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CN108250716B - A polysiloxane-allyl compound modified polyphenylene ether resin composition and its prepreg, laminate and printed circuit board - Google Patents

A polysiloxane-allyl compound modified polyphenylene ether resin composition and its prepreg, laminate and printed circuit board Download PDF

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CN108250716B
CN108250716B CN201611241815.4A CN201611241815A CN108250716B CN 108250716 B CN108250716 B CN 108250716B CN 201611241815 A CN201611241815 A CN 201611241815A CN 108250716 B CN108250716 B CN 108250716B
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polysiloxane
polyphenylene ether
ether resin
allyl compound
resin composition
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CN108250716A (en
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黄增彪
成浩冠
丘威平
魏婷
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Shengyi Technology Co Ltd
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    • 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
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/061—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of metal
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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    • 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
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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    • 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
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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
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B32B2260/023—Two or more layers
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • 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
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
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    • 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
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    • C08J2483/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • 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
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Abstract

本发明提供一种聚硅氧烷‑烯丙基化合物改性的聚苯醚树脂组合物及其预浸料、层压板和印制电路板，所述聚硅氧烷‑烯丙基化合物改性的聚苯醚树脂组合物包括聚苯醚树脂和具有式I所示结构的聚硅氧烷‑烯丙基化合物，相对于100重量份聚苯醚树脂，所述组合物中聚硅氧烷‑烯丙基化合物的含量为15‑80重量份。本发明在聚苯醚树脂组合物中加入聚硅氧烷‑烯丙基化合物，得到的组合物具备较低的介电常数和较低的介电损耗因子，耐热性能和吸湿性能优异，同时解决了组合物与金属箔粘合性能差的应用弱点，提高覆铜板的层间粘合力，在无需另外添加阻燃剂的条件下也能达到UL94V‑0的燃烧等级，真正做到无卤无磷阻燃的效果。The present invention provides a polyphenylene ether resin composition modified by a polysiloxane-allyl compound and its prepreg, laminate and printed circuit board, wherein the polysiloxane-allyl compound modified The polyphenylene ether resin composition comprises a polyphenylene ether resin and a polysiloxane-allyl compound having a structure shown in formula I, relative to 100 parts by weight of the polyphenylene ether resin, the polysiloxane-allyl compound in the composition is The content of the allyl compound is 15-80 parts by weight. In the present invention, polysiloxane-allyl compound is added to the polyphenylene ether resin composition, and the obtained composition has lower dielectric constant and lower dielectric loss factor, excellent heat resistance and moisture absorption, and at the same time It solves the application weakness of poor adhesion between the composition and the metal foil, improves the interlayer adhesion of the copper clad laminate, and can reach the UL94V‑0 combustion level without the need for additional flame retardants, and is truly halogen-free. Phosphorus-free flame retardant effect.

Description

Polysiloxane-allyl compound modified polyphenyl ether resin composition, and prepreg, laminated board and printed circuit board thereof
Technical Field
The invention belongs to the technical field of copper-clad plate materials, and relates to a polysiloxane-allyl compound modified polyphenyl ether resin composition, and a prepreg, a laminated board and a printed circuit board thereof.
Background
The polyphenylene oxide resin has excellent properties such as higher glass transition temperature, better dimensional stability, lower water absorption rate, smaller linear expansion coefficient, and particularly has very excellent low dielectric constant and low dielectric loss because a molecular structure contains a large amount of benzene ring structures and weakly polar groups. However, the resin is thermoplastic resin and has the defects of high melting point, difficult processing, poor solvent resistance and the like. Nevertheless, polyphenylene ethers still attract great attention and modification in terms of their excellent chemical properties, physical properties, electrical properties, and the like. For example, reactive groups are introduced at the ends or side ends of polyphenylene ether molecules, so that the polyphenylene ether molecules are converted into thermosetting resin. Current modifications have made increasing progress. Meanwhile, the modified resin still needs to be additionally added with a halogen-containing or phosphorus-containing flame retardant, and the cured resin can reach the combustion grade of UL 94V-0.
CN 102161823 discloses the preparation of high frequency circuit board using modified polyphenylene ether, modified polybutadiene or modified butadiene/styrene copolymer resin composition. Although the board has excellent comprehensive performance, the modified polybutadiene or the modified butadiene/styrene copolymer reduces the heat resistance and the interlayer adhesion of the board, and the modified polymer has a polar group, so that the substrate has the problems of increased water absorption and deteriorated dielectric property.
CN 102993683 discloses a method for copolymerizing an organosilicon compound containing unsaturated double bonds and a modified polyphenylene ether resin to prepare a thermosetting resin plate with excellent comprehensive properties such as heat resistance, dimensional stability, low water absorption, dielectric property and the like. However, when the organosilicon compound is used for crosslinking, the bonding capability of the plate and the copper foil is poor, and a flame retardant is required to be additionally added to achieve the combustion grade of UL 94V-0.
CN103709718A discloses a thermosetting resin composition comprising a thermosetting resin and a diallyl compound, wherein the diallyl compound can provide the thermosetting resin composition with excellent dielectric properties, high heat resistance and low water absorption, but the composition also needs to be added with a halogen-based and/or phosphorus-based flame retardant to achieve a desired flame retardant effect.
Therefore, in the field, a resin composition which has good flame retardancy without adding other flame retardant components and can improve the heat resistance stability, dielectric property, moisture absorption and adhesive property with a metal foil of a copper-clad plate is desired.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a polysiloxane-allyl compound modified polyphenyl ether resin composition, a prepreg thereof, a laminated board and a printed circuit board, wherein the composition has a lower dielectric constant and a lower dielectric loss factor, has excellent heat resistance and moisture absorption performance, simultaneously solves the application weakness of poor adhesion performance of the composition and a metal foil, can achieve the combustion grade of UL94V-0 under the conditions of no halogen and no phosphorus without adding a flame retardant, and really achieves the effects of no halogen and no phosphorus.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides a polysiloxane-allyl compound modified polyphenylene ether resin composition, the composition comprising a polyphenylene ether resin and a polysiloxane-allyl compound, the content of the polysiloxane-allyl compound in the composition being 15 to 80 parts by weight relative to 100 parts by weight of the polyphenylene ether resin, the polysiloxane-allyl compound having a structure represented by formula I:
Figure BDA0001196329650000021
Figure BDA0001196329650000031
wherein R is1And R2Independently is any one of substituted or unsubstituted C1-C4 linear alkyl, substituted or unsubstituted C1-C4 branched alkyl, substituted or unsubstituted C4-C10 naphthenic base or substituted or unsubstituted phenyl; r3Is substituted or unsubstituted C1-C4 linear alkyl, substituted or unsubstituted C1-C4 branched alkyl, substituted or unsubstituted C4-C10 cycloalkyl, substituted or unsubstituted phenyl or
Figure BDA0001196329650000032
Wherein R is any one of substituted or unsubstituted C1-C4 straight-chain alkyl, substituted or unsubstituted C1-C4 branched-chain alkyl, substituted or unsubstituted C4-C10 naphthenic base or substituted or unsubstituted phenyl, and m is an integer of 1-6; r4Is substituted or unsubstituted C1-C4 straight chain alkyl, substituted or unsubstituted C1-C4 branched chain alkyl, hydroxyl or
Figure BDA0001196329650000033
Any one of the above; r5Is any one of substituted or unsubstituted C1-C4 straight-chain alkyl, substituted or unsubstituted C1-C4 branched-chain alkyl, -O-or-S-; n is an integer of 4 to 50.
The content of the polysiloxane-allyl compound in the composition is 15 to 80 parts by weight, for example, 15 parts by weight, 18 parts by weight, 20 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, or 80 parts by weight, relative to 100 parts by weight of the polyphenylene ether resin.
In the present invention, since the polysiloxane-allyl compound is a halogen-free and phosphorus-free compound, the substituent of the group in the present invention does not contain a halogen and a phosphorus atom.
In the present invention, R1、R2、R3、R4Or R, the substituted or unsubstituted C1-C4 linear alkyl can be substituted or substituted C1, C2, C3 or C4 linear alkylAlkyl radicals, e.g. -CH3、-CH2CH3or-CH2CH2CH3Etc., preferably-CH3(ii) a The substituted or unsubstituted C1-C4 branched alkyl group can be a substituted or substituted C1, C2, C3, or C4 branched alkyl group, e.g.
Figure BDA0001196329650000034
The substituted or unsubstituted C4-C10 cycloalkyl group may be a substituted or unsubstituted C4, C5, C6, C7, C8, C9, or C10 cycloalkyl group, and may be, for example, a substituted or unsubstituted C4, C5, C7, C9, or C10 cycloalkyl group
Figure BDA0001196329650000041
Etc.; the substituted or unsubstituted phenyl group may be
Figure BDA0001196329650000042
And the like.
In the present invention, at R5The substituted or unsubstituted C1-C4 linear alkyl group can be a substituted or substituted C1, C2, C3 or C4 linear alkyl group, such as-CH2-、-CH2CH2-、-CH2CH2CH2-or-CH2CH2CH2CH2-; the substituted or unsubstituted C1-C4 branched alkyl group can be substituted or substituted C1, C2, C3 or C4 branched alkyl, and is preferably-C (CH)3)2-or-CH (CH)3)-。
Preferably, R1And R2Independently methyl or phenyl.
Preferably, R3Selected from methyl, phenyl or
Figure BDA0001196329650000043
Any one of them.
Preferably, R4Selected from methyl, hydroxy or
Figure BDA0001196329650000044
Any one of them.
Preferably, R5Is selected from-C (CH)3)2-、-CH(CH3)-、-CH2Any one of-O-or-S-.
In the present invention, m is an integer of 1 to 6, for example m may be 1, 2, 3, 4, 5 or 6.
In the present invention, n is an integer of 4 to 50, for example, n may be 4, 5, 6, 7, 8, 9, 10, 12, 15, 18, 20, 22, 24, 26, 28, 30, 33, 35, 38, 40, 42, 44, 46, 48 or 50.
Preferably, the polysiloxane-allyl compound is any one of or a combination of at least two of the compounds having the structure shown in the following formulas a-e:
Figure BDA0001196329650000045
Figure BDA0001196329650000051
wherein n is an integer from 4 to 50.
Preferably, the preparation method of the polysiloxane-allyl compound comprises the following steps: the diallyl compound shown in the formula II and hydrogenous polysiloxane shown in the formula III are subjected to hydrosilylation reaction to obtain polysiloxane-allyl compound shown in the formula I, wherein the reaction formula is as follows:
Figure BDA0001196329650000061
wherein R is1、R2、R3、R4And R5And n is as defined above.
Preferably, the diallyl compound represented by the formula II is selected from any one or a combination of at least two of diallyl bisphenol a diglycidyl ether, 2' -diallyl bisphenol a, 2' -diallyl bisphenol E, 2' -diallyl bisphenol F and 2,2' -diallyl bisphenol S, preferably diallyl bisphenol a diglycidyl ether, and more preferably 2,2' -diallyl bisphenol a diglycidyl ether.
Preferably, the hydrogenpolysiloxanes of formula III contain 0.05 to 0.46% by weight of hydrogen directly attached to silicon, for example 0.06%, 0.08%, 0.1%, 0.13%, 0.15%, 0.18%, 0.2%, 0.25%, 0.28%, 0.3%, 0.35%, 0.38%, 0.4%, 0.43% or 0.45%.
Preferably, the molar ratio of vinyl groups in the diallyl compound of formula II to silicon-hydrogen bonds in the hydrogenpolysiloxane of formula III is (2.4-2): 1, e.g. 2.4:1, 2.3:1, 2.2:1, 2.1:1 or 2: 1.
Preferably, the hydrosilylation reaction is carried out in the presence of a catalyst, the catalyst being a platinum-containing catalyst;
preferably, the platinum-containing catalyst is a Speier catalyst and/or a Karsted catalyst;
preferably, the platinum-containing catalyst is chloroplatinic acid (H)2PtCl6) And/or a platinum-containing catalyst represented by the following molecular structural formula:
Figure BDA0001196329650000071
the molecular formula of which can be expressed as Pt2[(CH2＝CHSiMe2)2O]3(abbreviated as Pt)2(dvs)3). In the formula described above, Pt forms a covalent bond with the double bond electrons on the siloxane to form the platinum-containing catalyst.
Preferably, the catalyst is used in an amount of 5 to 25ppm (ppm means parts per million, so that 5 to 25ppm may be written herein as 0.0005% to 0.0025%) based on the mass of the hydrogenpolysiloxane of formula III, for example 5ppm, 8ppm, 10ppm, 13ppm, 15ppm, 18ppm, 20ppm, 22ppm or 25 ppm.
Preferably, the hydrosilylation reaction is carried out in an organic solvent, which is any one or a combination of at least two of toluene, xylene, tetrahydrofuran, or DMF, preferably toluene.
Preferably, the temperature of the hydrosilylation reaction is 55-85 ℃, such as 56 ℃, 58 ℃, 60 ℃, 63 ℃, 65 ℃, 68 ℃, 70 ℃, 73 ℃, 75 ℃, 78 ℃, 80 ℃, 82 ℃ or 84 ℃.
Preferably, the hydrogenpolysiloxane of formula III in the hydrosilylation reaction is added dropwise to the reaction system containing the diallyl compound of formula II.
Preferably, the hydrosilylation reaction is carried out in the presence of a protective gas, preferably nitrogen.
Preferably, the hydrosilylation reaction is carried out with stirring.
Preferably, the reaction is stopped after the completion of the reaction of the hydrogenpolysiloxane of formula III.
The method for judging whether the hydrogenpolysiloxane shown in the formula III completely reacts or not in the invention comprises the following steps: and detecting a signal peak of Si-H in the reaction liquid by utilizing infrared spectroscopy, wherein if the signal peak disappears or is extremely weak, the hydrogenpolysiloxane shown in the formula III completely reacts, otherwise, the hydrogenpolysiloxane does not completely react, and the reaction needs to be continued.
Preferably, the polyphenylene ether resin is any one or a combination of at least two of modified polyphenylene ether resins having a structure represented by formula IV:
Figure BDA0001196329650000081
wherein X is selected from a vinyl-containing group; a is selected from
Figure BDA0001196329650000082
M is selected from the group consisting of a covalent bond, -CH2-、-C(CH3)2-、-CH(CH3)-、-O-、-SO2-, -S-or carbonyl; r11、R21、R31And R41Independently selected from any one of hydrogen, substituted or unsubstituted C1-C4 straight chain alkyl, substituted or unsubstituted C1-C4 branched chain alkyl or substituted or unsubstituted phenyl; r12、R22、R32And R42Independently selected from any one of substituted or unsubstituted C1-C4 linear alkyl, substituted or unsubstituted C1-C4 branched alkyl or substituted or unsubstituted phenyl; a and b are independently integers from 1 to 100.
Preferably, X is selected from
Figure BDA0001196329650000083
Any one of them.
In the present invention, at R11、R21、R31And R41The substituted or unsubstituted C1-C4 linear alkyl group may be a substituted or substituted C1, C2, C3 or C4 linear alkyl group, e.g., -CH2-、-CH2CH2-、-CH2CH2CH2-or-CH2CH2CH2CH2-; the substituted or unsubstituted C1-C4 branched alkyl group can be substituted or substituted C1, C2, C3 or C4 branched alkyl, and is preferably-C (CH)3)2-or-CH (CH)3) -; the substituted or unsubstituted phenyl group may be
Figure BDA0001196329650000091
And the like.
In the present invention, a and b may be independently 1, 3,5, 8, 10, 12, 15, 18, 20, 30, 40, 50, 60, 70, 80, 90 or 100, and specific integer values therebetween, which are not intended to be exhaustive or to be included in the range for brevity.
Preferably, the polysiloxane-allyl compound-modified polyphenylene ether resin composition of the present invention further comprises a curing accelerator.
Preferably, the curing accelerator is contained in the composition in an amount of 0.3 to 3 parts by weight, for example, 0.3 part by weight, 0.5 part by weight, 0.8 part by weight, 1 part by weight, 1.3 parts by weight, 1.5 parts by weight, 1.8 parts by weight, 2 parts by weight, 2.3 parts by weight, 2.5 parts by weight, 2.8 parts by weight or 3 parts by weight, relative to 100 parts by weight of the polyphenylene ether resin.
Preferably, the curing accelerator is a peroxide that initiates a free radical reaction;
preferably, the curing accelerator is di-tert-butyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, cumyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-3, 5, 5-trimethylhexanoate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, 1-di-tert-butyl peroxy-3, 5, 5-trimethylcyclohexane, 1-di-tert-butyl peroxycyclohexane, 2-di (tert-butyl peroxy) butane, bis (4-tert-butylcyclohexyl) peroxydicarbonate, hexadecyl peroxydicarbonate, tetradecyl peroxydicarbonate, dipentyl hexylperoxide, dicumyl peroxide, di-n-butyl peroxy-butyrate, di-tert-butyl peroxy-butyl peroxydicarbonate, any one or a mixture of at least two of bis (t-butylperoxyisopropyl) benzene, 2, 5-dimethyl-2, 5-di-t-butylperoxyhexane, 2, 5-dimethyl-2, 5-di-t-butylperoxyhexyne, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-amyl hydroperoxide, t-butyl cumyl peroxide, diisopropylbenzene hydroperoxide, tert-butyl peroxycarbonate-2-ethyl hexanoate, t-butyl peroxy2-ethylhexyl carbonate, n-butyl 4, 4-di (t-butylperoxy) valerate, methyl ethyl ketone peroxide or cyclohexane peroxide.
Preferably, the composition further comprises an inorganic filler.
Preferably, the content of the inorganic filler in the composition is 0 to 350 parts by weight excluding 0, for example, 1 part by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, 100 parts by weight, 130 parts by weight, 150 parts by weight, 180 parts by weight, 200 parts by weight, 250 parts by weight, 280 parts by weight, 300 parts by weight, or 350 parts by weight, with respect to 100 parts by weight of the polyphenylene ether resin.
Preferably, the inorganic filler is selected from any one or a mixture of at least two of crystalline silica, amorphous silica, spherical silica, fused silica, titanium dioxide, silicon carbide, glass fiber, alumina, aluminum nitride, boron nitride, barium titanate or strontium titanate.
In another aspect, the present invention provides a resin cement obtained by dissolving or dispersing the polysiloxane-allyl compound-modified polyphenylene ether resin composition of the present invention in a solvent.
Preferably, the solvent is one or a combination of at least two of ketones, hydrocarbons, ethers, esters or aprotic solvents, preferably one or a mixture of at least two of acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, methanol, ethanol, primary alcohols, ethylene glycol monomethyl ether, propylene glycol methyl ether acetate, ethyl acetate, N-dimethylformamide or N, N-diethylformamide. The solvents can be used alone or in combination. The addition amount of the solvent can be determined by those skilled in the art according to the viscosity of the selected resin, so that the viscosity of the resin glue solution is moderate, and the curing is convenient, and the invention is not limited to this.
In another aspect, the present invention provides a cover film prepared from the resin glue solution as described above.
In another aspect, the present invention provides a prepreg comprising a reinforcing material and attached thereto by impregnation drying a polysiloxane-allyl compound-modified polyphenylene ether resin composition as described above.
Preferably, the reinforcing material is used in an amount of 50 to 230 parts by weight, for example, 60 parts by weight, 80 parts by weight, 100 parts by weight, 120 parts by weight, 140 parts by weight, 160 parts by weight, 180 parts by weight, 200 parts by weight or 220 parts by weight, based on 100 parts by weight of the total polysiloxane-allyl compound-modified polyphenylene ether resin composition.
In the present invention, the reinforcing material is selected from carbon fibers, glass fiber cloth, aramid fibers or non-woven fabric, preferably glass fiber cloth.
In another aspect, the present invention provides an insulating panel comprising at least one sheet of prepreg as described above.
In another aspect, the present invention provides a laminate comprising at least one prepreg as described above.
In another aspect, the present invention provides a metal-clad laminate comprising one or at least two stacked prepregs as described above, and a metal foil on one or both sides of the stacked prepregs.
In another aspect, the present invention provides a printed circuit board comprising one or at least two superimposed prepregs as described above.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the polysiloxane-allyl compound is added into the polyphenyl ether resin composition, so that the obtained composition has a lower dielectric constant, a lower dielectric loss factor and excellent heat resistance and moisture absorption performance, the application weakness of poor bonding performance between the composition and a metal foil is solved, the interlayer bonding force of the copper-clad plate is improved, the UL94V-0 combustion grade can be achieved under the condition of not adding a flame retardant, and the effect of really halogen-free phosphorus-free flame retardation is achieved.
Drawings
FIG. 1 is a graph showing the results of IR spectroscopy characterization of a polysiloxane-allyl compound prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The materials used in the following examples and comparative examples are shown in table 1.
TABLE 1
Figure BDA0001196329650000121
Example 1
In this example, a polysiloxane-allyl compound of formula I was prepared from 2,2' -diallylbisphenol A and hydrogenpolysiloxane HWG17606 by hydrosilylation as follows:
completely dissolving diallyl bisphenol A and a catalyst chloroplatinic acid by using a proper amount of toluene, mixing, heating to 60 ℃ in advance, dropwise adding hydrogen-containing polysiloxane with a metered amount under stirring in a nitrogen atmosphere, continuously reacting until a signal peak (about 2145cm < -1 >) of an Si-H bond in an infrared spectrum of a reaction mixed solution disappears or is very weak and a signal peak (about 1635cm < -1 >) of allyl remains strong, stopping heating, and removing the solvent under reduced pressure to obtain the polysiloxane-allyl compound, wherein the structure of the polysiloxane-allyl compound is shown as a formula d.
The infrared spectrum of the polysiloxane-allyl compound obtained is characterized as shown in FIG. 1. from FIG. 1, it can be seen that the signal peak of Si-H bond (2146.03cm-1) is very weak, while the signal peak of allyl group (1632.38cm-1) is very strong.
And (3) dissolving MX9000 and the compound of the formula d prepared by using a proper amount of solvent, adding curing agent DCP and inorganic filler which are dissolved in advance, and fully dispersing to obtain the resin glue solution composition.
And (3) soaking the composition on glass fiber cloth, and heating for 2-20min in an oven at the temperature of 110-200 ℃ to prepare the prepreg. And (3) overlapping and combining a plurality of prepregs, covering copper foils on the upper surface and the lower surface of the prepregs, and then placing the prepregs into a vacuum hot press to press for 1.5 to 3 hours at the temperature of 170-210 ℃ and under the pressure of 1 to 2kg to obtain the laminated board or the copper-clad plate prepared from the composition. The mixture ratio of the composition and the performance of the laminated board or the copper-clad board prepared by the composition are shown in a table 2.
Example 2
In this example, a polysiloxane-allyl compound of formula I was prepared from 3,3 '-diallyl-4, 4' diphenol ether diglycidyl ether and hydrogenpolysiloxane HWG17606 by hydrosilylation as follows:
dissolving 3,3 '-diallyl-4, 4' -biphenol ether diglycidyl ether and 10ppm Karstd catalyst completely with appropriate amount of toluene, mixing, preheating to 70 deg.C, adding hydrogen-containing polysiloxane dropwise under stirring in nitrogen atmosphere, and reacting until the signal peak of Si-H bond (2145 cm) in infrared spectrum of the reaction mixture solution-1Nearby) disappeared or was very faint, while the allyl signal peak (1635 cm)-1Nearby), stopping heating, and removing the solvent under reduced pressure to obtain the polysiloxane-allyl compound with the structure shown in the formula a.
And (3) dissolving MX9000 and the compound of the formula a prepared by using a proper amount of solvent, adding curing agent DCP and inorganic filler which are dissolved in advance, and fully dispersing to obtain the resin glue solution composition.
And (3) soaking the composition on glass fiber cloth, and heating for 2-20min in an oven at the temperature of 110-200 ℃ to prepare the prepreg. And (3) overlapping and combining a plurality of prepregs, covering copper foils on the upper surface and the lower surface of the prepregs, and then placing the prepregs into a vacuum hot press to press for 1.5 to 3 hours at the temperature of 170-210 ℃ and under the pressure of 1 to 2kg to obtain the laminated board or the copper-clad plate prepared from the composition. The mixture ratio of the composition and the performance of the laminated board or the copper-clad board prepared by the composition are shown in a table 2.
Example 3
In this example, polysiloxane-allyl compounds of formula I were prepared from 1, 1-bis (3,3 '-diallyl-4, 4' xylene) methane and hydrogenpolysiloxane HWG17606 by hydrosilylation as follows:
completely dissolving 1, 1-bis (3,3 '-diallyl-4, 4' -xylene) methane and 10ppm Karstd catalyst by using a proper amount of toluene, mixing, heating to 85 ℃ in advance, dropwise adding a metered amount of hydrogenpolysiloxane under stirring in a nitrogen atmosphere, continuously reacting until a signal peak (around 2145cm < -1 >) of an Si-H bond in an infrared spectrum of a reaction mixed solution disappears or is very weak and an allyl signal peak (around 1635cm < -1 >) is still strong, stopping heating, and removing the solvent under reduced pressure to obtain the polysiloxane-allyl compound, wherein the structure of the polysiloxane-allyl compound is shown in a formula b.
And (3) dissolving MX9000 and the compound of the formula b prepared by using a proper amount of solvent, adding curing agent DCP and inorganic filler which are dissolved in advance, and fully dispersing to obtain the resin glue solution composition.
And (3) soaking the composition on glass fiber cloth, and heating for 2-20min in an oven at the temperature of 110-200 ℃ to prepare the prepreg. And (3) overlapping and combining a plurality of prepregs, covering copper foils on the upper surface and the lower surface of the prepregs, and then placing the prepregs into a vacuum hot press to press for 1.5 to 3 hours at the temperature of 170-210 ℃ and under the pressure of 1 to 2kg to obtain the laminated board or the copper-clad plate prepared from the composition. The mixture ratio of the composition and the performance of the laminated board or the copper-clad board prepared by the composition are shown in a table 2.
Examples 4 to 7
The composition differences of the compositions of the embodiments 4-5 and the embodiment 2 are that the types of the polyphenyl ether resin are different, and the compositions of other materials, the preparation of glue solution, the preparation of prepreg and the preparation method of the copper-clad plate are the same as those of the embodiment 2. The difference between the embodiment 6 and the embodiment 1 is that the type and the addition amount of the curing agent are different, and the preparation methods of other materials, glue solution preparation, prepreg preparation and copper-clad plate are the same as the embodiment 1. The difference between the embodiment 7 and the embodiment 1 is that the composition in the embodiment 7 is not added with inorganic filler, and the preparation methods of other materials, glue solution preparation, prepreg preparation and copper-clad plate are the same as the embodiment 1. The mixture ratio of the composition and the performance of the laminated board or the copper-clad board prepared by the composition are shown in a table 2.
Comparative examples 1 to 2
The specific preparation method of comparative examples 1-2 was the same as that of example 1, except that the ratio of the polysiloxane-allyl compound in the polyphenylene ether resin composition was different from that of the corresponding examples. The mixture ratio of the composition and the performance of the laminated board or the copper-clad board prepared by the composition are shown in a table 2.
Comparative example 3
In this example, a resin composition was obtained by dispersing 3,3 '-diallyl-4, 4' -biphenol ether diglycidyl ether, polyphenylene ether, and the like in a suitable amount of a methyl ethyl ketone/toluene mixed solvent without adding hydrogen-containing polysiloxane, and adding a previously dissolved curing accelerator and an inorganic filler.
The composition is impregnated on glass fiber cloth and heated for 2-20min in an oven at the temperature of 110-200 ℃ to prepare the prepreg. A plurality of prepregs are overlapped and coated with copper foils on the upper surface and the lower surface, and then the prepregs are put into a vacuum hot press and pressed for 1.5 to 3 hours at the temperature of 170-210 ℃ and under the pressure of 1 to 2kg, so as to obtain the laminated board or the copper-clad plate prepared by the composition. The mixture ratio of the composition and the performance of the laminated board or the copper-clad board prepared by the composition are shown in a table 2.
Comparative example 4
A resin composition was obtained by dispersing a hydrogen-containing polysiloxane, an allyl compound, a platinum-containing catalyst, a polyphenylene ether resin, etc. in a suitable amount of a methyl ethyl ketone/toluene mixed solvent, and adding a previously dissolved curing accelerator and an inorganic filler in the respective material ratios of example 1.
The composition is impregnated on glass fiber cloth and heated for 2-20min in an oven at the temperature of 110-200 ℃ to prepare the prepreg. A plurality of prepregs are overlapped and coated with copper foils on the upper surface and the lower surface, and then the prepregs are put into a vacuum hot press and pressed for 1.5 to 3 hours at the temperature of 170-210 ℃ and under the pressure of 1 to 2kg, so as to obtain the laminated board or the copper-clad plate prepared by the composition. The mixture ratio of the composition and the performance of the laminated board or the copper-clad board prepared by the composition are shown in a table 2.
TABLE 2
Figure BDA0001196329650000161
The above performance test method is as follows:
peel Strength (PS): IPC-TM-6502.4.8 was used for the test
Combustibility: UL94 vertical burn test
Dielectric constant and dielectric loss tangent: IPC-TM-650SPDR method
As can be seen from the performance characterization result data in Table 2, the copper-clad plate prepared under the halogen-free and phosphorus-free conditions has excellent flame retardant property which can reach UL94V-0 grade and the peel strength of 0.83N-cm by adding the polysiloxane-allyl compound into the composition-1The dielectric constant can be less than 3.79, the dielectric loss tangent can be less than 0.008, and the composite material has good dielectric property and adhesive property. When the polysiloxane-allyl compound is not used and is changed into diallyl bisphenol A diglycidyl ether (comparative example 3), the flame retardance of the copper clad laminate can only reach UL94V-2 grade; when the amount of the polysiloxane-allyl compound used is too small relative to 100 parts by weight of the polyphenylene ether resin (comparative example 1), the copper clad laminate has flame retardancy only up to UL94V-1 rating, and when the amount of the polysiloxane-allyl compound used is too large relative to 100 parts by weight of the polyphenylene ether resin (comparative example 2), the copper clad laminate has flame retardancy up to UL94V-0 rating, but the copper clad laminate has peeling propertyThe strength is only 0.46N cm-1The normal use of the copper-clad plate is influenced; when the raw materials are physically blended without hydrosilylation (comparative example 4), the burning grade is V-2, the dielectric property is relatively worst, and the peeling strength is very low due to the existence of the single polysiloxane component, so that the application of the raw materials on a copper-clad plate is not facilitated.
The applicant states that the above embodiments are only preferred embodiments of the present invention, and the present invention is not limited to the above embodiments, i.e. it does not mean that the present invention must rely on the above embodiments to be implemented. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.

Claims (39)

1.一种用于制备介电常数达到3.79以下的覆铜板的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，所述组合物包括聚苯醚树脂和聚硅氧烷-烯丙基化合物，相对于100重量份聚苯醚树脂，所述组合物中聚硅氧烷-烯丙基化合物的含量为15-80重量份，所述聚硅氧烷-烯丙基化合物具有式I所示结构：1. A polysiloxane-allyl compound-modified polyphenylene ether resin composition for preparing a copper clad laminate with a dielectric constant of less than 3.79 is characterized in that the composition comprises polyphenylene ether resin and A polysiloxane-allyl compound, relative to 100 parts by weight of the polyphenylene ether resin, the content of the polysiloxane-allyl compound in the composition is 15-80 parts by weight, and the polysiloxane- The allyl compound has the structure shown in formula I:
Figure DEST_PATH_IMAGE002
Figure DEST_PATH_IMAGE002
 式I；formula I; 其中，R1和R2独立地为取代或未取代的C1-C4直链烷基、取代或未取代的C1-C4支链烷基、取代或未取代的C4-C10环烷基或者取代或未取代的苯基中的任意一种；R3为取代或未取代的C1-C4直链烷基、取代或未取代的C1-C4支链烷基、取代或未取代的C4-C10环烷基、取代或未取代的苯基或者
Figure DEST_PATH_IMAGE004
中的任意一种，其中R为取代或未取代的C1-C4直链烷基、取代或未取代的C1-C4支链烷基、取代或未取代的C4-C10环烷基或者取代或未取代的苯基中的任意一种，m为1-6的整数；R4为取代或未取代的C1-C4直链烷基、取代或未取代的C1-C4支链烷基、羟基或
Figure DEST_PATH_IMAGE006
中的任意一种；R5为取代或未取代的C1-C4直链烷基、取代或未取代的C1-C4支链烷基、-O-或-S-中的任意一种；n为12-50的整数；Wherein, R 1 and R 2 are independently substituted or unsubstituted C1-C4 straight-chain alkyl, substituted or unsubstituted C1-C4 branched-chain alkyl, substituted or unsubstituted C4-C10 cycloalkyl or substituted or unsubstituted C4-C10 cycloalkyl Any of unsubstituted phenyl groups; R 3 is substituted or unsubstituted C1-C4 straight-chain alkyl, substituted or unsubstituted C1-C4 branched alkyl, substituted or unsubstituted C4-C10 cycloalkane phenyl, substituted or unsubstituted phenyl or
Figure DEST_PATH_IMAGE004
Any one of, wherein R is substituted or unsubstituted C1-C4 straight-chain alkyl, substituted or unsubstituted C1-C4 branched alkyl, substituted or unsubstituted C4-C10 cycloalkyl or substituted or unsubstituted C1-C10 cycloalkyl Any one of substituted phenyl, m is an integer of 1-6; R 4 is substituted or unsubstituted C1-C4 straight chain alkyl, substituted or unsubstituted C1-C4 branched alkyl, hydroxyl or
Figure DEST_PATH_IMAGE006
Any one of; R 5 is any one of substituted or unsubstituted C1-C4 straight-chain alkyl, substituted or unsubstituted C1-C4 branched alkyl, -O- or -S-; n is an integer from 12 to 50; 所述聚苯醚树脂为具有式IV所示结构的改性聚苯醚树脂中的任意一种或至少两种的组合：The polyphenylene ether resin is any one or a combination of at least two of the modified polyphenylene ether resins having the structure shown in formula IV:
Figure DEST_PATH_IMAGE008
Figure DEST_PATH_IMAGE008
 式IVFormula IV 其中，X选自含乙烯基的基团；A选自
Figure DEST_PATH_IMAGE010
，M选自共价键、-CH2-、-C(CH3)2-、-CH(CH3)-、-O-、-SO2-、-S-或羰基；R11、R21、R31和R41独立地选自氢、取代或未取代的C1-C4直链烷基、取代或未取代的C1-C4支链烷基或取代或未取代的苯基中的任意一种；R12、R22、R32和R42独立地选自取代或未取代的C1-C4直链烷基、取代或未取代的C1-C4支链烷基或取代或未取代的苯基中的任意一种；a和b独立地为1-100的整数。wherein, X is selected from vinyl-containing groups; A is selected from
Figure DEST_PATH_IMAGE010
, M is selected from covalent bond, -CH 2 -, -C(CH 3 ) 2 -, -CH(CH 3 )-, -O-, -SO 2 -, -S- or carbonyl; R 11 , R 21 , R 31 and R 41 are independently selected from any one of hydrogen, substituted or unsubstituted C1-C4 straight-chain alkyl, substituted or unsubstituted C1-C4 branched alkyl or substituted or unsubstituted phenyl ; R 12 , R 22 , R 32 and R 42 are independently selected from substituted or unsubstituted C1-C4 straight chain alkyl, substituted or unsubstituted C1-C4 branched chain alkyl or substituted or unsubstituted phenyl Any of ; a and b are independently integers from 1 to 100. 2.根据权利要求1所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，R1和R2独立地为甲基或苯基。2 . The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 1 , wherein R 1 and R 2 are independently methyl or phenyl. 3 . 3.根据权利要求1所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，R3选自甲基、苯基或
Figure DEST_PATH_IMAGE012
中的任意一种。3. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 1, wherein R is selected from methyl, phenyl or
Figure DEST_PATH_IMAGE012
any of the . 4.根据权利要求1所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，R4选自甲基、羟基或
Figure DEST_PATH_IMAGE013
中的任意一种。4. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 1 , wherein R is selected from methyl, hydroxyl or
Figure DEST_PATH_IMAGE013
any of the . 5.根据权利要求1所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，R5选自-C(CH3)2-、-CH(CH3)-、-CH2-、-O-或-S-中的任意一种。5. The polysiloxane-allyl compound modified polyphenylene ether resin composition according to claim 1, wherein R 5 is selected from -C(CH 3 ) 2 -, -CH(CH 3 )-, -CH 2 -, -O- or -S-. 6.根据权利要求1所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，所述聚硅氧烷-烯丙基化合物为具有如下式a-e所示结构的化合物中的任意一种或至少两种的组合：6. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 1, wherein the polysiloxane-allyl compound is represented by the following formulae a-e Any one or a combination of at least two of the compounds of structure:
Figure DEST_PATH_IMAGE015
Figure DEST_PATH_IMAGE015
 式a；formula a;
Figure DEST_PATH_IMAGE017
Figure DEST_PATH_IMAGE017
 式b；formula b;
Figure DEST_PATH_IMAGE019
Figure DEST_PATH_IMAGE019
 式c；formula c;
Figure DEST_PATH_IMAGE021
Figure DEST_PATH_IMAGE021
 式d；formula d;
Figure DEST_PATH_IMAGE023
Figure DEST_PATH_IMAGE023
 式e；formula e; 其中n为12-50的整数。where n is an integer from 12 to 50. 7.根据权利要求1所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，所述聚硅氧烷-烯丙基化合物的制备方法为：式II所示二烯丙基化合物与式III所示含氢聚硅氧烷发生硅氢加成反应得到式I所示聚硅氧烷-烯丙基化合物，反应式如下：7. The polyphenylene ether resin composition modified by a polysiloxane-allyl compound according to claim 1, wherein the preparation method of the polysiloxane-allyl compound is: formula II The shown diallyl compound and the hydrogen-containing polysiloxane shown in formula III generate a hydrosilylation reaction to obtain a polysiloxane-allyl compound shown in formula I, and the reaction formula is as follows:
Figure DEST_PATH_IMAGE025
，
Figure DEST_PATH_IMAGE025
, 其中，n为12-50的整数。Wherein, n is an integer of 12-50. 8.根据权利要求7所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，式II所示二烯丙基化合物选自二烯丙基双酚A二缩水甘油醚、2,2'-二烯丙基双酚A、2,2'-二烯丙基双酚E、2,2'-二烯丙基双酚F或2,2'-二烯丙基双酚S中的任意一种或至少两种的组合。8. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 7, wherein the diallyl compound shown in formula II is selected from diallyl bisphenol A Diglycidyl ether, 2,2'-diallylbisphenol A, 2,2'-diallylbisphenol E, 2,2'-diallylbisphenol F or 2,2'-bisphenol Any one or a combination of at least two of allylbisphenol S. 9.根据权利要求7所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，式II所示二烯丙基化合物选自二烯丙基双酚A二缩水甘油醚。9 . The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 7 , wherein the diallyl compound shown in formula II is selected from diallyl bisphenol A. 10 . Diglycidyl ether. 10.根据权利要求7所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，式II所示二烯丙基化合物选自2,2'-二烯丙基双酚A二缩水甘油醚。10. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 7, wherein the diallyl compound represented by formula II is selected from 2,2'-diene Propylbisphenol A diglycidyl ether. 11.根据权利要求7所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，式III所示含氢聚硅氧烷中与硅直接相连的氢的重量百分含量为0.05-0.46%。11. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 7, wherein the hydrogen directly connected to silicon in the hydrogen-containing polysiloxane shown in formula III The weight percentage is 0.05-0.46%. 12.根据权利要求7所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，式II所示二烯丙基化合物中乙烯基与式III所示含氢聚硅氧烷中硅氢键的摩尔比为（2.4-2）:1。12. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 7, wherein in the diallyl compound shown in formula II, the vinyl group and the compound shown in formula III contain The molar ratio of silicon-hydrogen bonds in the hydrogen polysiloxane is (2.4-2):1. 13.根据权利要求7所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，所述硅氢加成反应在催化剂存在下进行，所述催化剂为含铂催化剂。13. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 7, wherein the hydrosilylation reaction is carried out in the presence of a catalyst, and the catalyst is a Platinum catalyst. 14.根据权利要求13所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，所述含铂催化剂为Speier催化剂和/或Karsted催化剂。14. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 13, wherein the platinum-containing catalyst is a Speier catalyst and/or a Karsted catalyst. 15.根据权利要求13所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，所述含铂催化剂为氯铂酸和/或如下分子结构式所示的含铂催化剂：15. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 13, wherein the platinum-containing catalyst is chloroplatinic acid and/or represented by the following molecular structural formula Platinum-containing catalysts:
Figure DEST_PATH_IMAGE027
。
Figure DEST_PATH_IMAGE027
. 16.根据权利要求13所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，所述催化剂的用量为式III所示含氢聚硅氧烷质量的5-25 ppm。16. polysiloxane-allyl compound modified polyphenylene ether resin composition according to claim 13, is characterized in that, the consumption of described catalyst is the hydrogen-containing polysiloxane quality shown in formula III 5-25 ppm. 17.根据权利要求13所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，所述硅氢加成反应在有机溶剂中进行，所述有机溶剂为甲苯、二甲苯、四氢呋喃或DMF中的任意一种或至少两种的组合。17. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 13, wherein the hydrosilylation reaction is carried out in an organic solvent, and the organic solvent is Any one or a combination of at least two of toluene, xylene, tetrahydrofuran, or DMF. 18.根据权利要求17所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，所述有机溶剂为甲苯。18. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 17, wherein the organic solvent is toluene. 19.根据权利要求7所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，所述硅氢加成反应的温度为55-85℃。19 . The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 7 , wherein the temperature of the hydrosilylation reaction is 55-85° C. 20 . 20.根据权利要求7所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，所述硅氢加成反应中式III所示含氢聚硅氧烷是以逐滴滴加的方式加入至含有式II所示二烯丙基化合物的反应体系中。20. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 7, wherein the hydrogen-containing polysiloxane shown in the formula III in the hydrosilylation reaction is a It is added dropwise to the reaction system containing the diallyl compound represented by formula II. 21.根据权利要求7所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，所述硅氢加成反应在保护性气体存在下进行。21. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 7, wherein the hydrosilylation reaction is carried out in the presence of a protective gas. 22.根据权利要求21所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，所述保护性气体为氮气。22. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 21, wherein the protective gas is nitrogen. 23.根据权利要求7所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，所述硅氢加成反应在搅拌下进行。23. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 7, wherein the hydrosilylation reaction is carried out under stirring. 24.根据权利要求7所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，待式III所示含氢聚硅氧烷反应完全后，停止反应。24. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 7, wherein the reaction is stopped after the reaction of the hydrogen-containing polysiloxane represented by formula III is completed. 25.根据权利要求1所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，X选自
Figure DEST_PATH_IMAGE029
、
Figure DEST_PATH_IMAGE031
、
Figure DEST_PATH_IMAGE033
或
Figure DEST_PATH_IMAGE035
中的任意一种。25. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 1, wherein X is selected from
Figure DEST_PATH_IMAGE029
,
Figure DEST_PATH_IMAGE031
,
Figure DEST_PATH_IMAGE033
or
Figure DEST_PATH_IMAGE035
any of the . 26.根据权利要求1所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，所述聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物还包括固化促进剂。26. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 1, wherein the polysiloxane-allyl compound-modified polyphenylene ether resin The composition also includes a cure accelerator. 27.根据权利要求26所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，相对于100重量份聚苯醚树脂，所述组合物中固化促进剂的含量为0.3-3重量份。27. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 26, characterized in that, relative to 100 parts by weight of the polyphenylene ether resin, a curing accelerator in the composition The content is 0.3-3 parts by weight. 28.根据权利要求26所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，所述固化促进剂为引发自由基反应的过氧化物。28. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 26, wherein the curing accelerator is a peroxide that initiates a free radical reaction. 29.根据权利要求26所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，所述固化促进剂为二叔丁基过氧化物、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、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、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、过氧化甲乙酮或过氧化环己烷中的任意一种或至少两种的混合物。29. The polysiloxane-allyl compound modified polyphenylene ether resin composition according to claim 26, wherein the curing accelerator is di-tert-butyl peroxide, dilauryl peroxide Acyl, dibenzoyl peroxide, cumyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, pivaloyl peroxypivalate, tert-butyl peroxypivalate, tert-butylperoxide Isobutyrate oxide, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, 1,1-di-tert-butyl peroxy -3,5,5-trimethylcyclohexane, 1,1-di-tert-butylcyclohexaneperoxide, 2,2-di(tert-butylperoxy)butane, bis(4-tert-butylcyclohexyl) ) Peroxydicarbonate, Cetyl Peroxydicarbonate, Myristate Peroxydicarbonate, Dip-pentyl peroxide, Dicumyl peroxide, Bis(tert-butyl isopropyl peroxide) base) benzene, 2,5-dimethyl-2,5-di-tert-butyl hexane peroxide, 2,5-dimethyl-2,5-di-tert-butyl hexyne peroxide, cumene peroxy Hydrogen oxide, p-amyl hydroperoxide, tert-butyl hydroperoxide, tert-butyl cumene peroxide, tert-butyl peroxycarbonate-2-ethylhexanoate, tert-butyl peroxycarbonate-2- Any one or a mixture of at least two of ethylhexyl ester, n-butyl 4,4-di(tert-butylperoxy)valerate, methyl ethyl ketone peroxide or cyclohexane peroxide. 30.根据权利要求1所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，所述组合物还包括无机填料。30. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 1, wherein the composition further comprises an inorganic filler. 31.根据权利要求30所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，相对于100重量份聚苯醚树脂，所述组合物中无机填料的含量为0-350重量份且不包括0。31. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 30, characterized in that, relative to 100 parts by weight of the polyphenylene ether resin, the amount of the inorganic filler in the composition The content is 0-350 parts by weight excluding 0. 32.根据权利要求30所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物，其特征在于，所述无机填料选自结晶型二氧化硅、无定形二氧化硅、球形二氧化硅、熔融二氧化硅、二氧化钛、碳化硅、玻璃纤维、氧化铝、氮化铝、氮化硼、钛酸钡或钛酸锶中的任意一种或至少两种的混合物。32. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 30, wherein the inorganic filler is selected from crystalline silica, amorphous silica, Any one or a mixture of at least two of spherical silica, fused silica, titanium dioxide, silicon carbide, glass fiber, alumina, aluminum nitride, boron nitride, barium titanate, or strontium titanate. 33.一种树脂胶液，其特征在于，所述树脂胶液是将如权利要求1-32中任一项所述的聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物溶解或分散在溶剂中得到。33. A resin glue, characterized in that the resin glue is a polyphenylene ether resin composition modified by the polysiloxane-allyl compound according to any one of claims 1-32 Dissolved or dispersed in solvents. 34.一种覆盖膜，其特征在于，所述覆盖膜由如权利要求33所述的树脂胶液制备得到。34. A cover film, characterized in that, the cover film is prepared from the resin glue solution of claim 33. 35.一种预浸料，其特征在于，所述预浸料包括增强材料以及通过含浸干燥后附着其上的如权利要求1-32中任一项所述聚硅氧烷-烯丙基化合物改性的聚苯醚树脂组合物。35. A prepreg, characterized in that the prepreg comprises a reinforcing material and the polysiloxane-allyl compound according to any one of claims 1 to 32 attached to it after being impregnated and dried Modified polyphenylene ether resin composition. 36.一种绝缘板，其特征在于，所述绝缘板包括至少一张如权利要求35所述的预浸料。36. An insulating board, characterized in that the insulating board comprises at least one prepreg as claimed in claim 35. 37.一种层压板，其特征在于，所述层压板包括至少一张如权利要求35所述的预浸料。37. A laminate comprising at least one prepreg of claim 35. 38.一种覆金属箔层压板，其特征在于，所述覆金属箔层压板包括一张或至少两张叠合的如权利要求35所述的预浸料，以及位于叠合后的预浸料的一侧或两侧的金属箔。38. A metal foil clad laminate, characterized in that the metal foil clad laminate comprises one or at least two superimposed prepregs as claimed in claim 35, and a prepreg after lamination foil on one or both sides of the material. 39.一种印制电路板，其特征在于，所述印制电路板包括一张或至少两张叠合的如权利要求35所述的预浸料。39. A printed circuit board, wherein the printed circuit board comprises one or at least two superimposed prepregs as claimed in claim 35.
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