 10 , R 11 and R 12 are each independently selected from substituted or unsubstituted C1-C8 linear alkyl, substituted or unsubstituted C 1 -C 8 branched alkyl, substituted or unsubstituted phenyl or Substituting or H atom; and at least one of R 10 , R 11 and R 12 is H atom; 0 ⁇ x ⁇ 100;
  • the silicon hydride resin of the present invention is selected from any one selected from the group consisting of the following silicon compound structures containing silicon hydrogen bonds:
  • R 13 is selected from a substituted or unsubstituted C 1 -C 12 linear alkyl group or a substituted or unsubstituted C 1 -C 12 branched alkyl group; 2 ⁇ y ⁇ 10, and y is a natural number.
  • the hydrosilylation catalyst of the present invention is a platinum catalyst.
  • the resin composition may further include an inorganic filler or/and a flame retardant, which can be added by a person skilled in the art according to actual needs.
  • an inorganic filler or/and a flame retardant which can be added by a person skilled in the art according to actual needs.
  • the inorganic filler of the present invention is selected from the group consisting of aluminum hydroxide, boehmite, silica, talc, mica, Any one or a mixture of at least two of barium sulfate, lithopone, calcium carbonate, wollastonite, kaolin, brucite, diatomaceous earth, bentonite, or pumice powder.
  • the flame retardant of the present invention is selected from any one or a combination of at least two of a halogen flame retardant, a phosphorus flame retardant or an inorganic flame retardant.
  • the halogen-free flame retardant is tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphine- 10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene, 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenan-10-oxidation Any one or a mixture of at least two of a substance, a phenoxyphosphazene compound, a zinc borate, a nitrogen-phosphorus expanded type, an organic polymer flame retardant, a phosphorus-containing phenol resin or a phosphorus-containing bismaleimide.
  • the modified polyphenylene ether resin, other doubles may be blended, stirred, and mixed by a known method.
  • the resin of the bond, the silicone hydrogen resin, the initiator, the hydrosilylation catalyst, the filler, and the like are prepared by stirring.
  • a resin glue obtained by dissolving or dispersing the resin composition in a solvent obtained by dissolving or dispersing the resin composition in a solvent.
  • the solvent may be exemplified by ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol-methyl ether, carbitol, butyl carbitol, acetone, methyl ethyl ketone, methyl ethyl ketone.
  • ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol-methyl ether, carbitol, butyl carbitol, acetone, methyl ethyl ketone, methyl ethyl ketone.
  • ketones such as methyl isobutyl ketone and cyclohexanone
  • aromatic hydrocarbons such as toluene, xylene, and mesitylene
  • esters such as ethoxyethyl acetate and ethyl acetate
  • N, N-II A nitrogen-containing solvent such as methylformamide, N,N-dimethylacetamide or N-methyl-2-pyrrolidone.
  • the solvent may be used singly or in combination of two or more kinds, and is preferably an aromatic hydrocarbon solvent such as toluene or xylene with acetone, methyl ethyl ketone, methyl ethyl ketone or methyl isobutyl ketone.
  • a ketone flux such as cyclohexanone is used in combination.
  • the amount of the solvent to be used can be selected by a person skilled in the art according to his own experience, so that the obtained resin glue can reach a viscosity suitable
  • an emulsifier may be added for dispersion, and the inorganic filler or the like may be uniformly dispersed in the glue.
  • a cured resin obtained by curing the resin composition is a cured resin obtained by curing the resin composition.
  • a prepreg comprising a reinforcing material and the resin composition adhered thereto by dipping and drying.
  • Exemplary of the reinforcing material may be carbon fiber, glass fiber cloth, aramid fiber or nonwoven fabric.
  • the carbon fibers are, for example, T300, T700, T800 of Toray Industries, Japan, and the aramid fibers such as Kevlar fibers, such as 7628 fiberglass cloth and 2116 fiberglass cloth.
  • a copper clad laminate comprising at least one of said prepregs.
  • a laminate comprising at least one of said prepregs.
  • a printed circuit board comprising at least one of said prepregs.
  • the present invention has the following beneficial effects:
  • the dielectric properties and low water absorption rate can greatly exert the application of polyphenylene ether resin in copper clad laminates, and can provide excellent dielectric properties, heat and humidity resistance and heat resistance required for high-frequency high-speed copper clad laminates;
  • Figure 1 shows the NMR spectrum of the modified resin d: 1H NMR (DMSO-d6, ppm) NMR spectrum: 0.029 ppm is the chemical shift of the methyl H atom on Si, 0.313 and 1.74 ppm is the methyl group on the tertiary carbon The chemical shift of the H atom, 2.117 ppm is the chemical shift of the methyl H atom on the benzene ring, 5.80-6.24 ppm is the chemical shift of the H atom on the silicon vinyl group, and 6.49-7.29 ppm is the chemical shift of the H atom on the benzene ring.
  • DMSO-d6, ppm 1H NMR (DMSO-d6, ppm) NMR spectrum: 0.029 ppm is the chemical shift of the methyl H atom on Si, 0.313 and 1.74 ppm is the methyl group on the tertiary carbon The chemical shift of the H atom, 2.117 ppm is the chemical shift of the methyl H atom
  • Sheet-like cured product With respect to the obtained cured product, the dielectric constant and the dielectric loss factor at 23 ° C and 1 GHz were measured by a plate capacitance method. The 5% weight loss temperature (Td 5%) under a nitrogen atmosphere was evaluated by TGA at a temperature increase rate of 10 ° C / min. The glass transition temperature was tested using DMA. The performance test results are shown in Table 1.
  • Sheet-like cured product With respect to the obtained cured product, the dielectric constant and the dielectric loss factor at 23 ° C and 1 GHz were measured by a plate capacitance method. The 5% weight loss temperature (Td 5%) under a nitrogen atmosphere was evaluated by TGA at a temperature increase rate of 10 ° C / min. The glass transition temperature was tested using DMA. The performance test results are shown in Table 1.
  • the dielectric constant and the dielectric loss factor at 23 ° C and 1 GHz were measured by a plate capacitance method.
  • the 5% weight loss temperature (Td 5%) under a nitrogen atmosphere was evaluated by TGA at a temperature increase rate of 10 ° C / min.
  • the glass transition temperature was tested using DMA. The performance test results are shown in Table 1.
  • the dielectric constant and the dielectric loss factor at 23 ° C and 1 GHz were measured by a plate capacitance method.
  • the 5% weight loss temperature (Td 5%) under a nitrogen atmosphere was evaluated by TGA at a temperature increase rate of 10 ° C / min.
  • the glass transition temperature was tested using DMA. The performance test results are shown in Table 1.
  • the processed gum solution was poured into molds, left for 2 hours at 120 deg.] C, after forming the mold in the vacuum lamination press cured 90min, curable pressure of 32kg / cm 2, the curing temperature 200 °C, to give a thickness of 0.5-2.0mm Sheet-like cured product.
  • the dielectric constant and the dielectric loss factor at 23 ° C and 1 GHz were measured by a plate capacitance method.
  • the 5% weight loss temperature (Td 5%) in a nitrogen atmosphere was evaluated by TGA at a heating rate of 10 ° C / min.
  • the glass transition temperature was tested using DMA.
  • the performance test results are shown in Table 1.
  • the dielectric constant and the dielectric loss factor at 23 ° C and 1 GHz were measured by a plate capacitance method.
  • the 5% weight loss temperature (Td 5%) under a nitrogen atmosphere was evaluated by TGA at a temperature increase rate of 10 ° C / min.
  • the glass transition temperature was tested using DMA. The performance test results are shown in Table 1.
  • the dielectric constant and the dielectric loss factor at 23 ° C and 1 GHz were measured by a plate capacitance method.
  • the 5% weight loss temperature (Td 5%) under a nitrogen atmosphere was evaluated by TGA at a temperature increase rate of 10 ° C / min.
  • the glass transition temperature was tested using DMA. The performance test results are shown in Table 1.
  • 77 parts by weight of methacrylate phenyl ether resin MX9000, 20 parts by weight of styrene-butadiene copolymer Ricon 100, and 3 parts by weight of dicumyl peroxide (DCP) are dissolved in an appropriate amount of methyl ethyl ketone solvent and adjusted to a suitable viscosity. Stir well. The gas was evacuated under vacuum for a period of time to remove bubbles and butanone from the gum system.
  • the processed gum solution was poured into molds, left for 2 hours at 120 deg.] C, after forming the mold in the vacuum lamination press cured 90min, curable pressure of 32kg / cm 2, the curing temperature 200 °C, to give a thickness of 0.5-2.0mm Sheet-like cured product.
  • the dielectric constant and the dielectric loss factor at 23 ° C and 1 GHz were measured by a plate capacitance method.
  • the 5% weight loss temperature (Td 5%) under a nitrogen atmosphere was evaluated by TGA at a temperature increase rate of 10 ° C / min.
  • the glass transition temperature was tested using DMA.
  • the performance test results are shown in Table 1.
  • Phenol formaldehyde linear phenolic resin 2812, South Korea Momentive.
  • Dicyclopentadiene type phenolic resin 9110, Changchun, Taiwan.
  • Biphenyl type phenolic resin 7851-H, Japan Minghe.
  • Methacrylate-based polyphenylene ether resin MX9000, Sabic.
  • Styrene-butadiene copolymer Ricon 100, Satomer.
  • Phenylsilicone resin SH303, Runhe Chemical.
  • Vinyl phenyl silicone resin SP606, Runhe Chemical.
  • test criteria or methods for the parameters involved in Table 1 are as follows:
  • Glass transition temperature (Tg) measured by DMA test according to the DMA test method specified in IPC-TM-650 2.4.24.4;
  • Td 5% Thermal decomposition temperature
  • Application Examples 1 and 2 show that the resin composition containing the unsaturated double bond silicone-modified polyphenylene ether resin synthesized by the present invention is cured as compared with a general vinyl phenyl silicone resin (using Comparative Example 1). The material has more excellent dielectric properties and a higher glass transition temperature.
  • Application Examples 3-5 indicate the present invention
  • the unsaturated double-bonded silicone-modified polyphenylene ether resin synthesized by Mingming also has better dielectric properties and higher dielectric properties than methacrylate-based polyphenylene ether resin (using Comparative Examples 2 and 3). Glass transition temperature and has a higher thermal decomposition temperature. Therefore, the silicone-modified polyphenylene ether resin containing an unsaturated double bond is a resin having superior comprehensive properties, and can be used for preparation of a high-frequency circuit substrate, and has great application value.

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Abstract

一种含有不饱和双键有机硅改性的聚苯醚树脂，以及含有该树脂的热固性树脂组合物、预浸料和层压板。该树脂把C＝C双键和硅氧基引入到聚苯醚端基中，同时结合了双键固化的低介电性和硅氧基的耐热性、耐候性、阻燃性、介电性能及低吸水率的优点。该树脂能够为高频高速覆铜板提供其所需的优良的介电性能、耐湿热性、耐热性。

Description

一种有机硅改性的聚苯醚树脂、制备方法及用途 技术领域
本发明属于覆铜板技术领域，涉及一种有机硅改性的聚苯醚树脂、制备方法及用途，进一步涉及一种含有不饱和双键有机硅改性的聚苯醚树脂、制备方法及其用途、制备方法及含有其的热固性树脂组合物、预浸料和层压板。
背景技术
随着近年来的信息通讯量的增加，高频印刷电路板的需求越来越高。为了减少高频带的传输损耗，电气特性优异的电气绝缘材成为覆铜板领域的研究重点。同时，使用这些电气绝缘材料的印刷基板或者电子零件为了在安装时能够应对高温的回流焊以及高多层组装，又需要材料具有高耐热性高玻璃化转变温度。聚苯醚树脂分子结构中含有大量的苯环结构，且无强极性基团，赋予了聚苯醚树脂优异的性能，如玻璃化转变温度高、尺寸稳定性好、线性膨胀系数小、吸水率低，尤其是出色的低介电常数、低介电损耗。在高频高速领域，具有双键结构的聚苯醚树脂的固化物由于具有良好的机械特性与优异介电性能，越来越成为高频印刷电路板的基板首选的树脂材料，其依靠端基的双键与其他含有双键的树脂通过自由基反应或自固化来制备层压板，具有高玻璃化转变温度，高耐热性，高耐湿热性的特点。
硅氧烷具有优异的耐热性、耐候性、阻燃性、介电性能及低吸水率，在聚苯醚树脂中同时引入不饱和双键和硅氧基团将进一步保证含有其树脂的固化物的耐热性、介电性及疏水性。
具有不饱和双键结构的聚苯醚树脂由于具有良好的机械特性与优异介电性能，越来越成为高频印刷电路板的基板首选的树脂材料。目前链端带有C＝C双 键聚苯醚树脂的方法，如公知的把链端带有羟基的聚苯醚树脂与烯基酰氯单体反应，生成烯基酸酯-聚苯醚化合物(SABIC，商品MX-9000)；或如CN104072751A所述在碱金属氢氧化物水溶液的存在下，在包括芳香烃和脂肪醇的溶剂中，使得末端具有酚性羟基的聚苯醚与乙烯基苄基卤化物在相转移催化剂的存在下反应，把反应物先后经过碱金属氢氧化物水溶液和盐酸洗涤后，得到乙烯基苄基-聚苯醚化合物。
本领域需要开发一种低介电、耐热性、耐候性、阻燃性、介电性能及低吸水率的聚苯醚树脂。
发明内容
针对现有技术存在的问题，本发明的目的在于提供一种有机硅改性的聚苯醚树脂、包含其的树脂组合物、树脂胶液、树脂固化物、预浸料、覆铜板、层压板和印制电路板。
本发明通过如下技术方案实现所述发明目的：
一种有机硅改性的聚苯醚树脂，所述聚苯醚树脂具有式(I)的结构：
Figure PCTCN2016099134-appb-000001
其中，R1选
Figure PCTCN2016099134-appb-000002
或
Figure PCTCN2016099134-appb-000003
R2为H、烯丙基或异烯丙基；
R3、R4和R5均各自独立地选自C1～C8取代或未取代的直链或支链烷基、C2～C8取代或未取代的直链或支链烯基、C5～C12取代或未取代的脂环基、C6～C20取代或未取代的芳香基或C6～C20的取代或未取代的芳氧基，优选地选自
Figure PCTCN2016099134-appb-000004
Figure PCTCN2016099134-appb-000005
或
Figure PCTCN2016099134-appb-000006
且R3、R4和R5中至少有一个为不饱和基团；R14选自H、C1～C14取代或未取代的直链或支链烷基、C5～C12取代或未取代的脂环基或C1～C14的烷氧基。
n1、n2均各自独立地为正整数，且满足4≤n1+n2≤25，例如n1+n2可以为5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23、24等。
优选地，所述n1、n2满足6≤n1+n2≤20，优选8≤n1+n2≤15；
优选地，所述聚苯醚树脂选自化合物
Figure PCTCN2016099134-appb-000007
Figure PCTCN2016099134-appb-000008
或
Figure PCTCN2016099134-appb-000009
所述化合物中的n1、n2均各自独立地为正整数，且满足4≤n1+n2≤25，优选6≤n1+n2≤20，进一步优选8≤n1+n2≤15。
一种本发明所述的有机硅改性的聚苯醚树脂的制备方法，当R3和R4均各自独立地选自C1～C8取代或未取代的直链或支链烷基、C2～C8取代或未取代的直链或支链烯基、C5～C12取代或未取代的脂环基或C6～C20取代或未取代的芳香基，且R5为C6～C20的取代或未取代的芳氧基，且R3、R4和R5中至少有一个为不饱和基团时，所述方法包括如下步骤：
(1)在无水溶剂中，使具有式(II)的二氯硅烷单体与具有式(III)结构的聚苯醚树脂混合，升温至第一温度进行第一反应；
(2)向反应体系中加入单官能酚类单体H-R5，升温至第二温度继续进行第二反应，得到式(I)结构的聚苯醚树脂；
Figure PCTCN2016099134-appb-000010
Figure PCTCN2016099134-appb-000011
其中，R1和n具有与权利要求1或2相同的意义；
或者，当R3、R4和R5均各自独立地选自C1～C8取代或未取代的直链或支链烷基、C2～C8取代或未取代的直链或支链烯基、C5～C12取代或未取代的脂环基或C6～C20取代或未取代的芳香基，且R3、R4和R5中至少有一个为不饱和基团时，所述方法包括如下步骤：
(a)在无水溶剂中，使具有式(IV)结构的一氯硅烷单体与具有式(III)结构的聚苯醚树脂混合，升温至第三温度进行第三反应，得到式(I)结构的酚醛树脂；
Figure PCTCN2016099134-appb-000012
其中，R1和n具有与权利要求1或2相同的意义；
优选地，当R3和R4各自独立地选自
Figure PCTCN2016099134-appb-000013
-CH3、
Figure PCTCN2016099134-appb-000014
或
Figure PCTCN2016099134-appb-000015
且R5为
Figure PCTCN2016099134-appb-000016
时，所述方法包括如下步骤：
(1)在无水溶剂中，使具有式(II)的二氯硅烷单体与具有式(III)结构的聚苯醚树脂混合，升温至第一温度进行第一反应；
(2)向反应体系中加入单官能酚类单体H-R5，升温至第二温度继续进行 第二反应，得到式(I)结构的聚苯醚树脂；
Figure PCTCN2016099134-appb-000017
Figure PCTCN2016099134-appb-000018
其中，R1、R14和n具有与权利要求1或2相同的意义；
或者，当R3、R4和R5均各自独立地选自
Figure PCTCN2016099134-appb-000019
-CH3、
Figure PCTCN2016099134-appb-000020
Figure PCTCN2016099134-appb-000021
或
Figure PCTCN2016099134-appb-000022
且R3、R4和R5中至少有一个为不饱和基团时，所述方法包括如下步骤：
(a)在无水溶剂中，使具有式(IV)结构的一氯硅烷单体与具有式(III)结构的聚苯醚树脂混合，升温至第三温度进行第三反应，得到式(I)结构的酚醛树脂；
Figure PCTCN2016099134-appb-000023
其中，R1和n具有与权利要求1或2相同的意义；
优选地，所述无水溶剂选自四氢呋喃、二氯甲烷、丙酮或丁酮中的任意1种或者任意2种的混合物；所述混合物例如四氢呋喃和二氯甲烷的混合物，二氯甲烷和丁酮的混合物，四氢呋喃和丁酮的混合物，丙酮、四氢呋喃和丁酮的混合物。
优选地，所述第一温度和第二温度均各自独立地选自0～60℃；第一反应时间和第二反应时间均各自独立地优选自2～24h，进一步优选3～22h，特别优选 4～20h；
优选地，第三温度选自0～60℃；例如2℃、5℃、10℃、15℃、20℃、25℃、30℃、35℃、40℃、45℃、50℃、55℃、58℃等，第三反应时间优选自2～24h，例如2h、3h、5h、6h、7h、9h、11h、13h、15h、16h、17h、19h、20h、22h、24h等，进一步优选3～22h，特别优选4～20h。
一种树脂组合物，所述树脂组合物含有本发明所述的有机硅改性的聚苯醚树脂。
所述树脂组合物还可以包括除式(I)结构的有机硅改性聚苯醚树脂以外的其它带有双键的树脂和引发剂，反应为自由基反应，所述树脂组合物中有机硅改性的聚苯醚树脂填加量优选为10-90重量份，其它带有双键的树脂填加量优选为10-90重量份，引发剂本领域技术人员可以根据实际需求添加。
本发明所述“除式(I)结构的有机硅改性聚苯醚树脂以外的其它带有双键的树脂”优选聚烯烃树脂或有机硅树脂。
所述聚烯烃树脂优选自苯乙烯-丁二烯共聚物、聚丁二烯或苯乙烯-丁二烯-二乙烯基苯共聚物中的任意1种或者至少2种的混合物；所述苯乙烯-丁二烯共聚物、聚丁二烯、苯乙烯-丁二烯-二乙烯基苯共聚物均可各自独立地被氨基改性、马来酸酐改性、环氧基改性、丙烯酸酯改性、羟基改性或羧基改性。
示例性地，所述“除式(I)结构的有机硅改性聚苯醚树脂以外的其它带有双键的树脂”选自Sartomer的苯乙烯-丁二烯共聚物R100、日本曹达的聚丁二烯B-1000或Sartomer的苯乙烯-丁二烯-二乙烯基苯共聚物R250。
作为本发明的一个具体实施方式，所述有机硅树脂选自如下含有不饱和双键的有机硅化合物结构中的任意一种：
Figure PCTCN2016099134-appb-000024
R6、R7和R8均独立地选自取代或未取代的C1～C8的直链烷基、取代或未取代的C1～C8支链烷基、取代或未取代的苯基或取代或未取代的C2～C10含C＝C的基团；且R6、R7和R8三者至少有一个为取代或未取代的C2～C10含C＝C的基团；0≤m≤100。
作为本发明的另一个具体实施方式，所述有机硅树脂选自如下含有不饱和双键的有机硅化合物结构中的任意一种：
Figure PCTCN2016099134-appb-000025
R9选自取代或未取代的C1～C12直链烷基或取代或未取代的C1～C12支链烷基；2≤p≤10，且p为自然数。
所述引发剂自由基引发剂，选自有机过氧化物引发剂。
优选地，本发明所述有机过氧化物选自二叔丁基过氧化物、过氧化二月桂酰、过氧化二苯甲酰、过氧化新癸酸异丙苯酯、过氧化新癸酸叔丁酯、过氧化特戊酸特戊酯、过氧化特戊酸叔丁酯、叔丁基过氧化异丁酸酯、叔丁基过氧化-3，5，5-三甲基己酸酯、过氧化乙酸叔丁酯、过氧化苯甲酸叔丁酯、1，1-二叔丁基过氧化-3，5，5-三甲基环己烷、1，1-二叔丁基过氧化环己烷、2，2-二(叔丁基过氧化)丁烷、双(4-叔丁基环己基)过氧化二碳酸酯、过氧化二碳酸酯十六酯、过氧化二碳酸酯十四酯、二特戊己过氧化物、二异丙苯过氧化物、双(叔丁基过氧化异丙基)苯、2，5-二甲基-2，5-二叔丁基过氧化己烷、2，5-二甲基-2，5-二叔丁基过氧化己炔、二异丙苯过氧化氢、异丙苯过氧化氢、特戊基过氧化氢、叔丁基过氧化氢、叔丁基过氧化异丙苯、二异丙苯过氧化氢、过氧化碳酸酯-2-乙基己酸叔丁酯、 叔丁基过氧化碳酸-2-乙基己酯、4，4-二(叔丁基过氧化)戊酸正丁酯、过氧化甲乙酮、过氧化环己烷中的任意一种或者至少两种的混合物。
所述树脂组合物还可以包括硅氢树脂和硅氢加成催化剂，反应为硅氢加成反应，树脂组合物中有机硅改性的聚苯醚树脂填加量与硅氢树脂填加量根据硅氢键和双键的当量来计算，硅氢加成催化剂本领域技术人员可以根据实际需求添加。
作为本发明的一个具体实施方式，本发明所述硅氢树脂选自选自如下含有硅氢键的有机硅化合物结构中的任意1种：
Figure PCTCN2016099134-appb-000026
R10、R11和R12均独立地选自取代或未取代的C1-C8的直链烷基、取代或未取代的C1～C8支链烷基、取代或未取代的苯基或取代或H原子；且R10、R11和R12三者至少有一个为H原子；0≤x≤100；
作为本发明的另一个具体实施方式，本发明所述硅氢树脂选自选自如下含有硅氢键的有机硅化合物结构中的任意1种：
Figure PCTCN2016099134-appb-000027
R13选自取代或未取代的C1～C12直链烷基或取代或未取代的C1～C12支链烷基；2≤y≤10，且y为自然数。
本发明所述硅氢加成催化剂为铂金催化剂。
优选地，所述树脂组合物还可以包括无机填料或/和阻燃剂，本领域技术人员可以根据实际需求添加。
本发明所述无机填料选自氢氧化铝、勃姆石、二氧化硅、滑石粉、云母、 硫酸钡、立德粉、碳酸钙、硅灰石、高岭土、水镁石、硅藻土、膨润土、或浮石粉中的任意一种或者至少两种的混合物。
本发明述阻燃剂选自卤系阻燃剂、磷系阻燃剂或无机阻燃剂中的任意一种或至少两种的组合。无卤阻燃剂为三(2，6-二甲基苯基)膦、10-(2，5-二羟基苯基)-9，10-二氢-9-氧杂-10-膦菲-10-氧化物、2，6-二(2，6-二甲基苯基)膦基苯、10-苯基-9，10-二氢-9-氧杂-10-膦菲-10-氧化物、苯氧基膦腈化合物、硼酸锌、氮磷系膨胀型、有机聚合物阻燃剂、含磷酚醛树脂或含磷双马来酰亚胺中的任意1种或者至少2种的混合物。
作为本发明所述不饱和双键有机硅改性的聚苯醚树脂组合物之一的制备方法，可以通过公知的方法配合、搅拌、混合所述的改性聚苯醚树脂、其他带有双键的树脂、硅氢树脂、引发剂、硅氢加成催化剂、填料等进行搅拌制备得到。
一种树脂胶液，所述树脂胶液为所述的树脂组合物溶解或分散在溶剂中得到。
示例性地，所述溶剂可以列举为乙基溶纤剂、丁基溶纤剂、乙二醇-甲醚、卡必醇、丁基卡必醇等醚类，丙酮、丁酮、甲基乙基酮、甲基异丁基酮、环己酮等酮类，甲苯、二甲苯、均三甲苯等芳香族烃类，乙氧基乙基乙酸酯、醋酸乙酯等酯类，N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、N-甲基-2-吡咯烷酮等含氮类溶剂。所述溶剂可以单独使用一种，也可以两种或者两种以上混合使用，优选甲苯、二甲苯等芳香族烃类溶剂与丙酮、丁酮、甲基乙基甲酮、甲基异丁基甲酮、环己酮等酮类熔剂混合使用。所述溶剂的使用量本领域技术人员可以根据自己的经验来选择，使得到的树脂胶液达到适于使用的粘度即可。
在所述的树脂组合物溶解或分散在溶剂的过程中，可以添加乳化剂，用以进行分散，可以使无机填料等在胶液中分散均匀。
一种树脂固化物，所述树脂固化物通过固化所述的树脂组合物得到。
一种预浸料，所述预浸料包括增强材料，及通过浸渍干燥后附着在其上的所述的树脂组合物。
所述增强材料示例性的可以是碳纤维、玻璃纤维布、芳族聚酰胺纤维或无纺布。
所述碳纤维例如有日本东丽公司的T300、T700、T800，所述芳香族聚酰胺纤维如Kevlar纤维，所述玻璃纤维布示例性的如：7628玻纤布、2116玻纤布。
一种覆铜板，所述覆铜板含有至少一张所述的预浸料。
一种层压板，所述层压板含有至少一张所述的预浸料。
一种印制电路板，所述印制电路板含有至少一张所述的预浸料。
与现有技术相比，本发明具有以下有益效果：
(1)本发明把C＝C双键和硅氧基引入到聚苯醚端基中，同时结合了双键固化的低介电和硅氧基的耐热性、耐候性、阻燃性、介电性能及低吸水率，更大地发挥聚苯醚树脂在覆铜板中的应用，能够提供高频高速覆铜板所需的优良的介电性能、耐湿热性、耐热性；
(2)本发明提供的有机硅改性的聚苯醚树脂的制备方法简单便捷，提纯容易。
附图说明
图1为制备实施例4提供的酸酐树脂d的核磁谱图。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。
本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
制备实施例1
将74重量份聚苯醚树脂MX90与1000mL无水四氢呋喃于装有搅拌器、滴液漏斗、温度计和导气管(通氮气)的反应釜中搅拌直至完全溶解成均匀的溶液，持续通氮气0.5～1小时除去反应釜中的水汽，并且整个反应过程中都保持通氮气。使反应釜内温度保持20℃以下，然后缓慢滴加17重量份二烯丙基二氯硅烷。滴加完毕后反应釜内保持20℃以下反应5～10小时，接着把温度升高到40～60℃反应10～22小时。随后滴加9重量份的苯酚于反应釜中，40～60℃下反应10～22小时。反应结束后通过减压蒸馏除去四氢呋喃，得到含有不饱和双键有机硅改性的聚苯醚树脂(改性树脂a)。
制备实施例2
将77重量份聚苯醚树脂MX90与1000mL无水四氢呋喃于装有搅拌器、滴液漏斗、温度计和导气管(通氮气)的反应釜中搅拌直至完全溶解成均匀的溶液，持续通氮气0.5～1小时除去反应釜中的水汽，并且整个反应过程中都保持通氮气。同时使反应釜内温度保持20℃以下，然后缓慢滴加14重量份甲基乙烯基二氯硅烷。滴加完毕后反应釜内保持20℃以下反应5～10小时，接着把温度升高到40～60℃反应10～22小时。随后滴加9重量份的苯酚于反应釜中，40～60℃下反应10～22小时。反应结束后通过减压蒸馏除去四氢呋喃，得到含有不饱和双键有机硅改性的聚苯醚树脂(改性树脂b)。
制备实施例3
将81重量份聚苯醚树脂MX90与1000mL无水四氢呋喃于装有搅拌器、滴液漏斗、温度计和导气管(通氮气)的反应釜中搅拌直至完全溶解成均匀的溶液， 持续通氮气0.5～1小时除去反应釜中的水汽，并且整个反应过程中都保持通氮气。同时使反应釜内温度保持20℃以下，然后缓慢滴加19重量份甲基苯基乙烯基一氯硅烷。滴加完毕后反应釜内保持20℃以下反应5～10小时，接着把温度升高到40～60℃反应10～22小时。反应结束后通过减压蒸馏除去四氢呋喃，得到含有不饱和双键有机硅改性的聚苯醚树脂(改性树脂c)。
制备实施例4
将83重量份聚苯醚树脂MX90与1000mL无水四氢呋喃于装有搅拌器、滴液漏斗、温度计和导气管(通氮气)的反应釜中搅拌直至完全溶解成均匀的溶液，持续通氮气0.5～1小时除去反应釜中的水汽，并且整个反应过程中都保持通氮气。同时使反应釜内温度保持20℃以下，然后缓慢滴加17重量份二甲基乙烯基一氯硅烷。滴加完毕后反应釜内保持20℃以下反应5-10小时，接着把温度升高到40-60℃反应10-22小时。反应结束后通过减压蒸馏除去四氢呋喃，得到含有不饱和双键有机硅改性的聚苯醚树脂(改性树脂d)。
图1给出了改性树脂d的核磁谱图：1H NMR(DMSO-d6，ppm)核磁图谱为：0.029ppm为Si上甲基H原子的化学位移，0.313和1.74ppm为叔碳上甲基H原子的化学位移，2.117ppm为苯环上甲基H原子的化学位移，5.80-6.24ppm为硅乙烯基上H原子的化学位移，6.49-7.29ppm为苯环上H原子的化学位移。
应用实施例1
将78重量份的实施例1中所制备的烯基有机硅改性的聚苯醚树脂(改性树脂a)、22重量份的苯基硅氢树脂SH303溶解于适量丁酮溶剂中，并调节至适合粘度。加入总计10ppm的铂金催化剂，搅拌均匀。在真空下抽气一段时间以除去 胶液体系中的气泡和丁酮。把处理完毕的胶液倒入模具中，50℃下放置1小时，成型后把模具在压机中真空层压固化90min，固化压力32kg/cm2，固化温度200℃，得到0.5～2.0mm厚的片状固化物。对于所得到的固化物，利用平板电容法测定23℃、1GHz的介电常数和介电损耗因数。利用TGA在10℃/min的升温速度下评价氮气气氛下的5％重量减少温度(Td5％)。利用DMA测试其玻璃化转变温度。性能测试结果示于表1。
应用实施例2
将77重量份的实施例3中所制备的烯基有机硅改性的聚苯醚树脂(改性树脂c)、23重量份的苯基硅氢树脂SH303溶解于适量丁酮溶剂中，并调节至适合粘度。加入总计10ppm的铂金催化剂，搅拌均匀。在真空下抽气一段时间以除去胶液体系中的气泡和丁酮。把处理完毕的胶液倒入模具中，50℃下放置1小时，成型后把模具在压机中真空层压固化90min，固化压力32kg/cm2，固化温度200℃，得到0.5～2.0mm厚的片状固化物。对于所得到的固化物，利用平板电容法测定23℃、1GHz的介电常数和介电损耗因数。利用TGA在10℃/min的升温速度下评价氮气气氛下的5％重量减少温度(Td5％)。利用DMA测试其玻璃化转变温度。性能测试结果示于表1。
应用实施例3
将99重量份的实施例2中所制备的烯基有机硅改性的聚苯醚树脂(改性树脂b)、3重量份的过氧化二异丙苯(DCP)溶解于适量丁酮溶剂中，并调节至适合粘度，搅拌均匀。在真空下抽气一段时间以除去胶液体系中的气泡和丁酮。把处理完毕的胶液倒入模具中，120℃下放置2小时，成型后把模具在压机中真 空层压固化90min，固化压力32kg/cm2，固化温度200℃，得到0.5-2.0mm厚的片状固化物。对于所得到的固化物，利用平板电容法测定23℃、1GHz的介电常数和介电损耗因数。利用TGA在10℃/min的升温速度下评价氮气气氛下的5％重量减少温度(Td5％)。利用DMA测试其玻璃化转变温度。性能测试结果示于表1。
应用实施例4
将99重量份的实施例4中所制备的烯基有机硅改性的聚苯醚树脂(改性树脂d)、3重量份的过氧化二异丙苯(DCP)溶解于适量丁酮溶剂中，并调节至适合粘度，搅拌均匀。在真空下抽气一段时间以除去胶液体系中的气泡和丁酮。把处理完毕的胶液倒入模具中，120℃下放置2小时，成型后把模具在压机中真空层压固化90min，固化压力32kg/cm2，固化温度200℃，得到0.5-2.0mm厚的片状固化物。对于所得到的固化物，利用平板电容法测定23℃、1GHz的介电常数和介电损耗因数。利用TGA在10℃/min的升温速度下评价氮气气氛下的5％重量减少温度(Td5％)。利用DMA测试其玻璃化转变温度。性能测试结果示于表1。
应用实施例5
将77重量份的实施例4中所制备的烯基有机硅改性的聚苯醚树脂(改性树脂d)、20重量份丁苯共聚物Ricon100、3重量份的过氧化二异丙苯(DCP)溶解于适量丁酮溶剂中，并调节至适合粘度，搅拌均匀。在真空下抽气一段时间以除去胶液体系中的气泡和丁酮。把处理完毕的胶液倒入模具中，120℃下放置2小时，成型后把模具在压机中真空层压固化90min，固化压力32kg/cm2，固化温度200℃，得到0.5-2.0mm厚的片状固化物。对于所得到的固化物，利用平板电容法测定23℃、1GHz的介电常数和介电损耗因数。利用TGA在10℃/min的升温 速度下评价氮气气氛下的5％重量减少温度(Td5％)。利用DMA测试其玻璃化转变温度。性能测试结果示于表1。
应用对比例1
将61重量份的乙烯基苯基硅树脂，39重量份的苯基硅氢树脂，加入总计10ppm的铂金催化剂，搅拌均匀。在真空下抽气一段时间以除去胶液体系中的气泡和丁酮。把处理完毕的胶液倒入模具中，50℃下放置5小时，成型后把模具在压机中真空层压固化90min，固化压力32kg/cm2，固化温度200℃，得到0.5-2.0mm厚的片状固化物。对于所得到的固化物，利用平板电容法测定23℃、1GHz的介电常数和介电损耗因数。利用TGA在10℃/min的升温速度下评价氮气气氛下的5％重量减少温度(Td5％)。利用DMA测试其玻璃化转变温度。性能测试结果示于表1。
应用对比例2
将97重量份的甲基丙烯酸酯基聚苯醚树脂MX9000、3重量份的过氧化二异丙苯(DCP)溶解于适量丁酮溶剂中，并调节至适合粘度，搅拌均匀。在真空下抽气一段时间以除去胶液体系中的气泡和丁酮。把处理完毕的胶液倒入模具中，120℃下放置2小时，成型后把模具在压机中真空层压固化90min，固化压力32kg/cm2，固化温度200℃，得到0.5-2.0mm厚的片状固化物。对于所得到的固化物，利用平板电容法测定23℃、1GHz的介电常数和介电损耗因数。利用TGA在10℃/min的升温速度下评价氮气气氛下的5％重量减少温度(Td5％)。利用DMA测试其玻璃化转变温度。性能测试结果示于表1。
应用对比例3
将77重量份的甲基丙烯酸酯基苯醚树脂MX9000、20重量份丁苯共聚物Ricon100、3重量份的过氧化二异丙苯(DCP)溶解于适量丁酮溶剂中，并调节至适合粘度，搅拌均匀。在真空下抽气一段时间以除去胶液体系中的气泡和丁酮。把处理完毕的胶液倒入模具中，120℃下放置2小时，成型后把模具在压机中真空层压固化90min，固化压力32kg/cm2，固化温度200℃，得到0.5-2.0mm厚的片状固化物。对于所得到的固化物，利用平板电容法测定23℃、1GHz的介电常数和介电损耗因数。利用TGA在10℃/min的升温速度下评价氮气气氛下的5％重量减少温度(Td5％)。利用DMA测试其玻璃化转变温度。性能测试结果示于表1。
实施例和对比例中所用的材料具体如下：
苯酚甲醛线性酚醛树脂：2812，韩国迈图。
双环戊二烯型酚醛树脂：9110，台湾长春。
联苯型酚醛树脂：7851-H，日本明和。
甲基丙烯酸酯基聚苯醚树脂：MX9000，Sabic。
丁苯共聚物：Ricon100，Satomer。
过氧化二异丙苯：上海高桥。
苯基硅氢树脂：SH303，润禾化工。
乙烯基苯基硅树脂：SP606，润禾化工。
表1中所涉及参数的检测标准或方法如下：
(1)玻璃化转变温度(Tg)：使用DMA测试，按照IPC-TM-650 2.4.24.4所规定的DMA测试方法进行测定；
(2)介电常数和介电损耗因子：按照IPC-TM-650 2.5.5.9的方法进行测试，测试频率为1GHz；
(3)热分解温度(Td5％)：根据热重分析法(TGA)，按照IPC-TM-650 2.4.24所规定的TGA方法进行测定。
表1应用实施例提供的覆铜箔层压板的性能测试结果
Figure PCTCN2016099134-appb-000028
表2应用对比例提供的覆铜箔层压板的性能测试结果
Figure PCTCN2016099134-appb-000029
应用实施例1和2表明含有本发明所合成的不饱和双键有机硅改性聚苯醚树脂的树脂组合物，与一般的乙烯基苯基硅树脂(应用对比例1)相比，其固化物具有更优异的介电特性，更高玻璃化转变温度。应用实施例3-5表明本发 明所合成的不饱和双键有机硅改性聚苯醚树脂，与甲基丙烯酸酯基聚苯醚树脂(应用对比例2和3)相比，也同样具有更优异的介电特性，更高玻璃化转变温度并且具有更高的热分解温度。因此该含有不饱和双键的有机硅改性聚苯醚树脂是一种综合性能更加优异的树脂，可用于高频电路基板的制备，具有较大应用价值。
应该注意到并理解，在不脱离后附的权利要求所要求的本发明的精神和范围的情况下，能够对上述详细描述的本发明做出各种修改和改进。因此，要求保护的技术方案的范围不受所给出的任何特定示范教导的限制。
申请人声明，本发明通过上述实施例来说明本发明的详细方法，但本发明并不局限于上述详细方法，即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (13)

  1. 一种有机硅改性的聚苯醚树脂，其特征在于，所述聚苯醚树脂具有式(I)的结构：
    Figure PCTCN2016099134-appb-100001
    其中，R1选
    Figure PCTCN2016099134-appb-100002
    R2为H、烯丙基或异烯丙基；
    R3、R4和R5均各自独立地选自C1～C8取代或未取代的直链或支链烷基、C2～C8取代或未取代的直链或支链烯基、C5～C12取代或未取代的脂环基、C6～C20取代或未取代的芳香基或C6～C20的取代或未取代的芳氧基，且R3、R4和R5中至少有一个为不饱和基团；
    n1、n2均各自独立地为正整数，且满足4≤n1+n2≤25。
  2. 如权利要求1所述的聚苯醚树脂，其特征在于，R3、R4和R5均各自独立地选自选自
    Figure PCTCN2016099134-appb-100003
    -CH3、
    Figure PCTCN2016099134-appb-100004
    R14选自H、C1～C14取代或未取代的直链或支链烷基、C5～C12取代或未取代的脂环基或C1～C14的烷氧基。
  3. 如权利要求1或2所述的聚苯醚树脂，其特征在于，所述n1、n2满足6≤n1+n2≤20。
  4. 如权利要求1-3任一项所述的聚苯醚树脂，其特征在于，8≤n1+n2≤15。
  5. 如权利要求1-4任一项所述的聚苯醚树脂，其特征在于，所述聚苯醚树脂选自化合物
    Figure PCTCN2016099134-appb-100005
    Figure PCTCN2016099134-appb-100006
    Figure PCTCN2016099134-appb-100007
    所述化合物中的n1、n2均各自独立地为正整数，且满足4≤n1+n2≤25，优选6≤n1+n2≤20，进一步优选8≤n1+n2≤15。
  6. 一种如权利要求1-5任一项所述的聚苯醚树脂的制备方法，其特征在于，当R3和R4均各自独立地选自C1～C8取代或未取代的直链或支链烷基、C2～C8取代或未取代的直链或支链烯基、C5～C12取代或未取代的脂环基或C6～C20取代或未取代的芳香基，且R5为C6～C20的取代或未取代的芳氧基，且R3、R4和R5中至少有一个为不饱和基团时，所述方法包括如下步骤：
    (1)在无水溶剂中，使具有式(II)的二氯硅烷单体与具有式(III)结构的聚苯醚树脂混合，升温至第一温度进行第一反应；
    (2)向反应体系中加入单官能酚类单体H-R5，升温至第二温度继续进行第二反应，得到式(I)结构的聚苯醚树脂；
    Figure PCTCN2016099134-appb-100008
    其中，R1和n具有与权利要求1或2相同的意义；
    或者，当R3、R4和R5均各自独立地选自C1～C8取代或未取代的直链或支链烷基、C2～C8取代或未取代的直链或支链烯基、C5～C12取代或未取代的脂环基或C6～C20取代或未取代的芳香基时，且R3、R4和R5中至少有一个为不饱和基团 所述方法包括如下步骤：
    (a)在无水溶剂中，使具有式(IV)结构的一氯硅烷单体与具有式(III)结构的聚苯醚树脂混合，升温至第三温度进行第三反应，得到式(I)结构的酚醛树脂；
    Figure PCTCN2016099134-appb-100009
    其中，R1和n具有与权利要求1或2相同的意义；
    优选地，当R3和R4各自独立地选自
    Figure PCTCN2016099134-appb-100010
    -CH3、
    Figure PCTCN2016099134-appb-100011
    Figure PCTCN2016099134-appb-100012
    且R5为
    Figure PCTCN2016099134-appb-100013
    时，所述方法包括如下步骤：
    (1)在无水溶剂中，使具有式(II)的二氯硅烷单体与具有式(III)结构的聚苯醚树脂混合，升温至第一温度进行第一反应；
    (2)向反应体系中加入单官能酚类单体H-R5，升温至第二温度继续进行第二反应，得到式(I)结构的聚苯醚树脂；
    其中，R1、R14和n具有与权利要求1或2相同的意义；
    或者，当R3、R4和R5均各自独立地选自
    Figure PCTCN2016099134-appb-100014
    -CH3、
    Figure PCTCN2016099134-appb-100015
    Figure PCTCN2016099134-appb-100016
    且R3、R4和R5中至少有一个为不饱和基团时，所述方法包括如下步骤：
    (a)在无水溶剂中，使具有式(IV)结构的一氯硅烷单体与具有式(III)结构的聚苯醚树脂混合，升温至第三温度进行第三反应，得到式(I)结构的酚醛树脂；
    Figure PCTCN2016099134-appb-100017
    其中，R1和n具有与权利要求1或2相同的意义；
    优选地，所述无水溶剂选自四氢呋喃、二氯甲烷、丙酮或丁酮中的任意1种或者任意2种的混合物；
    优选地，所述第一温度和第二温度均各自独立地选自0～60℃；第一反应时间和第二反应时间均各自独立地优选自2～24h，进一步优选3～22h，特别优选4～20h；
    优选地，第三温度选自0～60℃；第三反应时间优选自2～24h，进一步优选3～22h，特别优选4～20h。
  7. 一种树脂组合物，其特征在于，所述树脂组合物含有权利要求1-5任一项所述的含有不饱和双键有机硅改性的聚苯醚树脂；
    优选地，所述树脂组合物还可以包括除式(I)结构的有机硅改性聚苯醚树脂以外的其它带有双键的树脂和引发剂；
    优选地，所述其它带有双键的树脂为聚烯烃树脂或有机硅树脂；
    优选地，所述聚烯烃树脂优选自苯乙烯-丁二烯共聚物、聚丁二烯或苯乙烯-丁二烯-二乙烯基苯共聚物中的任意1种或者至少2种的混合物；
    优选地，所述苯乙烯-丁二烯共聚物、聚丁二烯、苯乙烯-丁二烯-二乙烯基苯共聚物均可各自独立地被氨基改性、马来酸酐改性、环氧基改性、丙烯酸酯改性、羟基改性或羧基改性；
    优选地，所述有机硅树脂选自如下含有不饱和双键的有机硅化合物结构中的任意一种：
    Figure PCTCN2016099134-appb-100018
    R6、R7和R8均独立地选自取代或未取代的C1～C8的直链烷基、取代或未取代的C1～C8支链烷基、取代或未取代的苯基或取代或未取代的C2～C10含C＝C的基团；且R6、R7和R8三者至少有一个为取代或未取代的C2～C10含C＝C的基团；0≤m≤100，
    或，
    Figure PCTCN2016099134-appb-100019
    R9选自取代或未取代的C1～C12直链烷基或取代或未取代的C1～C12支链烷基；2≤p≤10，且p为自然数；
    优选地，所述树脂组合物还可以包括硅氢树脂和硅氢加成催化剂；
    优选地，所述硅氢树脂选自如下含有硅氢键的有机硅化合物结构中的任意1种：
    Figure PCTCN2016099134-appb-100020
    R10、R11和R12均独立地选自取代或未取代的C1-C8的直链烷基、取代或未取代的C1～C8支链烷基、取代或未取代的苯基或取代或H原子；且R10、R11和R12三者至少有一个为H原子；0≤x≤100，
    或，
    Figure PCTCN2016099134-appb-100021
    R13选自取代或未取代的C1～C12直链烷基或取代或未取代的C1～C12支链烷基；2≤y≤10，且y为自然数；
    优选地，所述树脂组合物还可以无机填料；
    优选地，所述树脂组合物还可以包括阻燃剂。
  8. 一种树脂胶液，其特征在于，所述树脂胶液为将权利要求7所述的树脂组合物溶解或分散在溶剂中得到。
  9. 一种树脂固化物，其特征在于，所述树脂固化物通过固化如权利要求7所述的树脂组合物得到。
  10. 一种预浸料，其特征在于，所述预浸料包括增强材料，及通过浸渍干燥后附着在其上的如权利要求7所述的树脂组合物。
  11. 一种覆铜板，其特征在于，所述覆铜板含有至少一张如权利要求10所述的预浸料。
  12. 一种层压板，其特征在于，所述层压板含有至少一张如权利要求10所述的预浸料。
  13. 一种印制电路板，其特征在于，所述印制电路板含有至少一张如权利要求10所述的预浸料。
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