CN110605880B - Thermosetting hydrocarbon polymer composition, prepreg prepared from thermosetting hydrocarbon polymer composition and thermosetting copper-clad plate - Google Patents

Thermosetting hydrocarbon polymer composition, prepreg prepared from thermosetting hydrocarbon polymer composition and thermosetting copper-clad plate Download PDF

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CN110605880B
CN110605880B CN201910723890.1A CN201910723890A CN110605880B CN 110605880 B CN110605880 B CN 110605880B CN 201910723890 A CN201910723890 A CN 201910723890A CN 110605880 B CN110605880 B CN 110605880B
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thermosetting
polymer composition
resin
hydrocarbon polymer
copper
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CN110605880A (en
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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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Abstract

The invention belongs to the field of communication materials, and particularly relates to a thermosetting hydrocarbon polymer composition, a prepreg prepared from the thermosetting hydrocarbon polymer composition and a thermosetting copper-clad plate. Firstly, preparing polyarylether-polyolefin block copolymer; and preparing the thermosetting hydrocarbon polymer composition with adjustable dielectric property, flame retardant property and the like. 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. Finally, the thermosetting copper-clad plate prepared from the prepreg, the film and the copper foil 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, good uniformity of various properties and obvious cost advantage, and is suitable for manufacturing a multilayer copper-clad plate. Therefore, the method has good industrial production basis and wide application prospect.

Description

Thermosetting hydrocarbon polymer composition, prepreg prepared from thermosetting hydrocarbon polymer composition and thermosetting copper-clad plate
Technical Field
The invention belongs to the technical field of communication materials, and particularly relates to a thermosetting hydrocarbon polymer composition, a prepreg prepared from the thermosetting hydrocarbon polymer composition and a thermosetting copper-clad plate.
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, people developed a thermosetting polyolefin-based copper-clad plate, and the dielectric property of the plate in the high-frequency field was improved. In order to further improve the copper foil peeling strength, glass transition temperature and mechanical strength of the board, vinyl modified polyarylether is introduced into a thermosetting polyolefin matrix. However, except for polystyrene, the polyarylether generally has poor compatibility with other resins, so that the resin phase separation in the composite prepreg substrate is serious, the adhesive force between the substrate resin and reinforcing materials such as filler and fiber cloth is poor, the thermal-mechanical property stability of the prepared copper-clad plate is general, the dielectric properties and the uniformity of thermal expansion coefficients of different parts are poor, the copper-clad plate is not suitable for manufacturing a multilayer copper-clad plate, and the requirements of the high-frequency and high-speed communication fields on the diversification and complication of the functions of the copper-clad plate material, high density of circuit arrangement and the like are difficult to meet. The common solution is to additionally introduce polydiene-styrene binary copolymer and derivatives thereof as a compatilizer to improve the compatibility between the thermosetting polyolefin matrix and the vinyl modified polyarylether.
The present invention provides another solution path. Firstly, preparing polyarylether-polyolefin block copolymer, on one hand, taking the polyarylether-polyolefin block copolymer as a compatilizer, and obviously enhancing the compatibility between polydiene and vinyl modified polyarylether and other matrix resins; on the other hand, the residual reactable carbon-carbon double bonds at the two ends of the board directly participate in the co-curing reaction of the matrix resin, so that the uniformity, the thermo-mechanical property and the stability of the board are ensured; and then is supplemented with filler, modified resin, flame retardant and other compatilizer resin with proper types and proportions to prepare the thermosetting hydrocarbon polymer composition with adjustable dielectric property, flame retardant property and the like. 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. Finally, the thermosetting copper clad laminate prepared by the prepreg, the film and the copper foil 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, good uniformity of various properties and obvious cost advantage, 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 field of current high-frequency and high-speed communication.
Disclosure of Invention
The invention aims to provide a thermosetting hydrocarbon polymer composition and a prepreg and a thermosetting copper-clad plate prepared from the thermosetting hydrocarbon polymer composition, firstly, a polyarylether-polyolefin block copolymer is prepared, and on one hand, the polyarylether-polyolefin block copolymer is taken as a compatilizer, so that the compatibility between polydiene and vinyl modified polyarylether and other matrix resins is obviously enhanced; on the other hand, the residual reactable carbon-carbon double bonds at the two ends of the board directly participate in the co-curing reaction of the matrix resin, so that the uniformity, the thermo-mechanical property and the stability of the board are ensured; and then is supplemented with filler, modified resin, flame retardant and other compatilizer resin with proper types and proportions to prepare the thermosetting hydrocarbon polymer composition with adjustable dielectric property, flame retardant property and the like. 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. Finally, the thermosetting copper clad laminate prepared by the prepreg, the film and the copper foil 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, good uniformity of various properties and obvious cost advantage, 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 field of current high-frequency and high-speed communication. Therefore, the method has good industrial production basis and wide application prospect.
The technical scheme adopted by the invention for solving the problems is as follows: a thermosetting hydrocarbon polymer composition and a prepreg and a thermosetting copper-clad plate prepared from the thermosetting hydrocarbon polymer composition comprise the following specific preparation steps:
s1, dissolving dihydroxy type or polyhydroxy type polyarylether resin and hydrogenated hydroxyl-terminated polyolefin resin in an organic solvent A, adding vinyl halide and alkali, stirring at a temperature of P1 for 0.5-120 h, adding an initiator A, and continuously stirring at a temperature of P2 for 1 min-48 h to obtain a reactive resin A solution;
s2, adding polydiene resin, vinyl-modified polyarylether resin and initiator B into the reactive resin A solution, and uniformly stirring to obtain the thermosetting hydrocarbon polymer composition;
s3, preparing a uniform dispersion liquid of a thermosetting hydrocarbon polymer composition with a solid content of 20-75 wt/v%, impregnating fiber cloth with the uniform dispersion liquid, and baking and drying to obtain a prepreg;
and S4, overlapping the prepreg and the copper foil covered on the surface together, and preparing the thermosetting copper-clad plate through a laminating process.
The further preferred technical scheme is as follows: in step S1, the dihydroxy or polyhydroxy polyarylether resin refers to a mixture of one or more of the following polymers with the following chemical structures in the molecular chain:
Figure 100002_DEST_PATH_IMAGE002
wherein R1, R2 and R3 each independently represent one of the following functional groups:
Figure DEST_PATH_IMAGE003
wherein R is37~R42Each independently generateC1-C12 hydrocarbon chains or aryl groups; preferred R1、R2And R3Is methylene;
wherein R is4、R5And R6Each independently represents H and a C1-C12 carbon hydrocarbon chain, preferably H and methyl;
wherein R is7~R36Each independently represents a C1-C12 hydrocarbon chain or an aryl group, preferably a methyl group;
wherein, T1、T2And T3Wherein not less than 2 functional groups are hydroxyl; t is4、T5And T6Wherein not less than 2 functional groups are hydroxyl; t is7、T8、T9And T10Not less than 2 functional groups are hydroxyl groups;
in addition, C1-C12 carbon hydrocarbon chains or aryl groups can be grafted on 3 and 5 positions of a molecular chain repeating unit of the dihydroxy type or polyhydroxy type polyarylether resin;
the number average molecular weight of the dihydroxy type or polyhydroxy type polyarylether resin is 600-10000, and the concentration of the dihydroxy type or polyhydroxy type polyarylether resin in a reactive resin A solution is less than or equal to 75 wt/v%.
The further preferred technical scheme is as follows: in step S1, while dissolving the dihydroxy or polyhydroxy polyarylether resin, monohydroxy polyarylether resin and hydroxy-terminated polydiene resin may be added, wherein the hydrogenated hydroxy-terminated polyolefin resin and the hydroxy-terminated polydiene resin have number average molecular weights of 600 to 10000 and both account for 10 to 60wt% of the dihydroxy or polyhydroxy polyarylether resin; the ratio of the hydroxyl-terminated polydiene resin to the hydrogenated hydroxyl-terminated polyolefin resin is controlled to be 0: 100-80: 20; the monohydroxy polyarylether resin has a number average molecular weight of more than 15000.
The further preferred technical scheme is as follows: in step S1, the organic solvent a includes one or a mixture of more of acetone, methyl ethyl ketone, methyl isobutyl ketone, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone, which are aprotic polar solvents, or a mixture of one or more of benzene, toluene, xylene, and nitrobenzene, which are aprotic polar solvents.
In step S1, the vinyl halide is one or a mixture of several of the following substances:
Figure DEST_PATH_IMAGE005
wherein X represents Cl, Br and I, preferably Br; r43Not specifically defined, preferably a C1-C4 hydrocarbon chain or aryl group; r44、R45And R46Each independently represents H, methyl and ethyl, preferably H;
the number of moles of the vinyl halide is the same as the total number of moles of hydroxyl groups contained in the dihydroxy or polyhydroxy polyarylether resin, the hydrogenated hydroxyl-terminated polyolefin resin, the monohydroxy polyarylether resin and the hydroxyl-terminated polydiene resin.
The further preferred technical scheme is as follows: in step S1, the alkali is one or a mixture of more of n-butyllithium, sec-butyllithium, tert-butyllithium, lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, potassium tert-butoxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, and potassium carbonate; the number of moles of the base is the same as the number of moles of the vinyl halide; the initiator A is one or a mixture of more of free radical initiators such as peroxide, azo compounds, redox systems and the like which can be dissolved in a solvent which can uniformly disperse the thermosetting hydrocarbon polymer composition.
The further preferred technical scheme is as follows: in step S1, the temperature P1 is-78 ℃ to 150 ℃, and when the boiling point of the organic solvent a is lower than 150 ℃, the upper limit of P1 is set to the boiling point of the organic solvent a, and when the freezing point of the organic solvent is higher than-78 ℃, the lower limit of P1 is set to the freezing point of the organic solvent a; the temperature P2 is 40-200 ℃, and when the boiling point of the organic solvent A is lower than 200 ℃, the upper limit of P2 is set to the boiling point of the organic solvent A.
The further preferred technical scheme is as follows: in step S2, the number average molecular weight of the polydiene resin is 400-20000; on average, 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 ratio of the dosage of the polydiene resin to the reactive resin A is 99: 1-20: 80;
the number average molecular weight of the vinyl-modified polyarylether resin is 400-10000, the vinyl exists in the terminal group or the side group of a polyarylether molecular chain, and the single vinyl-modified polyarylether molecular chain contains more than or equal to 2 vinyl groups; the ratio of the amount of the vinyl-modified polyarylether resin to the amount of the reactive resin A is 80: 20-1: 99.
The further preferred technical scheme is as follows: in step S2, a filler, a flame retardant, a compatibilizer, and a modified resin may be added while the polydiene resin is added, and each initiator B independently represents one or a mixture of several radical initiators, such as a peroxide, an azo compound, and a redox system, that are soluble in a solvent in which the thermosetting hydrocarbon polymer composition is uniformly dispersed;
in the step S1, the dosage of the initiator A accounts for 0.01-5 wt% of the reactive resin A; in the step (2), the amount of the initiator B accounts for 0.001-8 wt% of the thermosetting hydrocarbon polymer composition;
the filler in the step S2 is SiO2、Al2O3、TiO2、ZnO、MgO、Bi2O3、AlN、Si3N4、SiC、BN、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 0-75 wt% of the thermosetting hydrocarbon polymer composition;
the flame retardant in the step S2 is one or a mixture of more of an aluminum magnesium flame retardant, a boron zinc flame retardant, a molybdenum tin flame retardant, a bromine flame retardant, antimony trioxide, a phosphorus flame retardant, a nitrogen flame retardant and derivatives thereof; the amount of the flame retardant accounts for 0-65 wt% of the thermosetting hydrocarbon polymer composition;
the compatilizer in the step S2 is one or a mixture of more of diene-styrene binary copolymer, diene-styrene-divinylbenzene ternary copolymer and derivatives thereof; wherein, the pendant group of the polydiene block of the single compatilizer polymer chain at least contains a reactive carbon-carbon double bond; the polydiene block accounts for 30-90 wt% of the compatilizer; the number average molecular weight of the compatilizer is 400-20000, and the usage amount of the compatilizer accounts for 0-30 wt% of the thermosetting hydrocarbon polymer composition;
the modified resin in the step S2 is one or a composite mixture of a plurality of diene-maleic anhydride copolymer, styrene-maleic anhydride copolymer and derivatives thereof; wherein, the lateral group of the polydiene block of a single diolefin-maleic anhydride copolymer chain at least contains a reactive carbon-carbon double bond, and the number average molecular weight of the diolefin-maleic anhydride copolymer is 500-150000; the number average molecular weight of the styrene-maleic anhydride copolymer is 500-30000; the amount of the modified resin accounts for 0-30 wt% of the thermosetting hydrocarbon polymer composition;
the further preferred technical scheme is as follows: in step S3, the solvent of the uniform dispersion liquid is one of water and an organic solvent or a mixture of several of water and an organic solvent, which can uniformly disperse the thermosetting hydrocarbon polymer composition;
the fiber cloth is one of electronic grade alkali-free glass fiber cloth such as 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 further preferred technical scheme is as follows: in step S4, the thermosetting copper-clad plate further includes a film, where the film is a mixture of one or more of fluoropolymers, polyimides, polyolefins, polyaromatic hydrocarbons, polyamides, polyether ketones, polyether ether ketones, polyaryl ethers, polyarylene sulfides, polyarylene ether sulfones, polyarylene sulfide sulfones, polyarylene ether ketones, polyarylene sulfide ketones, polyether sulfone ketones, polyarylene ether sulfone nitriles, polyarylene sulfide sulfone nitriles, polyphenylquinoxalines, phenolic resins, epoxy resins, cyanate resins, polyesters, polycarbonates, polyurethanes, and polyoxymethylenes, and derivatives thereof;
in the step S4, 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 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 thermosetting hydrocarbon polymer composition, a prepreg and a thermosetting copper clad laminate prepared from the composition by the following embodiments. However, this example is provided only as an illustration and not as a limitation of the invention.
Example 1
16 parts of a hydroxyl-terminated polyphenylene ether resin (A)Sabic SA 90) and 4 parts of hydrogenated hydroxyl-terminated polyolefin resin (Krasol HLBH-P2000) were dissolved in 100 parts of methyl ethyl ketone, and 2.7 parts of 3-bromopropylene and 2.5 parts of potassium tert-butoxide were added, and stirred for 2 hours under reflux condensation; then adding 0.03 initiator dibenzoyl peroxide (Qinfeng chemical engineering), and continuing stirring for 5 hours under the condition of condensation reflux to obtain a reactive resin A solution; subsequently, 65 parts of vinyl-terminated modified polyphenylene ether (Sabic SA 9000), 35 parts of polybutadiene (kleiviral Ricon 130), 8 parts of polybutadiene-maleic anhydride copolymer (kleiviral Ricon130MA 8), 12 parts of polystyrene-maleic anhydride copolymer (kleiviral SMA 1000), and 22 parts of TiO were further added to the reactive resin a solution2(Tech. Zhonghuamei science and technology in Tianjin), 50 parts of flame retardant magnesium hydroxide (American jaba MAGNIFIN H-5), 20 parts of secondary flame retardant decabromodiphenylethane (Shandonghai Wang chemical) and 350 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 of the first stage is 75 ℃ and the baking time is 7min, the baking temperature of 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 270 ℃ to obtain the thermosetting carbon-hydrogen polymer-based copper-clad plate.
Example 2
13 parts of hydroxyl-terminated polyphenylene ether resin (Sabic SA 90), 4 parts of hydrogenated hydroxyl-terminated polyolefin resin (Krasol HLBH-P2000) and 3 parts of monohydroxypolyether resin (Mn = 13000) were dissolved in a mixed solvent of 50 parts of methyl ethyl ketone and 50 parts of DMF, and 2.3 parts of 3-bromopropylene and 2.14 parts of potassium t-butoxide were added thereto at 80 parts of DMFoStirring for 2 hours under C; then adding 0.03 initiator dibenzoyl peroxide (Qinfeng chemical engineering), and continuing stirring for 5 hours at 80 ℃ to obtain a reactive resin A solution; subsequently, 35 parts of vinyl-terminated polyphenylene ether (Sabic SA 9000), 30 parts of vinyl-terminated polyphenylene ether (OPE-2 St, Mn = 1200), and 41 parts of polybutadiene (krevillion Ricon 130) were further added to the reactive resin a solution) 8 parts of polybutadiene-maleic anhydride copolymer (Krevili Ricon130MA 8), 6 parts of polystyrene-maleic anhydride copolymer (Krevili SMA 1000) and 22 parts of TiO2(Tech. Zhonghuamei science and technology in Tianjin), 50 parts of flame retardant magnesium hydroxide (American jaba MAGNIFIN H-5), 20 parts of secondary flame retardant decabromodiphenylethane (Shandong sea king chemical) and 350 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 (Qin Feng chemical industry), and further stirring uniformly; dipping glue with 1080 glass fiber cloth, and baking and drying to obtain prepreg, wherein the baking temperature in the first stage is 75 ℃, the baking time is 7min, and the baking temperature in the second stage is 250oC, the 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 270 ℃ to obtain the thermosetting carbon-hydrogen polymer-based copper-clad plate.
Example 3
Dissolving 16 parts of hydroxyl-terminated polyphenylene ether resin (Sabic SA 90) and 4 parts of hydrogenated hydroxyl-terminated polyolefin resin (Krasol HLBH-P2000) in 100 parts of methyl ethyl ketone, adding 2.7 parts of 3-bromopropylene and 2.5 parts of potassium tert-butoxide, and stirring for 2 hours under the condition of condensation reflux; then adding 0.03 initiator dibenzoyl peroxide (Qinfeng chemical engineering), and continuing stirring for 5 hours under the condition of condensation reflux to obtain a reactive resin A solution; subsequently, 60 parts of vinyl-terminated modified polyphenylene ether (Sabic SA 9000), 30 parts of polybutadiene (kleiviral Ricon 130), 2.5 parts of polydiene-styrene-divinylbenzene terpolymer (kleiviral Ricon 257), 4 parts of polybutadiene-maleic anhydride copolymer (kleiviral Ricon130MA 8), 6 parts of polystyrene-maleic anhydride copolymer (kleiviral SMA 1000), 35 parts of polytetrafluoroethylene pre-sinter (santong avene), 8 parts of SiO were further added to the solution of the reactive resin a2(Xinyihongrun), 28 parts of flame retardant magnesium hydroxide (American Yabao MAGNIFIN H-5), 18 parts of flame retardant decabromodiphenylethane (Shandonghai Wang chemical) and 350 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 (Qinfeng)Chemical industry), further stirring uniformly; dipping glue with 1080 glass fiber cloth, and baking and drying to obtain prepreg, wherein the baking temperature in the first stage is 75 ℃, the baking time is 7min, and the baking temperature in the second stage is 250oC, the 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 280 ℃ to obtain the thermosetting carbon-hydrogen polymer-based copper-clad plate.
Example 4
13 parts of hydroxyl-terminated polyphenylene ether resin (Sabic SA 90), 4 parts of hydrogenated hydroxyl-terminated polyolefin resin (Krasol HLBH-P2000) and 3 parts of monohydroxypolyether resin (Mn = 13000) were dissolved in a mixed solvent of 100 parts of DMF, and 2.3 parts of 3-bromopropylene and 2.14 parts of potassium tert-butoxide were added thereto at 80 parts of DMFoStirring for 2 hours under C; then adding 0.03 initiator dicumyl peroxide at 120 deg.CoC, continuously stirring for 3 hours to obtain a reactive resin A solution; subsequently, 20 parts of vinyl-terminated polyphenylene ether (Sabic SA 9000), 35 parts of vinyl-terminated polyphenylene ether (OPE-2 St, Mn = 1200), 40 parts of polybutadiene (kleiviri Ricon 130), 4 parts of polybutadiene-maleic anhydride copolymer (kleiviri Ricon130MA 8), 4 parts of polystyrene-maleic anhydride copolymer (kleiviri SMA 1000), 35 parts of polytetrafluoroethylene pre-sinter (santorie), 8 parts of SiO were added to the solution of reactive resin a2(Xinyihongrun), 28 parts of flame retardant magnesium hydroxide (American Yabao MAGNIFIN H-5), 18 parts of flame retardant decabromodiphenylethane (Shandonghai Wang chemical) and 350 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 dicumyl peroxide, and further stirring uniformly; dipping glue by adopting 1080 glass fiber cloth, and baking and drying to obtain a prepreg, wherein the baking temperature in the first stage is 75 DEGoC, the time is 7min, and the second stage baking temperature is 250oC, the 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/cm2At a temperature of 280oAnd C, laminating for 8 hours to obtain the thermosetting carbon-hydrogen polymer-based copper-clad plate.
Example 5
Dissolving 15 parts of hydroxyl-terminated polyphenylene ether resin (Sabic SA 90) and 3 parts of hydrogenated hydroxyl-terminated polyolefin resin (Krasol HLBH-P2000) in 100 parts of methyl ethyl ketone, adding 2.7 parts of 3-bromopropylene and 2.5 parts of potassium tert-butoxide, and stirring for 2 hours under the condition of condensation reflux; then adding 0.03 initiator dibenzoyl peroxide (Qinfeng chemical engineering), and continuing stirring for 5 hours under the condition of condensation reflux to obtain a reactive resin A solution; then, to the reactive resin A solution were further added 30 parts of vinyl-terminated modified polyphenylene ether (OPE-2 St, Mn = 1200), 70 parts of polybutadiene (Kliviri Ricon 130), 4 parts of polybutadiene-maleic anhydride copolymer (Kliviri Ricon130MA 8), 6 parts of polystyrene-maleic anhydride copolymer (Kliviri SMA 1000), 40 parts of polytetrafluoroethylene pre-sinter (Shandongtuoyue), 23 parts of flame retardant magnesium hydroxide (American jabao MAGNIFIN H-5), 18 parts of flame retardant decabromodiphenylethane (Shandong sea King chemical) and 350 parts of DMF solvent in 80 parts of DMF solventoStirring for 24 hours under C, fully dissolving and uniformly dispersing; cooling to room temperature, adding 1.5 parts of dicumyl 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 75oC, the time is 7min, and the second stage baking temperature is 250oC, the 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/cm2At a temperature of 280oAnd C, laminating for 8 hours to obtain the thermosetting carbon-hydrogen polymer-based copper-clad plate.
Example 6
13 parts of hydroxyl-terminated polyphenylene ether resin (Sabic SA 90), 4 parts of hydrogenated hydroxyl-terminated polyolefin resin (Krasol HLBH-P2000) and 3 parts of monohydroxypolyether resin (Mn = 13000) were dissolved in a mixed solvent of 50 parts of methyl ethyl ketone and 50 parts of DMF, and 2.3 parts of 3-bromopropylene and 2.14 parts of potassium t-butoxide were added thereto at 80 parts of DMFoStirring for 2 hours under C; then adding 0.03 initiator dibenzoyl peroxide (Qin Feng chemical engineering) at 80 deg.CoC, continuously stirring for 5 hours to obtain a reactive resin A solution; then, 30 parts of terminal vinyl group modifier was further added to the reactive resin A solutionDecorative polyphenylene ether (OPE-2 St, Mn = 1200), 75 parts of polybutadiene (Klebsiella Ricon 130), 5 parts of polybutadiene-maleic anhydride copolymer (Klebsiella Ricon130MA 8), 40 parts of polytetrafluoroethylene pre-sinter (Shandong Yue), 23 parts of flame retardant magnesium hydroxide (American jabo MAGNIFIN H-5), 18 parts of secondary flame retardant decabromodiphenylethane (Shandong Hai Wang chemical) and 350 parts of DMF solvent in 80 parts of DMFoStirring for 24 hours under C, 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 75oC, the time is 7min, and the second stage baking temperature is 250oC, the 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/cm2At a temperature of 280oAnd C, laminating for 8 hours to obtain the thermosetting carbon-hydrogen polymer-based copper-clad plate.
Example 7
Dissolving 13 parts of hydroxyl-terminated polyphenylene ether resin (Sabic SA 90), 4 parts of hydrogenated hydroxyl-terminated polyolefin resin (Krasol HLBH-P2000) and 3 parts of hydroxyl-terminated polybutadiene (Mn =2100, hydroxyl content-0.9 mol/kg) in 100 parts of methyl ethyl ketone, adding 3.02 parts of 2-chloroethyl acrylate and 2.5 parts of potassium tert-butoxide, and stirring for 2 hours under the condition of condensation reflux; then adding 0.03 initiator dibenzoyl peroxide (Qinfeng chemical engineering), and continuing stirring for 5 hours under the condition of condensation reflux to obtain a reactive resin A solution; subsequently, 65 parts of vinyl-terminated modified polyphenylene ether (Sabic SA 9000), 35 parts of polybutadiene (kleiviral Ricon 130), 8 parts of polybutadiene-maleic anhydride copolymer (kleiviral Ricon130MA 8), 12 parts of polystyrene-maleic anhydride copolymer (kleiviral SMA 1000), and 22 parts of TiO were further added to the reactive resin a solution2(Tech. Zhonghuamei science and technology in Tianjin), 50 parts of flame retardant magnesium hydroxide (American jaba MAGNIFIN H-5), 20 parts of secondary flame retardant decabromodiphenylethane (Shandong sea king chemical) and 350 parts of DMF solvent in 80 parts ofoStirring for 24 hours under C, fully dissolving and uniformly dispersing; cooled to room temperature, 1.2 parts dicumyl peroxide are addedFurther stirring uniformly; dipping glue by adopting 1080 glass fiber cloth, and baking and drying to obtain a prepreg, wherein the baking temperature in the first stage is 75 DEGoC, the time is 7min, and the second stage baking temperature is 250oC, the 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/cm2At a temperature of 270 deg.CoAnd C, laminating for 8 hours to obtain the thermosetting carbon-hydrogen polymer-based copper-clad plate.
Example 8
Dissolving 16 parts of hydroxyl-terminated polyphenylene ether resin (Sabic SA 90) and 4 parts of hydrogenated hydroxyl-terminated polyolefin resin (Krasol HLBH-P2000) in 100 parts of methyl ethyl ketone, adding 2.7 parts of 3-bromopropylene and 0.014 part of 1.6M n-butyllithium/n-hexane solution, and stirring for 2 hours under the condition of condensation reflux; then adding 0.03 initiator dibenzoyl peroxide (Qinfeng chemical engineering), and continuing stirring for 5 hours under the condition of condensation reflux to obtain a reactive resin A solution; subsequently, 60 parts of vinyl-terminated modified polyphenylene ether (Sabic SA 9000), 30 parts of polybutadiene (kleiviral Ricon 130), 2.5 parts of polydiene-styrene-divinylbenzene terpolymer (kleiviral Ricon 257), 4 parts of polybutadiene-maleic anhydride copolymer (kleiviral Ricon130MA 8), 6 parts of polystyrene-maleic anhydride copolymer (kleiviral SMA 1000), 35 parts of polytetrafluoroethylene pre-sinter (santong avene), 8 parts of SiO were further added to the solution of the reactive resin a2(Xinyihongrun), 28 parts of flame retardant magnesium hydroxide (American Yabao MAGNIFIN H-5), 18 parts of flame retardant decabromodiphenylethane (Shandonghai Wang chemical) and 350 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 dicumyl peroxide, and further stirring uniformly; dipping glue by adopting 1080 glass fiber cloth, and baking and drying to obtain a prepreg, wherein the baking temperature in the first stage is 75 DEGoC, the time is 7min, and the second stage baking temperature is 250oC, the 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/cm2At a temperature of 280oAnd C, laminating for 8 hours to obtain the thermosetting carbon-hydrogen polymer-based copper-clad plate.
Example 9
Dissolving 16 parts of hydroxyl-terminated polyphenylene ether resin (Sabic SA 90) and 4 parts of hydrogenated hydroxyl-terminated polyolefin resin (Krasol HLBH-P2000) in 100 parts of methyl ethyl ketone, adding 3.02 parts of 4-bromobutene and 2.5 parts of potassium tert-butoxide, and stirring for 2 hours under the condition of condensation reflux; then adding 0.03 initiator dibenzoyl peroxide (Qinfeng chemical engineering), and continuing stirring for 5 hours under the condition of condensation reflux to obtain a reactive resin A solution; subsequently, 65 parts of vinyl-terminated modified polyphenylene ether (Sabic SA 9000), 35 parts of polybutadiene (kleiviral Ricon 130), 8 parts of polybutadiene-maleic anhydride copolymer (kleiviral Ricon130MA 8), 12 parts of polystyrene-maleic anhydride copolymer (kleiviral SMA 1000), and 22 parts of TiO were further added to the reactive resin a solution2(Tech. Zhonghuamei science and technology in Tianjin), 50 parts of flame retardant magnesium hydroxide (American jaba MAGNIFIN H-5), 20 parts of secondary flame retardant decabromodiphenylethane (Shandong sea king chemical) and 350 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 dicumyl peroxide, and further stirring uniformly; dipping glue by adopting 1080 glass fiber cloth, and baking and drying to obtain a prepreg, wherein the baking temperature in the first stage is 75 DEGoC, the time is 7min, the baking temperature in the second stage is 250 ℃, and the 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 270 ℃ to obtain the thermosetting carbon-hydrogen polymer-based copper-clad plate.
Table 1 comparative prepreg examples parametric testing
Figure DEST_PATH_IMAGE007
Table 2 copper clad laminate embodiments parameter test comparison
Figure DEST_PATH_IMAGE009
Firstly, preparing polyarylether-polyolefin block copolymer, on one hand, taking the polyarylether-polyolefin block copolymer as a compatilizer, and obviously enhancing the compatibility between polydiene and vinyl modified polyarylether and other matrix resins; on the other hand, the residual reactable carbon-carbon double bonds at the two ends of the board directly participate in the co-curing reaction of the matrix resin, so that the uniformity, the thermo-mechanical property and the stability of the board are ensured; and then is supplemented with filler, modified resin, flame retardant and other compatilizer resin with proper types and proportions to prepare the thermosetting hydrocarbon polymer composition with adjustable dielectric property, flame retardant property and the like. 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. Finally, the thermosetting copper clad laminate prepared by the prepreg, the film and the copper foil 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, good uniformity of various properties and obvious cost advantage, 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 field of current high-frequency and high-speed communication.
In conclusion, the invention has good industrial production basis and wide application prospect.
While the embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various modifications can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention. These are non-inventive modifications, which are intended to be protected by patent laws within the scope of the claims appended hereto.

Claims (9)

1. A thermosetting copper-clad plate prepared from a thermosetting hydrocarbon polymer composition is characterized by comprising the following specific preparation steps:
s1, dissolving polyhydroxy polyarylether resin and hydrogenated hydroxyl-terminated polyolefin resin in an organic solvent A, adding vinyl halide and alkali, stirring at a temperature of P1 for 0.5-120 h, adding an initiator A, and continuously stirring at a temperature of P2 for 1 min-48 h to obtain a reactive resin A solution;
s2, adding polydiene resin, vinyl-modified polyarylether resin and initiator B into the reactive resin A solution, and uniformly stirring to obtain the thermosetting hydrocarbon polymer composition;
s3, preparing a uniform dispersion liquid of the thermosetting hydrocarbon polymer composition with the solid content of 20-75 wt/v%, impregnating fiber cloth with the uniform dispersion liquid, and baking and drying to obtain a prepreg;
and S4, overlapping the prepreg and the copper foil covered on the surface together, and preparing the thermosetting copper-clad plate through a laminating process.
2. The thermosetting copper-clad plate prepared from the thermosetting hydrocarbon polymer composition according to claim 1, wherein the thermosetting hydrocarbon polymer composition comprises the following components in percentage by weight: in step S1, while the polyhydroxy polyarylether resin is dissolved, a monohydroxy polyarylether resin and a hydroxy-terminated polydiene resin may be added, wherein the hydrogenated hydroxy-terminated polyolefin resin and the hydroxy-terminated polydiene resin both have number average molecular weights of 600 to 10000 and together account for 10 to 60wt% of the polyhydroxy polyarylether resin; the ratio of the hydroxyl-terminated polydiene resin to the hydrogenated hydroxyl-terminated polyolefin resin is controlled to be 0: 100-80: 20; the monohydroxy polyarylether resin has a number average molecular weight of more than 15000.
3. The thermosetting copper-clad plate prepared from the thermosetting hydrocarbon polymer composition according to claim 1, wherein the thermosetting hydrocarbon polymer composition comprises the following components in percentage by weight: in step S1, the organic solvent a includes one or a mixture of more of acetone, methyl ethyl ketone, methyl isobutyl ketone, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone, which are aprotic polar solvents, or a mixture of one or more of benzene, toluene, xylene, and nitrobenzene, which are aprotic polar solvents.
4. The thermosetting copper-clad plate prepared from the thermosetting hydrocarbon polymer composition according to claim 2, wherein in step S1, the vinyl halide is one or a mixture of several of the following substances:
Figure DEST_PATH_IMAGE002
wherein X represents Cl, Br and I; r44, R45 and R46 each independently represent H, methyl or ethyl, and the number of moles of the vinyl halide is the same as the total number of moles of hydroxyl groups contained in the polyhydroxy polyarylether resin, the hydrogenated hydroxyl-terminated polyolefin resin, the monohydroxy polyarylether resin and the hydroxyl-terminated polydiene resin.
5. The thermosetting copper-clad plate prepared from the thermosetting hydrocarbon polymer composition according to claim 1, wherein the thermosetting hydrocarbon polymer composition comprises the following components in percentage by weight: in step S1, the alkali is one or a mixture of more of n-butyllithium, sec-butyllithium, tert-butyllithium, lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, potassium tert-butoxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, and potassium carbonate; the number of moles of the base is the same as the number of moles of the vinyl halide; the initiator A is one or a mixture of several of peroxide, azo compound and redox system free radical initiator which can be dissolved in a solvent capable of uniformly dispersing the thermosetting hydrocarbon polymer composition.
6. The thermosetting copper-clad plate prepared from the thermosetting hydrocarbon polymer composition according to claim 1, wherein the thermosetting hydrocarbon polymer composition comprises the following components in percentage by weight: in step S1, the temperature P1 is-78 ℃ to 150 ℃, and when the boiling point of the organic solvent a is lower than 150 ℃, the upper limit of P1 is set to the boiling point of the organic solvent a, and when the freezing point of the organic solvent is higher than-78 ℃, the lower limit of P1 is set to the freezing point of the organic solvent a; the temperature P2 is 40-200 ℃, and when the boiling point of the organic solvent A is lower than 200 ℃, the upper limit of P2 is set to the boiling point of the organic solvent A.
7. The thermosetting copper-clad plate prepared from the thermosetting hydrocarbon polymer composition according to claim 1, wherein the thermosetting hydrocarbon polymer composition comprises the following components in percentage by weight: in step S2, a filler, a flame retardant, a compatibilizer, and a modified resin may be added simultaneously with the addition of the polydiene resin.
8. The thermosetting copper-clad plate prepared from the thermosetting hydrocarbon polymer composition according to claim 1, wherein the thermosetting hydrocarbon polymer composition comprises the following components in percentage by weight: in step S3, the solvent of the uniform dispersion liquid is one of water and an organic solvent, or a mixture of several of water and an organic solvent, which can uniformly disperse the thermosetting hydrocarbon polymer composition.
9. The thermosetting copper-clad plate prepared from the thermosetting hydrocarbon polymer composition according to claim 1, wherein the thermosetting hydrocarbon polymer composition comprises the following components in percentage by weight: in step S4, the thermosetting copper-clad plate further includes a film, where the film is one or a mixture of more of fluoropolymer, polyimide, polyolefin, polyaromatic hydrocarbon, polyamide, polyether ketone, polyether ether ketone, polyaryl ether, polyarylene sulfide, polyarylene ether sulfone, polyarylene sulfide sulfone, polyaryl ether ketone, polyarylene sulfide ketone, polyether sulfone ketone, polyarylene ether sulfone nitrile, polyarylene sulfide sulfone nitrile, polyphenylquinoxaline, phenolic resin, epoxy resin, cyanate resin, polyester, polycarbonate, polyurethane, and polyoxymethylene.
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