CN108659504B - Composition of crosslinkable hydrocarbon polymer and prepreg and thermosetting copper-clad plate prepared from composition - Google Patents
Composition of crosslinkable hydrocarbon polymer and prepreg and thermosetting copper-clad plate prepared from composition Download PDFInfo
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- 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
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- 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
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- 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
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- 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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- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
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- 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
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- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
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- 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
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- 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
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/204—Di-electric
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- 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
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/308—Heat stability
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/546—Flexural strength; Flexion stiffness
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- 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
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- 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
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- 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 composition of a crosslinkable hydrocarbon polymer, a prepreg and a thermosetting copper-clad plate prepared from the composition, which have the advantages of excellent dielectric property, high mechanical strength, high glass transition temperature and heat resistance, low thermal expansion coefficient, high copper foil peel strength and good uniformity of various properties, are suitable for manufacturing a multilayer copper-clad plate, and can meet various performance requirements of diversification and complication of functions of the copper-clad plate material in the field of high-frequency and high-speed communication. Therefore, the method has good industrial production basis and wide application prospect.
Description
Technical Field
The invention belongs to the field of communication materials, and particularly relates to a composition of a crosslinkable hydrocarbon polymer, and a prepreg and a thermosetting copper-clad plate prepared from the 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, low thermal expansion coefficient, 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, 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.
Later, polyphenyl ether-based thermosetting copper clad laminates have been developed to improve the dielectric properties of the plates in the high frequency field. At present, thermosetting polyphenylene ether resins can be classified into two major types, namely side vinyl modification and terminal vinyl modification. In the preparation process of the side vinyl modified polyphenyl ether, substances with strong reactivity, high risk and high toxicity such as butyl lithium and the like are required, the production process is very complex, and the commercialization is not realized at present. Vinyl-terminated modified polyphenylene ethers have been commercialized, however, the curing process thereof requires the addition of an additional crosslinking agent. For example, CN1745142A and WO2006/023371a1 adopt TAIC, unsaturated olefin monomer and the like as small-molecule crosslinking curing agents of thermosetting polyphenylene ether, however, in the production processes of gumming, prepreg baking and the like, such small-molecule crosslinking curing agents are very volatile, which results in difficult control of the curing degree of polyphenylene ether and the quality of prepreg, and serious pollution. To solve this problem, CN102807658B and CN103467967A were modified with a polymeric crosslinking curing agent such as polydiene. However, polyphenylene ethers generally have poor compatibility with other resins, except polystyrene, resulting in severe phase separation of the resins in the prepreg composite matrix and poor adhesion between the matrix resin and reinforcing materials such as fillers and fiber cloths. The copper-clad plate prepared by the method has general thermal-mechanical stability, and poor uniformity of dielectric properties and thermal expansion coefficients of different parts, is not suitable for manufacturing a multilayer copper-clad plate, and is difficult to meet various requirements of diversification and complication of functions, high density of circuit arrangement and the like of the copper-clad plate material in the fields of high frequency and high speed communication.
Disclosure of Invention
The invention provides a composition of a crosslinkable hydrocarbon polymer, and a prepreg and a thermosetting copper-clad plate prepared from the 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 filler, flame retardant and initiator in proper types and proportions to prepare the composition of the crosslinkable hydrocarbon polymer. The polydiene-styrene-divinylbenzene terpolymer effectively increases the compatibility between the two matrix resins of the polyphenylene oxide and the polydiene; the existence of the maleic anhydride graft copolymer further enhances the interaction among the filler, the matrix resin and the compatilizer, and improves the dispersibility of the filler in the composition. Then, the uniform dispersion liquid of the composition is soaked by fiber cloth, and the prepreg with uniform gel content, strong resin adhesive force, smooth surface, and proper toughness and viscosity is prepared by baking and other steps. The invention also relates to a thermosetting copper-clad plate prepared from a prepreg, a film and a copper foil prepared from the composition of the cross-linkable hydrocarbon polymer, which has the advantages of 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 plate, and can meet various performance requirements of diversified and complicated functions of the copper-clad plate material in the fields of high frequency and high speed communication.
The invention provides a composition of crosslinkable hydrocarbon polymer, which is characterized by comprising more than six types of components including matrix resin, compatilizer, modified resin, filler, flame retardant and initiator.
In the invention, 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 contains more than or equal to 2 vinyl functional groups, and the amount of 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 contains more than or equal to 3 reactive carbon-carbon double bonds in total, and the dosage of the polydiene accounts for 5-95 wt% of the matrix resin.
In the invention, the compatilizer is one or a mixture of a plurality of polydiene-styrene-divinylbenzene terpolymer and derivatives thereof; wherein the pendant group of the polydiene block of a single compatibilizer chain contains at least one reactive carbon-carbon double bond; the polystyrene 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 consumption of the compatilizer accounts for 1-90 wt% of the crosslinkable hydrocarbon polymer composition.
In the invention, 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 1-40 wt% of the crosslinkable hydrocarbon polymer composition.
In the invention, the filler is SiO2、Al2O3、TiO2、ZnO、MgO、Bi2O3、AlN、Si3N4、SiC、Al(OH)3、Mg(OH)2、BaxSr1-xTiO3(x=1~0)、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 inorganic fillers such as 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 organic fillers such as polytetrafluoroethylene pre-sintering materials, ultra-high molecular weight polyethylene fibers, Kevlar fibers, polyimide, polyetherimide, polyether ether ketone and polyphenylene sulfide; the filler accounts for 1-80 wt% of the crosslinkable hydrocarbon polymer composition.
In the invention, 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 1-65 wt% of the crosslinkable hydrocarbon polymer composition.
In the invention, the initiator is one or a mixture of more of peroxide, azo compound, redox system and other free radical initiators which can be dissolved in a solvent for uniformly dispersing the crosslinkable hydrocarbon polymer composition, and the dosage of the initiator accounts for 0.01-5 wt% of the crosslinkable hydrocarbon polymer composition.
The invention also provides a prepreg prepared from the crosslinkable hydrocarbon polymer composition, which is characterized by comprising the following specific steps:
(1) preparing a uniform dispersion liquid of the crosslinkable hydrocarbon polymer composition with the solid content of 20-75 wt/v%;
(2) soaking the fiber cloth in the uniform dispersion liquid, and baking and drying to obtain a prepreg;
in the invention, the solvent of the uniform dispersion liquid of the crosslinkable hydrocarbon polymer composition is one of water and an organic solvent or a mixture of several of water and the organic solvent which can uniformly disperse the crosslinkable hydrocarbon polymer composition; the fiber cloth is one of electronic grade alkali-free glass fiber cloth of 106, 1080 or 2116 and the like, carbon fiber, boron fiber, Kevlar, polyimide, polytetrafluoroethylene, polyester and the like; 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.
The invention further provides a thermosetting copper-clad plate prepared from a prepreg prepared from the crosslinkable hydrocarbon polymer composition, which 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 150-350 ℃, and the laminating pressure is 70-170 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.
Therefore, the method has good industrial production basis and wide application prospect.
Detailed Description
The following examples further illustrate the crosslinkable hydrocarbon polymer composition and the prepreg and thermosetting copper clad laminate prepared from the crosslinkable hydrocarbon polymer composition. However, this example is provided only as an illustration and not as a limitation of the invention.
Example 1
65 parts of vinyl-terminated modified polyphenylene ether (Sabic SA 9000), 35 parts of polybutadiene (Klivili Ricon 130), 20 parts of polydiene-styrene-divinylbenzene terpolymer (Klivili Ricon 257), 8 parts of polybutadiene-maleic anhydride copolymer (Klivili Ricon130MA 8), 12 parts of polystyrene-maleic anhydride copolymer (Klivili SMA 1000) and 22 parts of TiO2(Tech of Tianjin Zhonghuamei), 50 parts of flame retardant magnesium hydroxide (American jaba MAGNIFIN H-5), 20 parts of secondary flame retardant decabromodiphenylethane (Shandonghai Wang chemical) and 450 parts of DMF solvent, stirring for 24h at 80 ℃, and fully dissolving-dispersing uniformly; cooling to room temperature, adding 1.2 parts of dibenzoyl peroxide (Qin Feng chemical industry), 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 8 hours at the temperature of 320 ℃ to obtain the thermosetting carbon-hydrogen polymer-based copper-clad plate.
Example 2
60 parts of polyphenyl ether modified by vinyl end groups (Sabic SA 9000), 30 parts of polybutadiene (Kliviley Ricon 130), 22.5 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), 35 parts of polytetrafluoroethylene pre-sintering material (Shandongduoyue), 8 parts of SiO2(Xinyihongrun), 28 parts of flame retardant magnesium hydroxide (American Yabao MAGNIFIN H-5), 18 parts of flame retardant decabromodiphenylethane (Shandonghai Wang 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 12 parts of dibenzoyl peroxide (Qinfeng chemical industry), 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 8 hours at the temperature of 330 ℃ to obtain the thermosetting carbon-hydrogen polymer-based copper-clad plate.
Example 3
Taking 20 parts of vinyl-terminated modified polyphenylene ether (Sabic SA 9000), 80 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 polytetrafluoroethylene pre-sintered material (Shandongye), 23 parts of flame retardant magnesium hydroxide (American jabao MAGNIFINH-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 (Qin Feng chemical industry), 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; stacking 10 prepregs, respectively attaching loz copper foils to both sides of the prepregs under a pressure of 90-110 kg/cm2And laminating for 8 hours at the temperature of 320 ℃ to obtain the thermosetting carbon-hydrogen polymer-based copper-clad plate.
Comparative example 1
65 parts of vinyl-terminated modified polyphenylene ether (Sabic SA 9000), 35 parts of polybutadiene (Klivili Ricon 130), 8 parts of polybutadiene-maleic anhydride copolymer (Klivili Ricon130MA 8), 12 parts of polystyrene-maleic anhydride copolymer (Klivili SMA 1000), and 22 parts of TiO2(Tech. Zhonghuamei science and technology in Tianjin), 50 parts of flame retardant magnesium hydroxide (American Yabao MAGNIFIN H-5), and 20 parts of secondary flame retardant decabromodiphenylethane (Shandong sea king)Chemical) and 435 parts of DMF solvent, stirring for 24 hours at 80 ℃, and fully dissolving-dispersing uniformly; cooling to room temperature, adding 1.15 parts of dibenzoyl peroxide (Qin Feng chemical industry), 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 8 hours at the temperature of 320 ℃ to obtain the thermosetting carbon-hydrogen polymer-based copper-clad plate.
Comparative example 2
65 parts of vinyl-terminated modified polyphenylene ether (Sabic SA 9000), 35 parts of polybutadiene (Kliviley Ricon 130), 20 parts of polydiene-styrene-divinylbenzene terpolymer (Kliviley Ricon 257) and 22 parts of TiO2(Tech of Tianjin Zhonghuamei), 50 parts of flame retardant magnesium hydroxide (American jaba MAGNIFIN H-5), 20 parts of secondary flame retardant decabromodiphenylethane (Shandonghai Wang chemical) and 450 parts of DMF solvent, stirring for 24h at 80 ℃, and fully dissolving-dispersing uniformly; cooling to room temperature, adding 1.2 parts of dibenzoyl peroxide (Qin Feng chemical industry), 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 8 hours at the temperature of 320 ℃ to obtain the thermosetting carbon-hydrogen polymer-based copper-clad plate.
As shown in Table 1, the polydiene-styrene-divinylbenzene terpolymer effectively increases the compatibility between the two matrix resins, namely polyphenylene oxide and polydiene, and the existence of the maleic anhydride graft copolymer further enhances the interaction among the filler, the matrix resin and the compatilizer, so that the dispersibility of the filler in the composition is improved, and therefore, the prepreg has the advantages of uniform gel content, strong resin adhesion, smooth surface, and proper toughness and viscosity. The thermosetting carbon-hydrogen polymer-based copper-clad plate prepared by the method 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 plate, and can meet various performance requirements of diversification and complication of functions of the copper-clad plate material in the field of high-frequency and high-speed communication.
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 (4)
1. The composition of crosslinkable hydrocarbon polymer is characterized by comprising six components of matrix resin, compatilizer, modified resin, filler, flame retardant and initiator;
the matrix resin is a composite mixture of one or more of vinyl modified polyphenyl ether and one or more of polydiene; 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 compatilizer is one or a mixture of more of polydiene-styrene-divinylbenzene terpolymer; wherein the pendant group of the polydiene block of a single compatibilizer chain contains at least one reactive carbon-carbon double bond; the polystyrene 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 1-90 wt% of the crosslinkable hydrocarbon polymer composition;
the modified resin is a composite mixture of one or more of diene-maleic anhydride copolymer and one or more of styrene-maleic anhydride copolymer; 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 accounts for 1-40 wt% of the crosslinkable hydrocarbon polymer composition;
the 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 fiber inorganic fillers, and also comprises 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 organic fillers; the filler is used in the amount of the crosslinkable filler0-80 wt% of a bihydrocarbon polymer composition;
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 and nitrogen flame retardant; the amount of the flame retardant accounts for 1-65 wt% of the crosslinkable hydrocarbon polymer composition;
the initiator is one or a mixture of more of peroxide, azo compound and redox system free radical initiator which can be dissolved in a solvent for uniformly dispersing the crosslinkable hydrocarbon polymer composition, and the dosage of the initiator accounts for 0.01-5 wt% of the crosslinkable hydrocarbon polymer composition.
2. A prepreg prepared by using the crosslinkable hydrocarbon polymer composition according to claim 1, characterized by comprising the specific steps of:
(1) preparing a uniform dispersion liquid of the crosslinkable hydrocarbon polymer composition with the solid content of 20-75 wt/v%;
(2) and soaking the fiber cloth in the uniform dispersion liquid, and baking and drying to obtain a prepreg.
3. The prepreg according to claim 2, wherein the solvent of the homogeneous dispersion of the crosslinkable hydrocarbon polymer composition is one of water, an organic solvent, or a mixture thereof, which can uniformly disperse the 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 and polyester 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.
4. A thermosetting copper-clad plate manufactured by adopting the prepreg according to claim 2 or 3 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 150-350 ℃, and the laminating pressure is 70-170 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;
the thickness of the thermosetting copper-clad plate is controlled to be 0.1-10 mm.
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| CN110605880B (en) * | 2019-08-07 | 2021-09-10 | 常州中英科技股份有限公司 | Thermosetting hydrocarbon polymer composition, prepreg prepared from thermosetting hydrocarbon polymer composition and thermosetting copper-clad plate |
| CN111393824B (en) * | 2020-04-23 | 2022-07-08 | 泰州市旺灵绝缘材料厂 | High-frequency high-speed resin composition |
| CN111574818B (en) * | 2020-05-25 | 2023-03-31 | 常州中英科技股份有限公司 | Polyarylether base composition containing reversible thermal shrinkage and cold expansion structural unit and prepreg and carbon-hydrogen copper-clad plate prepared from polyarylether base composition |
| CN111534076A (en) * | 2020-05-25 | 2020-08-14 | 常州中英科技股份有限公司 | Polyarylether base composition containing reversible thermal shrinkage and cold expansion structural unit and prepreg and thermosetting copper-clad plate prepared from polyarylether base composition |
| CN112111144A (en) * | 2020-09-28 | 2020-12-22 | 常州中英科技股份有限公司 | Low-expansion crosslinkable hydrocarbon polymer composition, prepreg prepared from low-expansion crosslinkable hydrocarbon polymer composition and thermosetting copper-clad plate |
| CN112111074B (en) * | 2020-09-28 | 2023-08-18 | 常州中英科技股份有限公司 | Uniform dispersion liquid of crosslinkable hydrocarbon resin composition, prepreg prepared from uniform dispersion liquid and high-heat-conductivity thermosetting copper-clad plate prepared from uniform dispersion liquid |
| CN113150457A (en) * | 2021-01-05 | 2021-07-23 | 广州辰东新材料有限公司 | Modified hydrocarbon-modified syndiotactic polystyrene composite material, copper-clad plate containing modified hydrocarbon-modified syndiotactic polystyrene composite material and preparation method of copper-clad plate |
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