CN112111144A - Low-expansion crosslinkable hydrocarbon polymer composition, prepreg prepared from low-expansion crosslinkable hydrocarbon polymer composition and thermosetting copper-clad plate - Google Patents

Low-expansion crosslinkable hydrocarbon polymer composition, prepreg prepared from low-expansion crosslinkable hydrocarbon polymer composition and thermosetting copper-clad plate Download PDF

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CN112111144A
CN112111144A CN202011039032.4A CN202011039032A CN112111144A CN 112111144 A CN112111144 A CN 112111144A CN 202011039032 A CN202011039032 A CN 202011039032A CN 112111144 A CN112111144 A CN 112111144A
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expansion
polymer composition
low
hydrocarbon polymer
crosslinkable hydrocarbon
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俞卫忠
俞丞
顾书春
冯凯
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Changzhou Zhongying Technology Co ltd
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Changzhou Zhongying Technology Co ltd
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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
    • 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
    • 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
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B27/12—Layered products comprising a layer of synthetic resin next to 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • 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
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2471/12—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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention belongs to the field of communication materials, and particularly relates to a low-expansion crosslinkable hydrocarbon polymer composition, and a prepreg and a thermosetting copper-clad plate prepared from the low-expansion crosslinkable hydrocarbon polymer composition. The negative expansion filler is added into the plate matrix, so that the thermal expansion coefficient of the material is effectively reduced; in addition, the prepared thermosetting copper-clad plate has excellent dielectric property, high mechanical strength, high glass transition temperature, high heat resistance, high copper foil peeling strength and good uniformity of various properties, is suitable for manufacturing a multilayer copper-clad plate, and can meet various performance requirements of diversification and complication of functions of a copper-clad plate material in the fields of high frequency and high speed communication.

Description

Low-expansion crosslinkable hydrocarbon polymer composition, prepreg prepared from low-expansion crosslinkable hydrocarbon polymer composition and thermosetting copper-clad plate
Technical Field
The invention belongs to the field of communication materials, and particularly relates to a low-expansion crosslinkable hydrocarbon polymer composition, and a prepreg and a thermosetting copper-clad plate prepared from the low-expansion crosslinkable hydrocarbon polymer composition.
Background
The copper-clad plate is widely applied to the fields of mobile phones, computers, wearable equipment, communication base stations, satellites, unmanned automobiles, unmanned aerial vehicles, intelligent robots and the like, and is one of key materials in electronic communication and information industries. The traditional thermosetting resin represented by epoxy resin, phenolic resin and cyanate resin has high thermo-mechanical property, high quality, low price, convenient processing and strong universality, and is a common material for manufacturing copper-clad plate base materials. Researchers continuously search and optimize formulas and process parameters to prepare various thermosetting copper-clad plates with qualified comprehensive performance, and the most basic requirements of each subdivided field of the electronic communication industry on the copper-clad plates are met. However, electronic products are rapidly developing towards miniaturization, light weight, thinning and multi-functionalization, and the copper-clad plate used as a main carrier of electronic components has higher and higher integration level and more obvious multi-layer trend, which requires that the copper-clad plate should have an extremely low thermal expansion coefficient. However, the dielectric constant and dielectric loss of the above-mentioned conventional thermosetting copper clad laminate are generally very high, so that they can only be used at low frequency, and cannot meet the higher performance requirement of the substrate material in the current high frequency and high speed communication field.
The invention discloses a carbon-hydrogen polymer copper-clad plate composition with the patent publication number of CN108676209A and the publication number of 2018.10.19, which comprises, by weight, 20-40 parts of polybutadiene, 15-30 parts of styrene-ethylene block copolymer, 15-25 parts of polyphenyl ether, 5-10 parts of cross-linking agent, 3-5 parts of curing agent and 20-40 parts of inorganic filler.
However, the copper-clad plate in the patent of the invention has the problems of large thermal expansion coefficient and poor overall performance.
Disclosure of Invention
The invention provides a low-expansion crosslinkable hydrocarbon polymer composition, and a prepreg and a thermosetting copper-clad plate prepared from the low-expansion crosslinkable hydrocarbon polymer composition.
In order to solve the problems in the background art, the invention takes the mixture of vinyl modified polyphenyl ether and polydiene or derivatives thereof as composite matrix resin, polydiene-styrene-divinylbenzene terpolymer or derivatives thereof as compatilizer, and the mixture of diene-maleic anhydride copolymer and styrene-maleic anhydride copolymer or derivatives thereof as composite modified resin, and is assisted with negative expansion filler and common filler, flame retardant and initiator in proper types and proportions to prepare the low-expansion crosslinkable hydrocarbon polymer composition. The uniform dispersion liquid of the composition is soaked by fiber cloth, and then the prepreg with uniform gel content, strong resin adhesive force, smooth surface, and proper toughness and viscosity is prepared by the steps of baking and the like. The negative expansion filler is added into the composite matrix resin, so that the apparent thermal expansion coefficient of the material is effectively reduced. Finally, the thermosetting copper clad laminate prepared by the prepreg, the film and the copper foil has excellent dielectric property, high mechanical strength, high glass transition temperature and heat resistance, low thermal expansion coefficient, high copper foil peeling strength and good uniformity of various properties, is suitable for manufacturing a multilayer copper clad laminate, and can meet various performance requirements of diversification and complication of functions of the copper clad laminate in the current high-frequency and high-speed communication field.
The invention provides a low-expansion crosslinkable hydrocarbon polymer composition, which comprises more than seven components of matrix resin, negative expansion filler, compatilizer, modified resin, auxiliary filler, flame retardant and initiator;
the negative expansion filler is ZrW2O8、HfW2O8、NaZr2(PO4)3、Sc2W3O12、NaTi2P3O12、CaTi4P6O24、CaZr4P6O24、KZr(PO4)3、LiZr(PO4)3、NbZr(PO4)3、BaTiO3、PbTiO3、ThP2O7、BiNiO3And PbNiO3One or a mixture of several of them; the negative expansion filler accounts for 1-40 wt% of the low-expansion crosslinkable hydrocarbon polymer composition.
The further preferred technical scheme is as follows: the matrix resin is a composite mixture of one or more of vinyl modified polyphenyl ether and derivatives thereof and one or more of polydiene and derivatives thereof; the number average molecular weight of the polyphenyl ether is 400-10000, the vinyl functional groups exist on the end group or the side group of the polyphenyl ether, a single macromolecular chain of the polyphenyl ether at least contains 2 vinyl functional groups, and the vinyl modified polyphenyl ether accounts for 5-95 wt% of the matrix resin; the number average molecular weight of the polydiene is 500-20000, the side group of a single polydiene polymer chain at least contains 3 reactive carbon-carbon double bonds in total, and the dosage of the polydiene accounts for 5-95 wt% of the matrix resin.
The further preferred technical scheme is as follows: the compatilizer is one or a mixture of more of diene-styrene-divinylbenzene terpolymer and derivatives thereof; wherein the pendant group of the diene block of a single chain of said compatibilizer comprises at least one reactive carbon-carbon double bond; the styrene block accounts for 10-60 wt% of the compatilizer; the divinylbenzene block accounts for 0.5-50 wt% of the compatilizer; the molecular weight of the compatilizer is 400-20000, and the usage amount of the compatilizer accounts for 1-20 wt% of the low-expansion crosslinkable hydrocarbon polymer composition.
The further preferred technical scheme is as follows: the modified resin is a composite mixture of one or more of a diene-maleic anhydride copolymer and derivatives thereof and one or more of a styrene-maleic anhydride copolymer and derivatives thereof; wherein a pendant group of a polydiene block of a single said diene-maleic anhydride copolymer chain contains at least one reactive carbon-carbon double bond; the number average molecular weight of the diene-maleic anhydride copolymer is 500-150000, and the amount of the diene-maleic anhydride copolymer accounts for 5-95 wt% of the modified resin; the number average molecular weight of the styrene-maleic anhydride copolymer is 500-30000, and the amount of the styrene-maleic anhydride copolymer accounts for 5-95 wt% of the modified resin; the amount of the modified resin is 1-20 wt% of the low-expansion crosslinkable hydrocarbon polymer composition.
The further preferred technical scheme is as follows: the auxiliary filler is SiO2、Al2O3、TiO2、ZnO、MgO、Bi2O3、AlN、Si3N4、SiC、BN、Al(OH)3、Mg(OH)2、BaTiO3、SrTiO3、Mg2TiO4、Bi2(TiO3)3、PbTiO3、NiTiO3、CaTiO3、ZnTiO3、Zn2TiO4、BaSnO3、Bi2(SnO3)3、CaSnO3、PbSnO3、MgSnO3、SrSnO3、ZnSnO3、BaZrO3、CaZrO3、PbZrO3、MgZrO3、SrZrO3、ZnZrO3One or a mixture of more of graphite oxide, graphite fluoride, talcum powder, mica powder, kaolin, clay, solid glass beads, hollow glass beads, glass fibers, basalt fibers and carbon fibers, and also one or a mixture of more of polytetrafluoroethylene pre-sintering materials, ultra-high molecular weight polyethylene fibers, Kevlar fibers, polyimide, polyetherimide, polyether ether ketone and polyphenylene sulfide; the auxiliary filler is used in an amount of 0 to 50wt% of the low-expansion crosslinkable hydrocarbon polymer composition.
The further preferred technical scheme is as follows: the flame retardant is one or a mixture of more of aluminum-magnesium flame retardant, boron-zinc flame retardant, molybdenum-tin flame retardant, bromine flame retardant, antimony trioxide, phosphorus flame retardant, nitrogen flame retardant and derivatives thereof; the amount of the flame retardant is 0-40 wt% of the low-expansion crosslinkable hydrocarbon polymer composition.
The further preferred technical scheme is as follows: the initiator is one or a mixture of more of peroxide, azo compound and free radical initiator of redox system which can be dissolved in solvent which enables the low-expansion crosslinkable hydrocarbon polymer composition to be uniformly dispersed, and the dosage of the initiator accounts for 0.01-5 wt% of the low-expansion crosslinkable hydrocarbon polymer composition.
A prepreg prepared by using a low-expansion crosslinkable hydrocarbon polymer composition comprises the following specific steps:
s1, preparing a uniform dispersion liquid of the low-expansion crosslinkable hydrocarbon polymer composition with the solid content of 30-70 wt/v%;
and S2, soaking the fiber cloth in the uniform dispersion liquid, and baking and drying to obtain a prepreg.
The further preferred technical scheme is as follows: the solvent of the uniform dispersion liquid is one of water and an organic solvent or a mixture of several solvents which can uniformly disperse the low-expansion crosslinkable hydrocarbon polymer composition;
the fiber cloth is one of 106, 1080 or 2116 electronic grade alkali-free glass fiber cloth, carbon fiber, boron fiber, Kevlar, polyimide, polytetrafluoroethylene, polyester and polytetrafluoroethylene fiber cloth;
the baking and drying are divided into two stages, wherein the baking and drying temperature of the first stage is 50-120 ℃, and the baking and drying time is 1-30 min; the second stage baking and drying temperature is 150-350 ℃, and the time is 1-30 min.
A thermosetting copper-clad plate prepared from a prepreg prepared from a low-expansion crosslinkable hydrocarbon polymer composition comprises the following specific steps: laminating a prepreg, a film and copper foil coated on the surface together, and preparing the thermosetting copper-clad plate by a laminating process; the number of the prepregs is more than or equal to 1, the number of the films is more than or equal to 0, and the number of the copper foils is 1 or 2;
the laminating temperature of the laminating process is 180-250 ℃, and the laminating pressure is 50-120 kg/cm2The laminating time is 0.5-24 h;
the film is one or a mixture of more of fluorine-containing polymer, polyimide, polyolefin, polyaromatic hydrocarbon, polyamide, polyether ketone, polyether ether ketone, polyaryl ether, polyaryl sulfide, polyaryl ether sulfone, polyaryl ether ketone, polyaryl sulfide ketone, polyether sulfone ketone, polyaryl ether nitrile sulfone, polyaryl sulfide nitrile sulfone, polyphenyl quinoxaline, phenolic resin, epoxy resin, cyanate resin, polycarbonate, polyurethane and polyformaldehyde and derivatives thereof;
the thickness of the thermosetting copper-clad plate is controlled to be 0.1-10 mm.
The invention has good industrial production basis and wide application prospect.
Detailed Description
The invention provides a low-expansion crosslinkable hydrocarbon polymer composition, and a prepreg and a thermosetting copper-clad plate prepared from the same. However, this example is provided only as an illustration and not as a limitation of the invention.
Example 1
Taking 70 parts of polyphenyl ether modified by terminal vinyl (Sabic SA 9000), 38 parts of polybutadiene (Kliviley Ricon 130), 22 parts of polydiene-styrene-divinylbenzene terpolymer (Kliviley Ricon 257), 12 parts of polybutadiene-maleic anhydride copolymer (Kliviley Ricon130MA 8), 8 parts of polystyrene-maleic anhydride copolymer (Kliviley SMA 1000), 12 parts of TiO210 parts of ZrW2O850 parts of flame retardant magnesium hydroxide (American Yabao MAGNIFIN H-5), 20 parts of flame retardant decabromodiphenylethane (Shandonghai Wang chemical) and 450 parts of DMF solvent, stirring for 24 hours at 80 ℃, and fully dissolving and uniformly dispersing; cooling to room temperature, adding 1.2 parts of dibenzoyl peroxide, and further stirring uniformly; dipping glue with 1080 glass fiber cloth, and baking and drying to obtain a prepreg, wherein the baking temperature in the first stage is 75 ℃ and the baking time is 7min, and the baking temperature in the second stage is 250 ℃ and the baking time is 15 min; stacking 10 prepregs, respectively attaching loz copper foils to both sides of the prepregs under a pressure of 85-105 kg/cm2And laminating for 4 hours at the temperature of 250 ℃ to obtain the thermosetting carbon-hydrogen polymer-based copper-clad plate.
Example 2
60 parts of vinyl-terminated modified polyphenylene ether (Sabic SA 9000), 36 parts of polybutadiene (Kliviley Ricon 130), 20 parts of polydiene-styrene-divinylbenzene terpolymer (Kliviley Ricon 257), 8 parts of polybutadiene-maleic anhydride copolymer (Kliviley Ricon130MA 8), 12 parts of polystyrene-maleic anhydride copolymer (Kliviley SMA 1000) and 22 parts of SiO218 parts of ZrW2O816 parts of BaTiO3(Shanghai Dian Yangyang), 28 parts of flame retardant magnesium hydroxide (American jaba MAGNIFIN H-5), 18 parts of secondary flame retardant decabromodiphenylethane (Shandong Haiwang chemical) and 450 parts of DMF solvent in 80 parts ofoStirring for 24 hours under C, fully dissolving and uniformly dispersing; cooling to room temperature, adding 1.2 parts of dibenzoyl peroxide, and further stirring uniformly; dipping glue with 1080 glass fiber cloth, and baking and drying to obtain a prepreg, wherein the baking temperature in the first stage is 75 ℃ and the baking time is 7min, and the baking temperature in the second stage is 250 ℃ and the baking time is 15 min; stacking 10 prepregs, respectively attaching loz copper foils to both sides of the prepregs under a pressure of 85-95 kg/cm2And laminating for 4 hours at the temperature of 250 ℃ to obtain the thermosetting carbon-hydrogen polymer-based copper-clad plate.
Example 3
40 parts of vinyl-terminated modified polyphenylene ether (Sabic SA 9000), 65 parts of polybutadiene (Kliviley Ricon 130), 18 parts of polydiene-styrene-divinylbenzene terpolymer (Kliviley Ricon 257), 4 parts of polybutadiene-maleic anhydride copolymer (Kliviley Ricon130MA 8), 6 parts of polystyrene-maleic anhydride copolymer (Kliviley SMA 1000), 40 parts of BaTiO316 parts of PbTiO323 parts of flame retardant magnesium hydroxide (American Yabao MAGNIFIN H-5), 18 parts of secondary flame retardant decabromodiphenylethane (Shandonghai Wang chemical) and 450 parts of DMF solvent, stirring for 24 hours at 80 ℃, and fully dissolving and uniformly dispersing; cooling to room temperature, adding 1.5 parts of dibenzoyl peroxide, and further stirring uniformly; impregnating polytetrafluoroethylene fiber woven cloth, and baking and drying to obtain a prepreg, wherein the baking temperature in the first stage is 75 ℃ and the baking time is 7min, and the baking temperature in the second stage is 250 ℃ and the baking time is 15 min; getLaminating 10 prepregs, respectively attaching loz copper foils on two sides, and pressing at 90-110 kg/cm2And laminating for 5 hours at the temperature of 250 ℃ to obtain the thermosetting carbon-hydrogen polymer-based copper-clad plate.
Comparative example 1
Taking 70 parts of polyphenyl ether modified by vinyl end (Sabic SA 9000), 38 parts of polybutadiene (Craivrilion 130), 22 parts of polydiene-styrene-divinylbenzene terpolymer (Craivrilion 257), 8 parts of polystyrene-maleic anhydride copolymer (Craivrilion SMA 1000), and 22 parts of TiO250 parts of flame retardant magnesium hydroxide (American Yabao MAGNIFIN H-5), 20 parts of flame retardant decabromodiphenylethane (Shandonghai Wang chemical) and 450 parts of DMF solvent, stirring for 24 hours at 80 ℃, and fully dissolving and uniformly dispersing; cooling to room temperature, adding 1.2 parts of dibenzoyl peroxide, and further stirring uniformly; dipping glue with 1080 glass fiber cloth, and baking and drying to obtain a prepreg, wherein the baking temperature in the first stage is 75 ℃ and the baking time is 7min, and the baking temperature in the second stage is 250 ℃ and the baking time is 15 min; stacking 10 prepregs, respectively attaching loz copper foils to both sides of the prepregs under a pressure of 85-105 kg/cm2And laminating for 4 hours at the temperature of 250 ℃ to obtain the thermosetting carbon-hydrogen polymer-based copper-clad plate.
Comparative example 2
Taking 70 parts of polyphenyl ether modified by vinyl end groups (Sabic SA 9000), 38 parts of polybutadiene (Kliviley Ricon 130), 12 parts of polybutadiene-maleic anhydride copolymer (Kliviley Ricon130MA 8), 8 parts of polystyrene-maleic anhydride copolymer (Kliviley SMA 1000), and 22 parts of TiO250 parts of flame retardant magnesium hydroxide (American Yabao MAGNIFIN H-5), 20 parts of flame retardant decabromodiphenylethane (Shandonghai Wang chemical) and 435 parts of DMF solvent, stirring for 24 hours at 80 ℃, and fully dissolving and uniformly dispersing; cooling to room temperature, adding 1.15 parts of dibenzoyl peroxide, and further stirring uniformly; dipping glue with 1080 glass fiber cloth, and baking and drying to obtain a prepreg, wherein the baking temperature in the first stage is 75 ℃ and the baking time is 7min, and the baking temperature in the second stage is 250 ℃ and the baking time is 15 min; laminating 10 prepregs, attaching loz copper foils to both surfaces of the prepregs respectively, and pressing90~110kg/cm2And laminating for 4 hours at the temperature of 250 ℃ to obtain the thermosetting carbon-hydrogen polymer-based copper-clad plate.
Comparative example 3
Taking 70 parts of polyphenyl ether modified by vinyl end (Sabic SA 9000), 38 parts of polybutadiene (Craivrion Ricon 130), 22 parts of polydiene-styrene-divinylbenzene terpolymer (Craivrion Ricon 257) and 22 parts of TiO250 parts of flame retardant magnesium hydroxide (American Yabao MAGNIFIN H-5), 20 parts of flame retardant decabromodiphenylethane (Shandonghai Wang chemical) and 450 parts of DMF solvent, stirring for 24 hours at 80 ℃, and fully dissolving and uniformly dispersing; cooling to room temperature, adding 1.2 parts of dibenzoyl peroxide, and further stirring uniformly; dipping glue with 1080 glass fiber cloth, and baking and drying to obtain a prepreg, wherein the baking temperature in the first stage is 75 ℃ and the baking time is 7min, and the baking temperature in the second stage is 250 ℃ and the baking time is 15 min; stacking 10 prepregs, respectively attaching loz copper foils to both sides of the prepregs under a pressure of 90-110 kg/cm2And laminating for 4 hours at the temperature of 250 ℃ to obtain the thermosetting carbon-hydrogen polymer-based copper-clad plate.
Figure DEST_PATH_IMAGE001
In conclusion, the invention has good industrial production basis and wide application prospect.
The above examples are not intended to limit the amount of the composition of the present invention. Any minor modifications, equivalent changes and modifications to the above embodiments in accordance with the technical spirit or composition ingredients or contents of the present invention are within the scope of the technical solution of the present invention.

Claims (10)

1. A low-expansion cross-linkable hydrocarbon polymer composition, which is characterized by comprising more than seven types of components including matrix resin, negative expansion filler, compatilizer, modified resin, auxiliary filler, flame retardant and initiator;
the negative expansion filler is ZrW2O8、HfW2O8、NaZr2(PO4)3、Sc2W3O12、NaTi2P3O12、CaTi4P6O24、CaZr4P6O24、KZr(PO4)3、LiZr(PO4)3、NbZr(PO4)3、BaTiO3、PbTiO3、ThP2O7、BiNiO3And PbNiO3One or a mixture of several of them; the negative expansion filler accounts for 1-40 wt% of the low-expansion crosslinkable hydrocarbon polymer composition.
2. The low-expansion crosslinkable hydrocarbon polymer composition as claimed in claim 1, wherein the matrix resin is a composite mixture of vinyl-modified polyphenylene ether and one or more of derivatives thereof, and polydiene and one or more of derivatives thereof; the number average molecular weight of the polyphenyl ether is 400-10000, the vinyl functional groups exist on the end group or the side group of the polyphenyl ether, a single macromolecular chain of the polyphenyl ether at least contains 2 vinyl functional groups, and the vinyl modified polyphenyl ether accounts for 5-95 wt% of the matrix resin; the number average molecular weight of the polydiene is 500-20000, the side group of a single polydiene polymer chain at least contains 3 reactive carbon-carbon double bonds in total, and the dosage of the polydiene accounts for 5-95 wt% of the matrix resin.
3. A low expansion crosslinkable hydrocarbon polymer composition as claimed in claim 1, wherein said compatibilizer is one or a mixture of diene-styrene-divinylbenzene terpolymer and derivatives thereof; wherein the pendant group of the diene block of a single chain of said compatibilizer comprises at least one reactive carbon-carbon double bond; the styrene block accounts for 10-60 wt% of the compatilizer; the divinylbenzene block accounts for 0.5-50 wt% of the compatilizer; the molecular weight of the compatilizer is 400-20000, and the usage amount of the compatilizer accounts for 1-20 wt% of the low-expansion crosslinkable hydrocarbon polymer composition.
4. The crosslinkable hydrocarbon polymer composition with low expansion as claimed in claim 1, wherein the modified resin is a composite mixture of one or more of diene-maleic anhydride copolymer and its derivatives, and one or more of styrene-maleic anhydride copolymer and its derivatives; wherein a pendant group of a polydiene block of a single said diene-maleic anhydride copolymer chain contains at least one reactive carbon-carbon double bond; the number average molecular weight of the diene-maleic anhydride copolymer is 500-150000, and the amount of the diene-maleic anhydride copolymer accounts for 5-95 wt% of the modified resin; the number average molecular weight of the styrene-maleic anhydride copolymer is 500-30000, and the amount of the styrene-maleic anhydride copolymer accounts for 5-95 wt% of the modified resin; the amount of the modified resin is 1-20 wt% of the low-expansion crosslinkable hydrocarbon polymer composition.
5. A low expansion crosslinkable hydrocarbon polymer composition according to claim 1 wherein the auxiliary filler is SiO2、Al2O3、TiO2、ZnO、MgO、Bi2O3、AlN、Si3N4、SiC、BN、Al(OH)3、Mg(OH)2、BaTiO3、SrTiO3、Mg2TiO4、Bi2(TiO3)3、PbTiO3、NiTiO3、CaTiO3、ZnTiO3、Zn2TiO4、BaSnO3、Bi2(SnO3)3、CaSnO3、PbSnO3、MgSnO3、SrSnO3、ZnSnO3、BaZrO3、CaZrO3、PbZrO3、MgZrO3、SrZrO3、ZnZrO3One or a mixture of more of graphite oxide, graphite fluoride, talcum powder, mica powder, kaolin, clay, solid glass microspheres, hollow glass microspheres, glass fibers, basalt fibers and carbon fibers, and also comprises a polytetrafluoroethylene pre-sintering material, ultra-high molecular weight polyethylene fibers, Kevlar fibers, polyimideOne or a mixture of more of polyetherimide, polyetheretherketone and polyphenylene sulfide; the auxiliary filler is used in an amount of 0 to 50wt% of the low-expansion crosslinkable hydrocarbon polymer composition.
6. A low expansion crosslinkable hydrocarbon polymer composition according to claim 1, wherein the flame retardant is a mixture of one or more of aluminum magnesium flame retardants, boron zinc flame retardants, molybdenum tin flame retardants, bromine flame retardants, antimony trioxide, phosphorus flame retardants, nitrogen flame retardants and derivatives thereof; the amount of the flame retardant is 0-40 wt% of the low-expansion crosslinkable hydrocarbon polymer composition.
7. The low-expansion crosslinkable hydrocarbon polymer composition according to claim 1, wherein the initiator is one or more of a peroxide, an azo compound and a radical initiator of a redox system soluble in a solvent for uniformly dispersing the low-expansion crosslinkable hydrocarbon polymer composition, and is used in an amount of 0.01 to 5wt% based on the low-expansion crosslinkable hydrocarbon polymer composition.
8. A prepreg prepared by using the low-expansion crosslinkable hydrocarbon polymer composition according to claim 1, which is characterized by comprising the following specific steps:
s1, preparing a uniform dispersion liquid of the low-expansion crosslinkable hydrocarbon polymer composition with the solid content of 30-70 wt/v%;
and S2, soaking the fiber cloth in the uniform dispersion liquid, and baking and drying to obtain a prepreg.
9. The prepreg according to claim 8, wherein the solvent of the uniform dispersion is one of water, an organic solvent, or a mixture thereof, which can uniformly disperse the low-swelling crosslinkable hydrocarbon polymer composition;
the fiber cloth is one of 106, 1080 or 2116 electronic grade alkali-free glass fiber cloth, carbon fiber, boron fiber, Kevlar, polyimide, polytetrafluoroethylene, polyester and polytetrafluoroethylene fiber cloth;
the baking and drying are divided into two stages, wherein the baking and drying temperature of the first stage is 50-120 ℃, and the baking and drying time is 1-30 min; the second stage baking and drying temperature is 150-350 ℃, and the time is 1-30 min.
10. A thermosetting copper-clad plate manufactured by using a prepreg prepared from the low-expansion crosslinkable hydrocarbon polymer composition according to claim 8 is characterized by comprising the following specific steps: laminating a prepreg, a film and copper foil coated on the surface together, and preparing the thermosetting copper-clad plate by a laminating process; the number of the prepregs is more than or equal to 1, the number of the films is more than or equal to 0, and the number of the copper foils is 1 or 2;
the laminating temperature of the laminating process is 180-250 ℃, and the laminating pressure is 50-120 kg/cm2The laminating time is 0.5-24 h;
the film is one or a mixture of more of fluorine-containing polymer, polyimide, polyolefin, polyaromatic hydrocarbon, polyamide, polyether ketone, polyether ether ketone, polyaryl ether, polyaryl sulfide, polyaryl ether sulfone, polyaryl ether ketone, polyaryl sulfide ketone, polyether sulfone ketone, polyaryl ether nitrile sulfone, polyaryl sulfide nitrile sulfone, polyphenyl quinoxaline, phenolic resin, epoxy resin, cyanate resin, polycarbonate, polyurethane and polyformaldehyde and derivatives thereof;
the thickness of the thermosetting copper-clad plate is controlled to be 0.1-10 mm.
CN202011039032.4A 2020-09-28 2020-09-28 Low-expansion crosslinkable hydrocarbon polymer composition, prepreg prepared from low-expansion crosslinkable hydrocarbon polymer composition and thermosetting copper-clad plate Pending CN112111144A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113665207A (en) * 2021-08-19 2021-11-19 郴州功田电子陶瓷技术有限公司 Method for efficiently reducing thermal expansion coefficient of polytetrafluoroethylene copper-clad plate

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CN108659504A (en) * 2018-05-17 2018-10-16 常州中英科技股份有限公司 A kind of composition of cross-linking hydrocarbon polymer and its prepreg and the heat curing type copper-clad plate of preparation

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108659504A (en) * 2018-05-17 2018-10-16 常州中英科技股份有限公司 A kind of composition of cross-linking hydrocarbon polymer and its prepreg and the heat curing type copper-clad plate of preparation

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113665207A (en) * 2021-08-19 2021-11-19 郴州功田电子陶瓷技术有限公司 Method for efficiently reducing thermal expansion coefficient of polytetrafluoroethylene copper-clad plate

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