CN112111176A

CN112111176A - Boron nitride-coated polytetrafluoroethylene composite filler, prepreg prepared from same and high-thermal-conductivity carbon-hydrogen copper-clad plate

Info

Publication number: CN112111176A
Application number: CN202011040146.0A
Authority: CN
Inventors: 俞卫忠; 俞丞; 顾书春; 冯凯
Original assignee: Changzhou Zhongying Technology Co ltd
Current assignee: Changzhou Zhongying Technology Co ltd
Priority date: 2020-09-28
Filing date: 2020-09-28
Publication date: 2020-12-22
Anticipated expiration: 2040-09-28
Also published as: CN112111176B

Abstract

The invention relates to a boron nitride coated polytetrafluoroethylene composite filler, a prepreg prepared from the boron nitride coated polytetrafluoroethylene composite filler and a high-thermal-conductivity carbon-hydrogen copper-clad plate. According to the invention, the boron nitride-coated polytetrafluoroethylene composite filler is prepared firstly, and then the prepreg is prepared. In the vacuum lamination process, the boron nitride-coated polytetrafluoroethylene composite filler can inhibit the orientation arrangement of boron nitride with a two-dimensional lamellar structure in the plane direction of the plate, and simultaneously, the introduction of polytetrafluoroethylene also reduces the dielectric constant of the plate, so that the prepared carbon-hydrogen copper-clad plate not only has higher thermal conductivity in the thickness direction, but also has excellent dielectric property, thermal-mechanical strength, dimensional stability and high copper foil peeling strength, and can meet various performance requirements of current high-frequency and high-speed communication fields on the function diversification and complication of the copper-clad plate material.

Description

Boron nitride-coated polytetrafluoroethylene composite filler, prepreg prepared from same and high-thermal-conductivity carbon-hydrogen copper-clad plate

Technical Field

The invention belongs to the field of communication materials, and particularly relates to a boron nitride-coated polytetrafluoroethylene composite filler, a prepreg prepared from the boron nitride-coated polytetrafluoroethylene composite filler and a high-thermal-conductivity carbon-hydrogen copper-clad plate.

Background

Electronic products are rapidly developing towards miniaturization, light weight, thinning and multi-functionalization, and copper-clad plates serving as main carriers of electronic components have higher and higher integration level and finer circuit arrangement. Therefore, the copper-clad plate has excellent insulation and thermo-mechanical properties, and also has good heat conduction and heat dissipation functions. Although the metal-based copper-clad plate has the best heat dissipation capability, the manufacturing cost is high, the production difficulty is high, and the metal-based copper-clad plate is mainly used for high-current modules. The ceramic substrates such as alumina-based, aluminum nitride-based and silicon nitride-based substrates also have good thermal conductivity, but have poor mechanical properties. The traditional thermosetting copper-clad plate represented by FR-4 has good insulation, high thermo-mechanical property, high quality, low price, convenient processing and strong universality, however, the thermal conductivity is extremely low, only 0.25W/m.K, and the dielectric constant and the dielectric loss are high, so that the traditional thermosetting copper-clad plate can only be used under low frequency. Therefore, people develop a polyphenylene ether and polydiene hydrocarbon polymer-based thermosetting copper-clad plate, and on one hand, the dielectric property of the substrate under high frequency is improved; on the other hand, by introducing a high filling amount of a heat conductive material such as boron nitride, aluminum nitride, or the like into the matrix resin, the thermal conductivity of the substrate is improved.

However, the compounding of the thermosetting resins and the heat-conducting filler is usually realized by a solution mixing method and then by the steps of gluing, baking, curing and the like, and in the process, the addition amount of the heat-conducting filler is very limited, so that the thermal conductivity of the copper-clad plate is very limited; meanwhile, the high-filling-amount high-heat-conductivity filler can also enable the dielectric constant of the copper-clad plate to be high, and the circuit design and processing of the copper-clad plate are seriously influenced; more importantly, the hexagonal crystal type high thermal conductivity filler represented by boron nitride and aluminum nitride has anisotropy, so that the thermal conductivity of the copper-clad plate in the thickness direction is far smaller than that in the plane direction, and the comprehensive performance is difficult to meet the current requirements of high speed, high frequency, no damage and large-capacity information transmission.

The patent publication No. CN111251676A, Chinese patent application publication No. 2020.06.09 discloses a high thermal conductivity modified polytetrafluoroethylene copper-clad plate and a preparation method thereof, firstly silane coupling agent is adopted to pretreat glass fiber cloth, then PTFE/PFEP/L-tryptophan modified graphene oxide dispersion glue solution is prepared, then the glass fiber cloth pretreated by the silane coupling agent is impregnated with the glue solution and dried to obtain an impregnated film, the impregnated film is laminated to a raw substrate with a specified thickness, and copper foils are covered on two sides of the raw substrate to carry out hot-pressing sintering, so that the modified PTFE copper-clad plate is obtained.

However, the copper-clad plate in the patent of the invention has the problems of poor heat conduction effect and general overall mechanical property.

Disclosure of Invention

The invention provides a boron nitride-coated polytetrafluoroethylene composite filler, a prepreg prepared from the boron nitride-coated polytetrafluoroethylene composite filler and a high-thermal-conductivity carbon-hydrogen copper-clad plate.

In order to solve the problems in the background art, the invention firstly effectively strips off the lamellar structure of the hexagonal boron nitride and reduces the stacking layer number of the hexagonal boron nitride through the ball milling process; then, rich hydroxyl groups are connected to the edge of the sheet layer through alkali treatment, and then a composite coupling agent is utilized to simultaneously modify amido/quaternary ammonium salt and carbon-carbon double bonds on the structure of the boron nitride sheet layer to prepare modified boron nitride; then, through the electrostatic interaction between the surfactant ammonium perfluorooctanoate in the polytetrafluoroethylene emulsion and the modified boron nitride, the modified boron nitride sheet is coated on the surface of the polytetrafluoroethylene micelle, most of the solvent is removed, and the coating structure is well fixed through freeze-drying; and finally, baking and frying at high temperature to remove the ammonium perfluorooctanoate and promote the partial degradation of the amino/quaternary ammonium salt grafted on the surface of the modified boron nitride, thereby preparing the boron nitride-coated polytetrafluoroethylene composite filler.

And then, preparing a sizing solution of the crosslinkable hydrocarbon polymer composition by using boron nitride to coat the polytetrafluoroethylene composite filler, the auxiliary high-thermal-conductivity filler, the crosslinkable matrix resin, the modified resin, other auxiliary fillers, the flame retardant and the initiator, and impregnating fiber cloth and then drying to prepare the prepreg, wherein the prepreg is uniform in gel content, strong in resin adhesive force, smooth in surface, and proper in toughness and viscosity.

During vacuum lamination, the boron nitride-coated polytetrafluoroethylene composite filler can inhibit the orientation arrangement of boron nitride with a two-dimensional lamellar structure in the plane direction of the plate to a certain extent; meanwhile, the auxiliary high-thermal-conductivity filler is introduced into the prepreg to fill the gap, so that the overlapping of the high-thermal-conductivity filler is further promoted, the formation of a percolation network of the high-thermal-conductivity filler in the thickness direction of the copper-clad plate is effectively improved, and the thermal conductivity of the plate is improved; meanwhile, the introduction of polytetrafluoroethylene can also reduce the dielectric constant of the plate, so that the prepared carbon-hydrogen copper-clad plate has high heat conductivity coefficient, excellent dielectric property, thermal-mechanical strength, dimensional stability and high copper foil peeling strength, 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.

The invention provides a boron nitride coated polytetrafluoroethylene composite filler, which is prepared by the following specific steps:

step 1, mixing hexagonal boron nitride D50= 10-40 um into a solvent A, and performing ball milling to prepare a uniform dispersion liquid; then, adding an alkali solution into the uniform dispersion liquid, carrying out ultrasonic reaction for 4-96 h at the temperature of 30-80 ℃, filtering and washing until the pH value of the filtrate is 7-8, and finally drying to prepare an activated boron nitride slice with a hydroxyl group at the edge of the slice layer;

step 2, preparing a water/alcohol mixed solution of a coupling agent, adjusting the pH value of the water/alcohol mixed solution to 2-5, and stirring and activating at 20-60 ℃ for 5-30 min to obtain an activated coupling agent solution; meanwhile, mixing the activated boron nitride slices into 0.5-5 wt% of water/alcohol mixed solution again, performing ball milling to disperse uniformly, adding an activated coupling agent solution, continuously stirring at 30-80 ℃ for reaction for 4-24 hours, filtering, washing, and drying to prepare modified boron nitride slices;

3, re-dispersing the modified boron nitride slices in water, uniformly dispersing the modified boron nitride slices through a ball milling process, mixing the modified boron nitride slices into polytetrafluoroethylene emulsion, uniformly stirring and mixing, standing the system for 12-96 hours, directly pouring clear water on the upper layer of the system, and removing water from the rest system through a freeze-drying process;

and 4, stir-frying the freeze-dried system at 270-380 ℃ for 10-60 min in an air atmosphere to obtain the boron nitride coated polytetrafluoroethylene composite filler.

The further preferred technical scheme is as follows: the solvent A in the step 1 is one or a mixture of water, methanol, ethanol or isopropanol;

the alkali in the step 1 is one or a mixture of several of lithium hydroxide, sodium hydroxide or potassium hydroxide;

the coupling agent in the step 2 is a mixture of a coupling agent A and a coupling agent B; the coupling agent A is one or a mixture of more of a coupling agent with terminal amine groups or a quaternary ammonium salt coupling agent; the coupling agent B is one or a mixture of several of coupling agents with reactive carbon-carbon double bonds; the weight ratio of the coupling agent A to the coupling agent B is controlled to be 10: 1-5: 1; the amount of the coupling agent accounts for 0.1-5 wt% of the activated boron nitride flake;

the modified boron nitride flakes in the step 3 account for 10-50 wt% of the polytetrafluoroethylene resin.

A prepreg prepared by coating a polytetrafluoroethylene composite filler with boron nitride specifically comprises the following preparation steps:

s1, mixing the boron nitride-coated polytetrafluoroethylene composite filler, the auxiliary high-thermal-conductivity filler, the cross-linkable matrix resin, the modified resin, other auxiliary fillers, the flame retardant and the initiator in an organic solvent, and stirring, shearing and dispersing uniformly to obtain a uniform dispersion liquid of the cross-linkable hydrocarbon resin composition with the solid content of 20-75 wt/v%;

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 boron nitride-coated polytetrafluoroethylene composite filler accounts for 5-40 wt% of the crosslinkable hydrocarbon resin composition in S1;

the auxiliary high-thermal-conductivity filler in the S1 is one or a mixture of more of aluminum nitride, boron nitride, silicon carbide, silicon nitride and diamond, and the using amount of the auxiliary high-thermal-conductivity filler accounts for 2-10 wt% of the crosslinkable hydrocarbon resin composition; the auxiliary high-thermal-conductivity filler can be of a lamellar structure, a spherical or amorphous structure, the particle size D50 is controlled to be 0.3-40 um, and the auxiliary high-thermal-conductivity filler can also be of a fibrous structure, the diameter of the fiber is 0.5-15 um, and the length of the fiber is 5-500 um;

the crosslinkable base resin in S1 is one or a mixture of a plurality of thermosetting polyarylether oligomer and polydiene; the thermosetting polyarylether oligomer is one or a mixture of several of vinyl modified polyphenyl ether and derivatives thereof, the number average molecular weight is controlled to be 400-4000, the vinyl exists on the end group or the side group of the polyphenyl ether, and the single macromolecular chain of the polyarylether at least contains 2 vinyl functional groups; the number average molecular weight of the polydiene is controlled to be 500-6000, and the 1, 2-vinyl content of the polydiene is more than or equal to 25%; the dosage of the thermosetting polyarylether oligomer and the polydiene is controlled to be 10: 90-50: 50; the crosslinkable matrix resin accounts for 15-70 wt% of the crosslinkable hydrocarbon resin composition;

the modified resin in S1 is one or a mixture of more of diene-maleic anhydride copolymers, and at least contains one reactive carbon-carbon double bond side group on a polydiene block of a single modified resin macromolecular chain; the number average molecular weight of the modified resin is controlled to be 500-20000, and the amount of the modified resin accounts for 0-10 wt% of the crosslinkable hydrocarbon resin composition;

the other auxiliary filler described in S1 is SiO₂、Al₂O₃、TiO₂、ZnO、MgO、Bi₂O₃、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 ultrahigh molecular weight polyethylene fibers, Kevlar fibers, polyimide, polyetherimide, polyether ether ketone and polyphenylene sulfide; the other auxiliary fillers account for 0-60 wt% of the crosslinkable hydrocarbon resin composition;

the flame retardant in S1 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 0-35 wt% of the crosslinkable hydrocarbon resin composition;

the initiator in S1 is one or a mixture of several of peroxide and azo compounds, the thermal decomposition temperature is more than or equal to 50 ℃ when the half-life period is 10 hours, and the dosage of the initiator accounts for 0.1-5 wt% of the crosslinkable hydrocarbon resin composition;

the organic solvent in S1 is one or a mixture of N, N-dimethylformamide, N-dimethylacetamide, benzene, toluene and xylene.

The further preferred technical scheme is as follows: the fiber cloth in S2 is one of electronic grade alkali-free glass fiber cloth, carbon fiber, boron fiber, Kevlar, polyimide, polytetrafluoroethylene, polyester fiber cloth and LCP fiber cloth;

the baking and drying in the S2 are divided into two stages, wherein the baking and drying temperature in the first stage is 50-120 ℃, and the baking and drying time is 1-30 min; the second stage baking and drying temperature is 140-180 ℃, and the time is 1-30 min.

A high-heat-conductivity type hydrocarbon copper-clad plate manufactured by prepregs 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 80-150 kg/cm²The laminating time is 0.5-18 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 high-heat-conductivity type hydrocarbon 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 boron nitride-coated polytetrafluoroethylene composite filler and the prepreg and the high-thermal-conductivity carbon-hydrogen copper-clad plate prepared by the same are further described in detail by embodiments below. However, this example is provided only as an illustration and not as a limitation of the invention.

Synthesis example 1

140 parts of BN (D50=20um) are mixed in 3000 parts of pure water, and after 30min of ball-milling dispersion, 70 parts of NaOH are added thereto, and 80 parts of NaOH is added^oC, after carrying out ultrasonic auxiliary reaction for 12 hours, filtering, washing for multiple times until the pH value of filtrate is 7-8, and filtering a filter cake at 90 DEG^oC, drying in a vacuum oven to obtain activated BN;

configuration 2wt% H₂100 portions of O/ethanol mixed solution are added with 2.5 portions of coupling agent KH550 and 0.28 portionCoupling agent KH570 in 55^oStirring for 5min under C, adjusting the pH value of the system to 3-5, and continuously stirring for 20min to obtain an activated composite coupling agent solution;

while adding 100 parts of activated BN to 1000 parts of 2wt% H₂Ball milling and dispersing for 10min in O/ethanol mixed solution, adding the activated composite coupling agent solution, and mixing at 60 deg.C^oC, continuously stirring for 4 hours, filtering, washing the product for multiple times until the pH value of the filtrate is between 7 and 8, and finally placing the filter cake at 90 DEG^oAnd C, drying in a vacuum oven to obtain the modified BN jointly modified by KH570/KH 550.

Synthesis example 2

configuration 2wt% H₂100 portions of O/ethanol mixed solution are added with 2.5 portions of coupling agent KH550 and 0.5 portion of coupling agent KH570 at 55 portions^oStirring for 5min under C, adjusting the pH value of the system to 3-5, and continuously stirring for 20min to obtain an activated composite coupling agent solution;

Synthesis example 3

Re-dispersing 90 parts of modified BN jointly modified by KH570/KH550, which is a product obtained in synthetic example 1, in 900 parts of water, performing ball milling for 20min, then mixing the dispersion liquid into 55 parts of polytetrafluoroethylene emulsion (with the solid content of 60 wt%), slowly stirring and uniformly mixing, standing the system for 42h, directly pouring out clear water on the upper layer of the system, soaking the whole remaining system in liquid nitrogen for freezing, and then performing freeze drying to fully remove water;

finally, the freeze-dried system is placed at 330 under an air atmosphere^oAnd C, stir-frying for 35min to obtain the boron nitride coated polytetrafluoroethylene composite filler.

Synthesis example 4

Re-dispersing 90 parts of modified BN (BN) jointly modified by KH570/KH550, which is a product obtained in synthetic example 1, in 900 parts of water, performing ball milling treatment for 20min, mixing the dispersion liquid into 150 parts of polytetrafluoroethylene emulsion (with the solid content of 60 wt%), slowly stirring and uniformly mixing, standing the system for 70h, directly pouring out clear water on the upper layer of the system, soaking the whole remaining system in liquid nitrogen for freezing, and then performing freeze drying to fully remove water;

finally, the freeze-dried system was placed in 340 deg.C under air atmosphere^oAnd C, stir-frying for 45min to obtain the boron nitride coated polytetrafluoroethylene composite filler.

Synthesis example 5

Re-dispersing 90 parts of modified BN jointly modified by KH570/KH550, which is a product obtained in synthetic example 1, in 900 parts of water, performing ball milling treatment for 20min, mixing the dispersion liquid into 37.5 parts of polytetrafluoroethylene emulsion (with the solid content of 60 wt%), slowly stirring and uniformly mixing, standing the system for 36h, directly pouring out clear water on the upper layer of the system, soaking the whole remaining system in liquid nitrogen for freezing, and then performing freeze drying to fully remove water;

finally, the freeze-dried system is placed at 330 under an air atmosphere^oAnd C, stir-frying for 30min to obtain the boron nitride coated polytetrafluoroethylene composite filler.

Synthesis example 6

Re-dispersing 90 parts of modified BN (BN) jointly modified by KH570/KH550, which is a product obtained in synthetic example 2, in 900 parts of water, performing ball milling treatment for 20min, mixing the dispersion liquid into 150 parts of polytetrafluoroethylene emulsion (with the solid content of 60 wt%), slowly stirring and uniformly mixing, standing the system for 75h, directly pouring out clear water on the upper layer of the system, soaking the whole remaining system in liquid nitrogen for freezing, and then performing freeze drying to fully remove water;

Example 1

Taking 18.5 parts of the product of synthesis example 3, namely, a boron nitride-coated polytetrafluoroethylene composite filler, 4 parts of alumina, 10 parts of silica, 30 parts of magnesium hydroxide, 6 parts of aluminum nitride, 9 parts of vinyl-terminated modified polyphenylene ether (Sabic SA 9000), 7 parts of polybutadiene (kleivirocon 154), 4 parts of polybutadiene (kleivirocon 156), 5 parts of polydiene-styrene-divinylbenzene terpolymer (kleivirocon 257), 3 parts of polybutadiene-maleic anhydride copolymer (kleivirocon 130MA 8) and 5 parts of decabromodiphenylethane, mixing in toluene, stirring at 50 ℃ for 24 hours to fully dissolve and disperse uniformly, cooling to room temperature, adding 0.9 part of dibenzoyl peroxide, and further stirring uniformly; dipping 1078 glass fiber cloth in glue, and baking and drying to obtain a prepreg, wherein the baking temperature in the first stage is 80 ℃ for 3min, and the baking temperature in the second stage is 140 ℃ for 1 min; stacking 9 prepregs, respectively attaching back adhesive copper foils to the upper and lower surfaces of the prepregs under a pressure of 70-90 kg/cm²And laminating for 2 hours at the temperature of 220 ℃ to obtain the high-thermal-conductivity thermosetting hydrocarbon polymer-based copper-clad plate.

Example 2

Taking 18.5 parts of the product of synthesis example 4, namely, a boron nitride-coated polytetrafluoroethylene composite filler, 4 parts of alumina, 10 parts of silica, 25 parts of magnesium hydroxide, 5 parts of aluminum nitride, 9 parts of vinyl-terminated modified polyphenylene ether (Sabic SA 9000), 7 parts of polybutadiene (kleivirocon 154), 4 parts of polybutadiene (kleivirocon 156), 5 parts of polydiene-styrene-divinylbenzene terpolymer (kleivirocon 257), 3 parts of polybutadiene-maleic anhydride copolymer (kleivirocon 130MA 8), 9 parts of decabromodiphenylethane and 3 parts of antimony trioxide, mixing the mixture in toluene, stirring the mixture at 50 ℃ for 24 hours to fully dissolve and disperse the mixture uniformly, then cooling the mixture to room temperature, adding 0.9 part of dibenzoyl peroxide, and further stirring the mixture uniformly; impregnating with 1078 glass fiber cloth, baking and dryingObtaining a prepreg, wherein the first-stage baking temperature is 80 ℃ and the time is 3min, and the second-stage baking temperature is 140 ℃ and the time is 1 min; stacking 9 prepregs, respectively attaching back adhesive copper foils to the upper and lower surfaces of the prepregs under a pressure of 70-90 kg/cm²And laminating for 2 hours at the temperature of 220 ℃ to obtain the high-thermal-conductivity thermosetting hydrocarbon polymer-based copper-clad plate.

Example 3

Taking 18.5 parts of the product of synthesis example 5, namely, a boron nitride-coated polytetrafluoroethylene composite filler, 6 parts of alumina, 10 parts of silica, 25 parts of magnesium hydroxide, 5 parts of aluminum nitride, 9 parts of vinyl-terminated modified polyphenylene ether (Sabic SA 9000), 7 parts of polybutadiene (kleivirocon 154), 6 parts of polybutadiene (kleivirocon 156), 3 parts of polydiene-styrene-divinylbenzene terpolymer (kleivirocon 257), 3 parts of polybutadiene-maleic anhydride copolymer (kleivirocon 130MA 8), 7.5 parts of decabromodiphenylethane and 2.5 parts of antimony trioxide, mixing the mixture in toluene, stirring the mixture at 50 ℃ for 24 hours to fully dissolve and uniformly disperse the mixture, cooling the mixture to room temperature, adding 0.7 part of dibenzoyl peroxide and 0.2 part of tert-butyl perbenzoate, and further stirring the mixture uniformly; dipping 1078 glass fiber cloth in glue, and baking and drying to obtain a prepreg, wherein the baking temperature in the first stage is 80 ℃ for 3min, and the baking temperature in the second stage is 140 ℃ for 1 min; stacking 9 prepregs, respectively attaching back adhesive copper foils to the upper and lower surfaces of the prepregs under a pressure of 70-90 kg/cm²And laminating for 2 hours at the temperature of 220 ℃ to obtain the high-thermal-conductivity thermosetting hydrocarbon polymer-based copper-clad plate.

Example 4

18.5 parts of the product of Synthesis example 6, namely, a boron nitride-coated polytetrafluoroethylene composite filler, 4 parts of alumina, 10 parts of quartz, 30 parts of magnesium hydroxide, 6 parts of aluminum nitride, 9 parts of a vinyl-terminated modified polyphenylene ether (Sabic SA 9000), 7 parts of polybutadiene (Kliviley Ricon 154), 4 parts of polybutadiene (Kliviley Ricon 156), 5 parts of a polydiene-styrene-divinylbenzene terpolymer (Kliviley Ricon 257), 3 parts of a polybutadiene-maleic anhydride copolymer (Kliviley Ricon130MA 8), and 5 parts of decabromodiphenylethane were mixed with methyl methacrylateStirring for 24h at 50 ℃ in benzene to fully dissolve and uniformly disperse, cooling to room temperature, adding 0.9 part of dibenzoyl peroxide, and further uniformly stirring; dipping 1078 glass fiber cloth in glue, and baking and drying to obtain a prepreg, wherein the baking temperature in the first stage is 80 ℃ for 3min, and the baking temperature in the second stage is 140 ℃ for 2 min; stacking 9 prepregs, respectively attaching back adhesive copper foils to the upper and lower surfaces of the prepregs under a pressure of 70-90 kg/cm²And laminating for 2 hours at the temperature of 220 ℃ to obtain the high-thermal-conductivity thermosetting hydrocarbon polymer-based copper-clad plate.

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

1. The boron nitride-coated polytetrafluoroethylene composite filler is characterized by comprising the following specific preparation methods:

2. The boron nitride-coated polytetrafluoroethylene composite filler according to claim 1, wherein the solvent A in step 1 is one or a mixture of water, methanol, ethanol or isopropanol;

3. A prepreg prepared by using the boron nitride-coated polytetrafluoroethylene composite filler according to claim 1, which is characterized by comprising the following specific preparation steps:

4. The prepreg according to claim 3, wherein the boron nitride-coated polytetrafluoroethylene composite filler in S1 accounts for 5-40 wt% of the crosslinkable hydrocarbon resin composition;

5. The prepreg according to claim 3, wherein the fiber cloth in S2 is one of an electronic grade alkali-free glass fiber cloth, a carbon fiber, a boron fiber, Kevlar, polyimide, polytetrafluoroethylene, a polyester fiber cloth and an LCP fiber cloth;

6. A high-thermal-conductivity type carbon-hydrogen copper-clad plate manufactured by adopting the prepreg according to claim 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 thickness of the high-heat-conductivity type hydrocarbon copper-clad plate is controlled to be 0.1-10 mm.