CN114437489A - Prepreg prepared from boron nitride modified by continuous method and high-thermal-conductivity thermosetting high-frequency copper-clad plate - Google Patents
Prepreg prepared from boron nitride modified by continuous method and high-thermal-conductivity thermosetting high-frequency copper-clad plate Download PDFInfo
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- B32B15/00—Layered products comprising a layer of metal
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- B32—LAYERED PRODUCTS
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
The invention belongs to the technical field of communication materials, and particularly relates to a prepreg prepared by adopting boron nitride modified by a continuous method, and a high-thermal-conductivity thermosetting high-frequency copper-clad plate. The invention prepares the uniform dispersion liquid of activated boron nitride, then prepares the activated coupling agent solution, and mixes with the uniform dispersion liquid of activated boron nitride to obtain modified boron nitride, then adds matrix resin and modified boron nitride in an internal mixer, and carries out internal mixing to prepare the thermosetting composite, finally carries out injection molding, extrusion, mould pressing or blade coating molding on the thermosetting composite and then carries out heating to prepare the prepreg, and the prepreg can be laminated with a film and a copper foil, and finally prepares the high-heat-conduction thermosetting high-frequency copper-clad plate through a laminating process.
Description
Technical Field
The invention belongs to the technical field of communication materials, and particularly relates to a prepreg prepared by adopting boron nitride modified by a continuous method, and a high-thermal-conductivity thermosetting high-frequency 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.
At present, the thermosetting hydrocarbon plate using polybutadiene as matrix resin is widely noticed due to the rapid development of 5G communication, and has the comprehensive advantages of low dielectric loss, low thermal expansion coefficient, high bending strength, high thermo-mechanical stability and the like.
However, the conventional polybutadiene-based thermosetting hydrocarbon plate is generally prepared into a prepreg by a sizing process, however, the polybutadiene resin can be crosslinked only when the vinyl content is more than or equal to 70%, and the relatively high vinyl content can reduce the aging resistance of the thermosetting hydrocarbon plate using the polybutadiene as the matrix resin.
In addition, as electronic products are rapidly developing towards miniaturization, light weight, thinning and multi-functionalization, the copper-clad plate used as a main carrier of electronic components has higher and higher integration requirements and more obvious multi-layer trend, which requires that the copper-clad plate also has extremely high heat conduction and heat dissipation performance.
The traditional response idea is to introduce a large amount of inorganic filler into the plate matrix to improve the heat conductivity of the polymer matrix, however, the process mainly has two problems of serious solvent pollution and very limited improvement of the heat conductivity and dielectric constant (Dk) of the plate matrix by the increment of the inorganic filler, and the current requirements of high speed, high frequency, no damage and large-capacity information transmission are difficult to meet.
Therefore, there is an urgent need for prepregs and copper-clad plates with outstanding aging resistance and yellowing resistance, excellent heat conduction and heat dissipation performance, and low solvent pollution during the production process.
The patent publication No. CN 109776864A, the published Japanese patent of China invention 2019.05.21, discloses a modified hexagonal boron nitride, which is prepared by the following method: s1: ultrasonically dispersing hexagonal boron nitride in a dihydromyricetin solution, stirring, filtering and drying to obtain dihydromyricetin modified hexagonal boron nitride BN @ DMY; s2: and (3) carrying out heat treatment on the BN @ DMY at the temperature of 200-250 ℃ for 4-6 h to obtain the modified hexagonal boron nitride.
However, the modified hexagonal boron nitride in the patent uses a large amount of solvent in the preparation process, so the problem of solvent pollution is serious after all.
In addition, the patent also discloses a prepreg, which comprises the following components in percentage by mass: 40-80% of epoxy resin matrix, 0.8-1.7% of curing agent system, 5-35% of glass fiber reinforced material, 22.9-31.9% of modified hexagonal boron nitride and 2.2-5.7% of binder.
However, the prepreg in the patent is relatively poor in heat conduction and heat dissipation performance, which is far from reaching the standard in the communication application environment which is nowadays more compact, lighter, higher-speed, higher-frequency and lossless.
Disclosure of Invention
The invention provides a prepreg prepared by boron nitride modified by a continuous method and a high-heat-conduction thermosetting high-frequency copper-clad plate, which can be prepared by preparing a uniform dispersion liquid of activated boron nitride, then preparing an activated coupling agent solution, mixing the activated coupling agent solution with the uniform dispersion liquid of the activated boron nitride to obtain modified boron nitride, then adding matrix resin and the modified boron nitride into an internal mixer, carrying out internal mixing to prepare a thermosetting compound, finally carrying out injection molding, extrusion, molding or blade coating molding on the thermosetting compound, then carrying out heating to prepare the prepreg, wherein the prepreg can be laminated with a film and a copper foil, and carrying out a laminating process to prepare the high-heat-conduction thermosetting high-frequency copper-clad plate.
The technical scheme adopted by the invention for solving the problems is as follows: a prepreg prepared from boron nitride modified by a continuous method sequentially comprises the following steps:
s1, preparing a uniform dispersion liquid of activated boron nitride;
s2, preparing an activated coupling agent solution, and mixing the activated coupling agent solution with the uniform dispersion liquid of the activated boron nitride to obtain modified boron nitride;
s3, adding matrix resin and the modified boron nitride into an internal mixer, and internally mixing to obtain a thermosetting composite;
s4, molding the thermosetting compound by an injection molding method, an extrusion method, a mould pressing method or a blade coating method, then heating to obtain the prepreg,
the matrix resin is maleic anhydride grafted polydiene resin with a side chain having an acrylate carbon-carbon double bond or a styrene carbon-carbon double bond,
the coupling agent is a mixture of a coupling agent with a terminal epoxy functional group and a coupling agent with a reactive carbon-carbon double bond.
In the present invention, the thickness of the prepreg is 0.1 to 10 mm.
The further preferred technical scheme is as follows: and S1, firstly, pouring boron nitride into the solvent a, performing ball milling to obtain a uniform dispersion liquid of the boron nitride, then adding an alkali solution into the uniform dispersion liquid of the boron nitride, performing ultrasonic reaction, and then adding an acid solution to obtain the uniform dispersion liquid of the activated boron nitride.
In the present invention, D50=1-40um of boron nitride, the solvent a, the solvent of the alkali solution, and the solvent of the acid solution may be one or a mixture of water, acetone, methanol, ethanol, and isopropanol, and the alkali may be one or a mixture of lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide, and potassium tert-butoxide.
In the invention, the temperature of ultrasonic reaction is 30-110 ℃, the reaction time is 4-96h, and the pH value of the acid solution added to the whole mixed system is 4-7.
The further preferred technical scheme is as follows: and S2, preparing a water/alcohol mixed solution of a coupling agent, adding acid for regulation, stirring and activating to obtain the activated coupling agent solution, then pouring the activated coupling agent solution into the uniform dispersion liquid of the activated boron nitride, washing with water after stirring, and then leaching with an organic solvent to obtain the modified boron nitride.
In the invention, the alcohol is one or a mixture of methanol, ethanol and isopropanol.
In the invention, the end point of the acid addition regulation is that the pH value is regulated to 2-5, and then the stirring activation operation is carried out, wherein the activation temperature is 20-60 ℃, and the activation time is 5-30 min.
In the invention, in the stirring and water washing operation of the modified boron nitride, the stirring temperature is 30-80 ℃, the stirring time is 4-24h, and the subsequent organic solvent leaching times are 1-3 times.
The further preferred technical scheme is as follows: in S3, an initiator is adopted to carry out banburying operation together with the matrix resin and the modified boron nitride, wherein the initiator is a free radical initiator.
In the invention, the cavity temperature during banburying is 20-70 ℃, and the rotating speed of a screw of the banbury mixer is 30-900 rpm.
In the invention, the decomposition temperature of the initiator is higher than the melting point of the matrix resin when the half-life period of the initiator is 1h, and is more than or equal to 90 ℃, and the dosage of the initiator accounts for 0.1-5wt% of the matrix resin.
The further preferred technical scheme is as follows: in S3, the modified resin a, the modified resin B, the auxiliary filler, the flame retardant, and the accelerator are further used, and banburying is performed together with the initiator, the matrix resin, and the modified boron nitride.
In the invention, the accelerant is one or a mixture of several of tertiary amine compounds, imidazole compounds, phosphine compounds, substituted urea compounds, phenolic compounds and boron trifluoride amine complexes, and also comprises one or a mixture of several of organic metal complexes or organic metal salts of copper, zinc, cobalt, aluminum and tin, and the accelerant accounts for 0.01-1.0wt% of the modified resin B.
In the invention, the matrix resin, the modified resin A, the modified resin B, the modified boron nitride, the auxiliary filler and the flame retardant are added into an internal mixer for internal mixing for 30-180min, then the initiator and the accelerator are added, and the internal mixing is continued for 5-60min to obtain the thermosetting composite.
In the invention, the cylinder temperature in the injection molding method and the extrusion method is 0-50 ℃ higher than the melting point of the matrix resin, but is lower than the decomposition temperature when the half-life period of the initiator is 0.1h, the retention time of the material in the cylinder is less than or equal to 3min, in the injection molding method, the extrusion method or the die pressing method, the die temperature and the temperature of a hot pressing roller are 0-100 ℃ higher than the decomposition temperature when the half-life period of the initiator is 3h, in the injection molding method and the die pressing method, the heat preservation time of the material in the die is 30s-30min, in the blade coating method, the thermosetting compound can be scraped on a substrate or a fiber cloth.
In the invention, the heating operation of S4 is divided into two stages, the baking temperature of the first stage is 10-30 ℃ higher than the decomposition temperature of the initiator when the half-life period is 1h, and the time is 10-120 min; the baking temperature of the second stage is 10-50 ℃ higher than the decomposition temperature of the initiator when the half-life period is 0.1h, and the time is 1-60 min.
The further preferred technical scheme is as follows: the modified resin A is one or a mixture of a plurality of vinyl modified polyarylether, diene-maleic anhydride copolymer, styrene-polydiene-styrene terpolymer and polydiene-styrene-divinylbenzene terpolymer.
In the invention, the number average molecular weight of the vinyl modified polyarylether is between 400-10000, and a single macromolecular chain of the vinyl modified polyarylether at least contains 2 reactive vinyl functional groups and is positioned on an end group or a side group of a main chain of the polyarylether; the number average molecular weight of the diene-maleic anhydride copolymer is between 500-15000, and the side group of the polydiene block at least contains a reactive carbon-carbon double bond; the number average molecular weight of the styrene-maleic anhydride copolymer is between 500-15000; the number average molecular weight of the polydiene-styrene-divinylbenzene terpolymer is between 1000-15000, the side group of the polydiene block at least contains a reactive carbon-carbon double bond, the proportion of the polystyrene block is 10-60%, and the proportion of the divinylbenzene block is 0.5-30%.
The further preferred technical scheme is as follows: the modified resin B is one or a mixture of more of bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol S epoxy resin, bisphenol F epoxy resin, dicyclopentadiene epoxy resin, naphthalene ring structure epoxy resin, biphenyl epoxy resin, heterocyclic epoxy resin, phenolic epoxy resin, organosilicon epoxy resin and cyanate ester modified epoxy resin.
The further preferred technical scheme is as follows: the number average molecular weight of the maleic anhydride grafted polydiene tree with the side chain belt acrylic ester carbon-carbon double bond or styrene carbon-carbon double bond is 1000-7000, wherein the content of 1, 2-vinyl is 10-90mol%, the grafting amount of the maleic anhydride accounts for 5-35mol% of the vinyl content in the polydiene, the content of the acrylic ester carbon-carbon double bond or styrene carbon-carbon double bond on the side chain accounts for 60-95mol% of the maleic anhydride content, and the dosage of the matrix resin accounts for 10-75wt% of the weight of the prepreg.
The further preferred technical scheme is as follows: the weight ratio of the coupling agent with the terminal epoxy functional group to the coupling agent with the reactive carbon-carbon double bond is 1: 2-5, and the dosage of the coupling agent accounts for 0.1-20wt% of the weight of the boron nitride.
A high-thermal-conductivity thermosetting high-frequency copper-clad plate prepared from prepregs is prepared by laminating the prepregs, a film and a copper foil together and preparing the high-thermal-conductivity thermosetting high-frequency copper-clad plate through a laminating process.
In the invention, the number of the prepregs is more than or equal to 1, the film can be omitted, the number of the copper foil is 1 or 2, the laminating temperature of the laminating process is 150-270 ℃, and the laminating pressure is 30-140kg/cm2The laminating time is 0.5-12 h.
In the present invention, the material of the membrane is one or more of fluoropolymer, polyimide, polyolefin, polyaromatic hydrocarbon, polyamide, polyether ketone, polyether ether ketone, polyarylether, polyarylene sulfide and polyarylether sulfone.
The present invention has the following advantages.
The first preparation method of the modified boron nitride is a continuous method, so that the times of filtration and washing are reduced, the use amount of a solvent and the output of byproducts are reduced, and the product does not need to be dried, thereby being beneficial to reducing the production cost, improving the production efficiency and reducing the environmental protection pressure.
And secondly, the maleic anhydride grafted polydiene resin with the side chain having an acrylate carbon-carbon double bond or a styrene carbon-carbon double bond contains a large amount of reaction type carbon-carbon double bonds, carboxyl and anhydride, so that a double cross-linking curing network is introduced into the prepreg: one is a network formed by curing carbon-carbon double bonds through free radical initiation, and the other is a network formed by curing epoxy groups, carboxyl groups, acid anhydrides and the like under the catalysis of an accelerator, and the double-crosslinking curing network is a structure strengthening network and a heat-conducting healing network, so that the curing degree of the prepreg can be obviously improved, and further the bending strength, the glass transition temperature (Tg), the anti-aging yellowing performance, the peeling strength and the heat conductivity of the copper-clad plate are improved.
Drawings
FIG. 1 is a table of physicochemical parameters of prepregs and copper-clad plates in each example and comparative example of the present invention.
FIG. 2 shows the results of the modified boron nitride grafting amount test in Synthesis example 1 of the present invention.
FIG. 3 shows the results of the modified boron nitride grafting amount test in Synthesis example 2 of the present invention.
FIG. 4 shows the results of the modified boron nitride grafting amount test in Synthesis example 3 of the present invention.
FIG. 5 shows the results of the modified boron nitride grafting amount test in Synthesis example 4 of the present invention.
FIG. 6 shows the results of the modified boron nitride grafting amount test in Synthesis example 5 of the present invention.
Detailed Description
The following description is merely exemplary of the present invention and is not intended to limit the scope of the invention.
Synthesis example 1
120 parts of boron nitride (BN, D50=10um) is mixed in 3500 parts of pure water, after ball milling and dispersion for 30min, 70 parts of NaOH is added, after ultrasonic auxiliary reaction for 8h at 80 ℃, acetic acid is added to adjust the pH value to 6-7, and the uniform dispersion liquid of activated boron nitride is obtained.
Configuration 2wt% H2Adding 0.7 part of coupling agent KH550 and 2.3 parts of coupling agent KH570 into 100 parts of O/ethanol mixed solution, stirring at 55 ℃ for 5min, adjusting the pH value of the system to 3-5, and continuously stirring for 15min to obtain activated coupling agent solution.
Pouring the activated coupling agent solution into the activated boron nitride uniform dispersion liquid, continuously stirring for 4 hours at the temperature of 60 ℃, filtering, and washing the product with water for multiple times until the pH value of the filtrate is between 7 and 8; and finally, washing the filter cake with ethanol and toluene in sequence to obtain the modified BN jointly modified by KH570/KH 550.
As shown in the attached figure 2, the grafting amount is tested by using TGA, and is specifically 1.041wt%, which shows that the modified boron nitride has the advantage of high edge hydroxyl group grafting rate and can be efficiently combined with amino/quaternary ammonium salt type and carbon-carbon double bond type composite coupling agents. (TGA test samples, dried in a vacuum oven at 90 ℃ C.)
Synthesis example 2
Mixing 120 parts of BN (D50=20um) in 3500 parts of pure water, performing ball milling dispersion for 30min, adding 80 parts of NaOH, performing ultrasonic auxiliary reaction at 80 ℃ for 12h, and then adding acetic acid to adjust the pH value to 6-7 to obtain the uniform dispersion liquid of activated boron nitride.
Configuration 2wt% H2Adding 0.8 part of coupling agent KH550 and 3.5 parts of coupling agent KH570 into 100 parts of O/ethanol mixed solution, stirring at 50 ℃ for 10min, adjusting the pH value of the system to 3-5, and continuously stirring for 20min to obtain activated coupling agent solution.
Pouring the activated coupling agent solution into the uniform dispersion liquid of the activated boron nitride, continuously stirring for 5 hours at the temperature of 60 ℃, filtering, and washing the product with water for multiple times until the pH value of the filtrate is between 7 and 8; and finally, washing the filter cake with ethanol and toluene in sequence to obtain the modified BN jointly modified by KH570/KH 550.
As shown in figure 3, the grafting amount is tested by using TGA, specifically 1.531wt%, which shows that the modified boron nitride has the advantage of high grafting rate of edge hydroxyl, and can be efficiently combined with amino/quaternary ammonium salt type and carbon-carbon double bond type composite coupling agents. (TGA test samples, dried in a vacuum oven at 90 ℃ C.)
Synthesis example 3
Mixing 120 parts of BN (D50=30um) in 3500 parts of pure water, performing ball milling dispersion for 30min, adding 70 parts of NaOH, performing ultrasonic auxiliary reaction at 90 ℃ for 12h, and then adding hydrochloric acid to adjust the pH value to be between 5 and 6 to obtain the uniform dispersion liquid of the activated boron nitride.
Configuration 2wt% H2Adding 1 part of coupling agent KH550 and 2.3 parts of coupling agent KH570 into 100 parts of O/ethanol mixed solution, stirring at 60 ℃ for 5min, adjusting the pH value of the system to 3-4, and continuously stirring for 20min to obtain activated coupling agent solution.
Pouring the activated coupling agent solution into the uniform dispersion liquid of the activated boron nitride, continuously stirring for 6 hours at 70 ℃, filtering, washing the product with water for multiple times until the pH value of the filtrate is between 7 and 8; and finally, washing the filter cake with ethanol and toluene in sequence to obtain the modified BN jointly modified by KH570/KH 550.
As shown in the attached figure 4, the grafting amount is tested by using TGA, and is specifically 1.108wt%, which shows that the modified boron nitride has the advantage of high grafting rate of edge hydroxyl, and can be efficiently combined with amino/quaternary ammonium salt type and carbon-carbon double bond type composite coupling agents. (TGA test specimens, first baked in a vacuum oven at 90 deg.C.)
Synthesis example 4
Mixing 120 parts of BN (D50=1um) in 3500 parts of pure water, performing ball milling dispersion for 30min, adding 60 parts of NaOH, performing ultrasonic auxiliary reaction at 80 ℃ for 8h, and then adding hydrochloric acid to adjust the pH value to be between 5 and 6 to obtain the uniform dispersion liquid of the activated boron nitride.
Configuration 2wt% H2Adding 0.5 part of coupling agent KH550 and 2 parts of coupling agent KH570 into 100 parts of O/ethanol mixed solution, stirring at 50 ℃ for 5min, adjusting the pH value of the system to 3-5, and continuously stirring for 15min to obtain activated coupling agent solution.
Pouring the activated coupling agent solution into the uniform dispersion liquid of the activated boron nitride, continuously stirring for 4 hours at 55 ℃, filtering, and washing the product with water for multiple times until the pH value of the filtrate is between 7 and 8; and finally, washing the filter cake with ethanol and toluene in sequence to obtain the modified BN jointly modified by KH570/KH 550.
As shown in figure 5, the grafting amount is measured by TGA, specifically 0.727wt%, which shows that the modified boron nitride has the advantage of high grafting rate of edge hydroxyl, and can be efficiently combined with amino/quaternary ammonium salt type and carbon-carbon double bond type composite coupling agents. (TGA test samples, dried in a vacuum oven at 90 ℃ C.)
Synthesis example 5
Mixing 120 parts of BN (D50=20um) in 3500 parts of pure water, performing ball milling dispersion for 30min, adding 60 parts of NaOH, performing ultrasonic auxiliary reaction for 10h at 70 ℃, and then adding acetic acid to adjust the pH value to 6-7 to obtain the uniform dispersion liquid of activated boron nitride.
Configuration 2wt% H2Adding 0.8 part of coupling agent KH550 and 3 parts of coupling agent KH570 into 100 parts of O/ethanol mixed solution, stirring at 55 ℃ for 5min, adjusting the pH value of the system to 3-5, and continuously stirring for 20min to obtain activated coupling agent solution.
Pouring the activated coupling agent solution into the uniform dispersion liquid of the activated boron nitride, continuously stirring for 5 hours at the temperature of 60 ℃, filtering, and washing the product with water for multiple times until the pH value of the filtrate is between 7 and 8; and finally, washing the filter cake with ethanol and toluene in sequence to obtain the modified BN jointly modified by KH570/KH 550.
As shown in fig. 6, TGA is used to test the grafting amount, specifically 1.380wt%, indicating that the modified boron nitride has the advantage of high grafting rate of edge hydroxyl groups, and can be efficiently combined with amine/quaternary ammonium salt type and carbon-carbon double bond type composite coupling agents. (TGA test samples, dried in a vacuum oven at 90 ℃ C.)
Comparative example 1
Mixing 120 parts of BN (D50=20um) in 3500 parts of pure water, stirring and dispersing for 30min, adding 80 parts of NaOH, carrying out ultrasonic-assisted reaction at 80 ℃ for 12h, and then adding acetic acid to adjust the pH value to 6-7, thus obtaining the uniform dispersion liquid of activated boron nitride.
Configuration 2wt% H2Adding 0.8 part of coupling agent KH550 and 3.5 parts of coupling agent KH570 into 100 parts of O/ethanol mixed solution, stirring at 50 ℃ for 10min, adjusting the pH value of the system to 3-5, and continuously stirring for 20min to obtain activated coupling agent solution.
Pouring the activated coupling agent solution into the uniform dispersion liquid of the activated boron nitride, continuously stirring for 5 hours at the temperature of 60 ℃, filtering, and washing the product with water for multiple times until the pH value of the filtrate is between 7 and 8; and finally, washing the filter cake with ethanol and toluene in sequence to obtain the modified BN jointly modified by KH570/KH 550.
In this comparative example 1, since BN was not subjected to the ball milling operation before dispersion, the relatively agglomerated, compact lamellar structure was maintained throughout the activation process, and the effect of the final lamellar edge grafting hydroxyl group operation was limited, the grafting amount was measured by TGA, specifically 0.268wt%, which was much lower than the above 5 synthetic examples. (TGA test samples, dried first in a vacuum oven at 90 ℃)
Example 1
55 parts of matrix resin (molecular weight is 3500; the content of 1,2 vinyl is 60-92%; the grafting amount of maleic anhydride is 25%; the carbon-carbon double bond of acrylic esters on the side chain accounts for 73mol% of maleic anhydride), 20 parts of vinyl-terminated polyphenylene oxide (Mn = 2300), 5 parts of SBS resin10 parts of bisphenol A epoxy resin, 50 parts of modified boron nitride, 20 parts of silicon oxide, 10 parts of aluminum oxide and 40 parts of decabromodiphenylethane which are products obtained in synthetic example 4 are added into a batch internal mixer together, the internal mixing temperature is set to be 25 ℃, the screw rotating speed of the internal mixer is set to be 30rpm, after internal mixing is carried out for 60min under the air atmosphere, 1.5 parts of dicumyl peroxide, 0.01 part of 1, 2-dimethylimidazole and 0.005 part of aluminum acetylacetonate are added, the temperature of a cavity of the internal mixer and the rotating speed of the screw are kept unchanged, and internal mixing is carried out for 20min under the air atmosphere continuously to obtain a thermosetting hydrocarbon polymer compound; then, transferring the compound into a flat cavity die with the thickness of 0.79mm, and obtaining a prepreg through die pressing, stripping and taking out; taking 1 prepreg and 2 copper foils under the pressure of 50-70kg/cm2And laminating for 4 hours at the temperature of 220 ℃ to obtain the thermosetting copper-clad plate with high heat conductivity.
Example 2
55 parts of matrix resin (molecular weight is 3500; the content of 1 and 2 vinyl is 60-92%; the grafting amount of maleic anhydride is 25%; acrylic ester carbon-carbon double bond on side chain accounts for 73mol% of maleic anhydride), 20 parts of vinyl-terminated polyphenylene oxide (Mn = 2300), 5 parts of SBS resin, 10 parts of bisphenol A type epoxy resin, 50 parts of the product of synthetic example 2, namely modified boron nitride, 20 parts of silicon oxide, 10 parts of aluminum oxide and 40 parts of decabromodiphenylethane are added together into a batch internal mixer, the internal mixing temperature is set to 35 ℃, the screw speed of the internal mixer is set to 30rpm, banburying for 60min in air atmosphere, then adding 1.5 parts of dicumyl peroxide, 0.01 part of 1, 2-dimethylimidazole and 0.005 part of aluminum acetylacetonate, keeping the temperature of a cavity of the banbury mixer and the rotating speed of a screw unchanged, and continuing to banbury for 20min in air atmosphere to obtain a thermosetting hydrocarbon polymer compound; subsequently, the composite was extruded to give a prepreg of 0.77mm thickness; taking 1 prepreg and 2 copper foils under the pressure of 60-80kg/cm2And laminating for 4 hours at the temperature of 200 ℃ to obtain the thermosetting copper-clad plate with high heat conductivity.
Example 3
60 portions of matrix resin (the molecular weight is 5200; the content of 1,2 vinyl is 80-90%; the grafting content of maleic anhydride is 28%; the carbon-carbon double bond of acrylic ester on the side chain is 78mol% of maleic anhydride)) 10 parts of vinyl-terminated polyphenyl ether (Mn = 2300), 5 parts of Keteng D1118 type SBS resin, 15 parts of bisphenol F type epoxy resin, 60 parts of the product of synthesis example 2, namely modified boron nitride, 20 parts of silicon oxide, 10 parts of aluminum oxide and 40 parts of decabromodiphenylethane are added into a batch internal mixer together, the internal mixer temperature is set to be 25 ℃, the screw rotating speed of the internal mixer is set to be 30rpm, after the internal mixing is carried out for 60min in the air atmosphere, 1.5 parts of dicumyl peroxide, 0.01 part of 1, 2-dimethylimidazole and 0.005 part of aluminum acetylacetonate are added, the cavity temperature of the internal mixer and the screw rotating speed are kept unchanged, and the internal mixing is carried out for 20min in the air atmosphere to obtain a thermosetting type hydrocarbon polymer compound; then, transferring the compound into a flat cavity die with the thickness of 0.79mm, and obtaining a prepreg through die pressing, stripping and taking out; taking 1 prepreg and 2 copper foils under the pressure of 50-80kg/cm2And laminating for 4 hours at the temperature of 230 ℃ to obtain the thermosetting copper-clad plate with high heat conductivity.
Example 4
70 parts of matrix resin (with the molecular weight of 4500, the content of 1 and 2 vinyl groups of 80-90 percent and the grafting amount of maleic anhydride of 28 percent, the double bond of acrylic ester carbon and carbon on the side chain accounting for 80mol percent of the maleic anhydride), 15 parts of vinyl-terminated polyphenyl ether (Mn = 2300), 5 parts of Keteng D1118 type SBS resin, 20 parts of bisphenol F type epoxy resin, 80 parts of the product of synthesis example 2, namely modified boron nitride, 10 parts of alumina and 40 parts of decabromodiphenylethane are added into a batch internal mixer together, the internal mixing temperature is set to be 25 ℃, the screw speed of the internal mixer is set to be 30rpm, banburying for 60min in air atmosphere, then adding 1.5 parts of dicumyl peroxide, 0.008 parts of 1, 2-dimethylimidazole and 0.0035 parts of aluminum acetylacetonate, keeping the temperature of a cavity of the banbury mixer and the rotating speed of a screw unchanged, and continuing to banbury for 20min in air atmosphere to obtain a thermosetting hydrocarbon polymer compound; then, adding toluene into the compound, stirring and mixing uniformly, then uniformly blade-coating the mixture on 1080 glass fiber cloth, and baking to obtain a prepreg; taking 6 sheets of the semi-solidified medium sheet and 2 sheets of copper foil, and pressing at 70-90kg/cm2And laminating for 4 hours at the temperature of 230 ℃ to obtain the thermosetting copper-clad plate with high heat conductivity.
Example 5
Taking 60 parts of matrixAdding resin (the molecular weight is 5200; the content of 1,2 vinyl is 80-90%; the grafting amount of maleic anhydride is 28%; the side chain is 78mol% of acrylic ester carbon-carbon double bonds in maleic anhydride), 20 parts of vinyl-terminated polyphenylene oxide (Mn = 2300), 5 parts of Keteng D1118 type SBS resin, 15 parts of bisphenol A type epoxy resin, 60 parts of the product of Synthesis example 1, namely modified boron nitride, 10 parts of alumina and 40 parts of decabromodiphenylethane into a batch internal mixer, setting the internal mixing temperature to be 25 ℃ and the screw speed of the internal mixer to be 30rpm, internally mixing for 60min in air atmosphere, then adding 1.5 parts of dicumyl peroxide, 0.008 parts of 1, 2-dimethylimidazole and 0.0035 parts of aluminum acetylacetonate, keeping the cavity temperature and the screw speed of the internal mixer constant, and continuously internally mixing for 20min in air atmosphere to obtain a thermosetting hydrocarbon polymer compound; then, transferring the compound into a flat cavity die with the thickness of 0.79mm, and obtaining a prepreg through die pressing, stripping and taking out; taking 1 prepreg and 2 copper foils under the pressure of 50-70kg/cm2And laminating for 4 hours at the temperature of 210 ℃ to obtain the thermosetting copper-clad plate with high heat conductivity.
Example 6
60 parts of matrix resin (with the molecular weight of 5200; the content of 1 and 2 vinyl groups of 80-90 percent; the grafting amount of maleic anhydride of 28 percent; the double bonds between the carbon and the carbon of the acrylic esters on the side chain account for 78mol percent of the maleic anhydride), 20 parts of vinyl-terminated polyphenylene oxide (Mn = 2300), 5 parts of Keteng D1118 type SBS resin, 15 parts of bisphenol A type epoxy resin, 60 parts of the product of Synthesis example 3, namely modified boron nitride, 20 parts of silicon oxide, 10 parts of aluminum oxide and 40 parts of decabromodiphenylethane are added into a batch internal mixer together, the internal mixing temperature is set to be 35 ℃, the screw speed of the internal mixer is set to be 30rpm, banburying for 60min in air atmosphere, then adding 1.5 parts of dicumyl peroxide, 0.008 parts of 1, 2-dimethylimidazole and 0.0035 parts of aluminum acetylacetonate, keeping the temperature of a cavity of the banbury mixer and the rotating speed of a screw unchanged, and continuing to banbury for 20min in air atmosphere to obtain a thermosetting hydrocarbon polymer compound; then, transferring the compound into a flat cavity die with the thickness of 0.79mm, and obtaining a prepreg through die pressing, stripping and taking out; taking 1 prepreg and 2 copper foils under the pressure of 60-90kg/cm2Laminating at 210 deg.C for 4h to obtainObtaining the thermosetting copper-clad plate with high heat conductivity.
Example 7
50 parts of matrix resin (molecular weight is 3500; the content of 1 and 2 vinyl is 60-92%; the grafting amount of maleic anhydride is 25%; the carbon-carbon double bond of acrylic esters on the side chain accounts for 73mol% of maleic anhydride), 25 parts of vinyl-terminated polyphenylene oxide (Mn = 2300), 5 parts of Keteng D1118 type SBS resin, 20 parts of bisphenol A type epoxy resin, 70 parts of the product of Synthesis example 5, namely modified boron nitride, 20 parts of silicon oxide, 10 parts of aluminum oxide and 40 parts of decabromodiphenylethane are added together into a batch internal mixer, the internal mixing temperature is set to be 25 ℃, the screw speed of the internal mixer is set to be 30rpm, banburying for 60min in air atmosphere, then adding 1.5 parts of dicumyl peroxide, 0.008 parts of 1, 2-dimethylimidazole and 0.0035 parts of aluminum acetylacetonate, keeping the temperature of a cavity of the banbury mixer and the rotating speed of a screw unchanged, and continuing to banbury for 20min in air atmosphere to obtain a thermosetting hydrocarbon polymer compound; then, adding toluene into the composite, stirring, blade-coating on glass fiber cloth, then placing in an oven, drying and curing at 130 ℃ for 3min, naturally cooling to room temperature, and stripping and taking out to obtain a prepreg; taking 6 sheets of the semi-solidified medium sheet and 2 sheets of copper foil, and pressing at 70-90kg/cm2And laminating for 4 hours at the temperature of 230 ℃ to obtain the thermosetting copper-clad plate with high heat conductivity.
Comparative example 2
Taking 65 parts of polybutadiene (Mn =2000, the content of 1, 2-ethylene is 91%), 20 parts of vinyl-terminated polyphenylene oxide (Mn = 2300), 5 parts of SBS resin, 50 parts of modified boron nitride, 20 parts of silicon oxide, 10 parts of aluminum oxide and 40 parts of decabromodiphenyl ethane which are products obtained in the synthetic example 4, adding the materials into a batch internal mixer, setting the internal mixing temperature to be 25 ℃ and the screw rotating speed of the internal mixer to be 30rpm, carrying out internal mixing for 60min in an air atmosphere, then adding 1.5 parts of dicumyl peroxide, keeping the cavity temperature of the internal mixer and the screw rotating speed unchanged, and carrying out internal mixing for 20min in the air atmosphere to obtain a thermosetting hydrocarbon polymer compound; then, transferring the compound into a flat cavity die with the thickness of 0.79mm, and obtaining a prepreg through die pressing, stripping and taking out; taking 1 prepreg and 2 copper foils under the pressure of 50-70kg/cm2At a temperature of 220 ℃And laminating for 4 hours to obtain the thermosetting copper-clad plate.
Finally, the physicochemical parameters of the prepreg and the copper-clad plate were tested for 7 total examples and 1 total comparative example, and the results are shown in fig. 1.
From fig. 1 we can see that:
1. the comparative example uses a conventional polybutadiene as the matrix resin, and compared with the matrix resin in the example, the side chain, i.e., the reactive carbon-carbon double bond, and the carboxyl, acid anhydride and other groups are absent, so that the double cross-linking curing network described in the application cannot be formed subsequently.
2. The double-crosslinking curing network is a structural curing and reinforcing network and a heat-conducting healing network, and both the networks are absent or deficient in comparative examples, and finally, the structural deficiency is that the bending strength is low and the peeling strength is low, and the deficiency in heat conduction is that the thermal expansion coefficient is too high and the thermal conductivity is low.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but 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 gist 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 (10)
1. A prepreg prepared from boron nitride modified by a continuous method is characterized by sequentially comprising the following steps:
s1, preparing a uniform dispersion liquid of activated boron nitride;
s2, preparing an activated coupling agent solution, and mixing the activated coupling agent solution with the uniform dispersion liquid of the activated boron nitride to obtain modified boron nitride;
s3, adding matrix resin and the modified boron nitride into an internal mixer, and internally mixing to obtain a thermosetting composite;
s4, molding the thermosetting compound by an injection molding method, an extrusion method, a mould pressing method or a blade coating method, then heating to obtain the prepreg,
the matrix resin is maleic anhydride grafted polydiene resin with a side chain having an acrylate carbon-carbon double bond or a styrene carbon-carbon double bond,
the coupling agent is a mixture of a coupling agent with a terminal epoxy functional group and a coupling agent with a reactive carbon-carbon double bond.
2. The prepreg according to claim 1, which is prepared from boron nitride modified by a continuous process, and is characterized in that: and S1, firstly, pouring boron nitride into the solvent a, performing ball milling to obtain a uniform dispersion liquid of the boron nitride, then adding an alkali solution into the uniform dispersion liquid of the boron nitride, performing ultrasonic reaction, and then adding an acid solution to obtain the uniform dispersion liquid of the activated boron nitride.
3. The prepreg according to claim 1, which is prepared from boron nitride modified by a continuous process, wherein: and S2, preparing a water/alcohol mixed solution of a coupling agent, adding acid for regulation, stirring and activating to obtain the activated coupling agent solution, then pouring the activated coupling agent solution into the uniform dispersion liquid of the activated boron nitride, washing with water after stirring, and then leaching with an organic solvent to obtain the modified boron nitride.
4. The prepreg according to claim 1, which is prepared from boron nitride modified by a continuous process, and is characterized in that: in S3, an initiator is adopted to carry out banburying operation together with the matrix resin and the modified boron nitride, wherein the initiator is a free radical initiator.
5. The prepreg according to claim 4, which is prepared from boron nitride modified by a continuous method, is characterized in that: in S3, modified resin a, modified resin B, an auxiliary filler, a flame retardant, and an accelerator are further used, and banburying is performed together with the initiator, the matrix resin, and the modified boron nitride.
6. The prepreg according to claim 5, which is prepared from boron nitride modified by a continuous process, wherein: the modified resin A is one or a mixture of a plurality of vinyl modified polyarylether, diene-maleic anhydride copolymer, styrene-polydiene-styrene terpolymer and polydiene-styrene-divinylbenzene terpolymer.
7. The prepreg according to claim 5, which is prepared from boron nitride modified by a continuous process, wherein: the modified resin B is one or a mixture of more of bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol S epoxy resin, bisphenol F epoxy resin, dicyclopentadiene epoxy resin, naphthalene ring structure epoxy resin, biphenyl epoxy resin, heterocyclic epoxy resin, phenolic epoxy resin, organosilicon epoxy resin and cyanate ester modified epoxy resin.
8. The prepreg according to claim 1, which is prepared from boron nitride modified by a continuous process, and is characterized in that: the number average molecular weight of the maleic anhydride grafted polydiene tree with the side chain belt acrylic ester carbon-carbon double bond or styrene carbon-carbon double bond is 1000-7000, wherein the content of 1, 2-vinyl is 10-90mol%, the grafting amount of the maleic anhydride accounts for 5-35mol% of the vinyl content in the polydiene, the content of the acrylic ester carbon-carbon double bond or styrene carbon-carbon double bond on the side chain accounts for 60-95mol% of the maleic anhydride content, and the dosage of the matrix resin accounts for 10-75wt% of the weight of the prepreg.
9. The prepreg according to claim 1, which is prepared from boron nitride modified by a continuous process, and is characterized in that: the weight ratio of the coupling agent with the terminal epoxy functional group to the coupling agent with the reactive carbon-carbon double bond is 1: 2-5, and the dosage of the coupling agent accounts for 0.1-20wt% of the weight of the boron nitride.
10. The high-thermal-conductivity thermosetting high-frequency copper-clad plate prepared from the prepreg according to claim 1 is characterized in that: and laminating the curing sheet, the film and the copper foil together, and preparing the high-thermal-conductivity thermosetting high-frequency copper-clad plate through a laminating process.
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| CN115572486A (en) * | 2022-10-18 | 2023-01-06 | 中科院广州化学有限公司 | Heat-conducting insulating polymer material composite film based on boron nitride filler and preparation method thereof |
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| CN115572486A (en) * | 2022-10-18 | 2023-01-06 | 中科院广州化学有限公司 | Heat-conducting insulating polymer material composite film based on boron nitride filler and preparation method thereof |
| CN115572486B (en) * | 2022-10-18 | 2024-03-29 | 中科院广州化学有限公司 | Heat-conducting insulating polymer material composite film based on boron nitride filler and preparation method thereof |
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