CN117165034B - Epoxy resin for high-frequency high-speed copper-clad plate and preparation method thereof - Google Patents
Epoxy resin for high-frequency high-speed copper-clad plate and preparation method thereof Download PDFInfo
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- CN117165034B CN117165034B CN202311294349.6A CN202311294349A CN117165034B CN 117165034 B CN117165034 B CN 117165034B CN 202311294349 A CN202311294349 A CN 202311294349A CN 117165034 B CN117165034 B CN 117165034B
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 70
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 77
- 229910052582 BN Inorganic materials 0.000 claims abstract description 70
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000002135 nanosheet Substances 0.000 claims abstract description 58
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 71
- 229910052796 boron Inorganic materials 0.000 claims description 71
- 238000003756 stirring Methods 0.000 claims description 67
- 238000001035 drying Methods 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 29
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 28
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 25
- 229910052731 fluorine Inorganic materials 0.000 claims description 25
- 239000011737 fluorine Substances 0.000 claims description 25
- 238000001914 filtration Methods 0.000 claims description 23
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000006228 supernatant Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 14
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 10
- 229960003493 octyltriethoxysilane Drugs 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 6
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 6
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010025 steaming Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 150000008064 anhydrides Chemical group 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
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- Laminated Bodies (AREA)
Abstract
The invention relates to the technical field of copper-clad plates, in particular to epoxy resin for a high-frequency high-speed copper-clad plate and a preparation method thereof. According to the invention, firstly, the hexagonal boron nitride is peeled into the hexagonal boron nitride nanosheets, the hexagonal boron nitride nanosheets have good heat resistance and dielectric properties, the service performance of the copper-clad plate can be improved, and in order to further strengthen the dielectric properties of the copper-clad plate, fluorine atoms are introduced into the hexagonal boron nitride nanosheets, so that the heat stability of the copper-clad plate can be improved, and meanwhile, the dielectric constant of the copper-clad plate can be reduced. According to the invention, the hexagonal boron nitride nanosheets and the silicon dioxide are further compounded together, the silicon dioxide has good fluidity and excellent dielectric property, the silicon dioxide can reduce the thermal expansion coefficient of the copper-clad plate, and the heat resistance of the copper-clad plate is improved.
Description
Technical Field
The invention relates to the technical field of copper-clad plates, in particular to epoxy resin for a high-frequency high-speed copper-clad plate and a preparation method thereof.
Background
With the development of electronic technology, electronic technology is increasingly applied in various industries, and electronic devices are gradually developed towards high frequency, high speed, high power and high integration. The demand of the high-frequency high-speed copper-clad plate is larger and larger, and the resin is one of important components affecting the performance of the high-frequency high-speed copper-clad plate. The epoxy resin is used as a thermosetting polymer resin, has the advantages of low cost, high crosslinking density, small shrinkage, high mechanical strength, good cohesiveness, heat resistance, chemical corrosion resistance and the like after being cured, and is commonly used as a copper-clad plate. However, epoxy resins have high dielectric constants and dielectric losses, and are not well suited for modern electronic products. Therefore, it is important to improve the heat resistance and dielectric properties of the epoxy resin used for the high-frequency and high-speed copper-clad plate.
In order to solve the problems, improve the heat resistance of the epoxy resin and reduce the dielectric constant and dielectric loss of the epoxy resin, the invention provides the epoxy resin for the high-frequency high-speed copper-clad plate and a preparation method thereof.
Disclosure of Invention
The invention aims to provide epoxy resin for a high-frequency high-speed copper-clad plate and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
the preparation method of the epoxy resin for the high-frequency high-speed copper-clad plate comprises the following steps:
step one: taking hexagonal boron nitride-silicon dioxide and deionized water, and uniformly stirring to obtain hexagonal boron nitride-silicon dioxide solution; uniformly stirring maleic anhydride and toluene solution, adding the mixture into hexagonal boron nitride-silicon dioxide solution, uniformly stirring, reacting at 95-100 ℃ for 6-8 hours, and drying to obtain modified hexagonal boron nitride-silicon dioxide;
step two: and uniformly stirring the epoxy resin, the solvent, the curing agent and the modified hexagonal boron nitride-silicon dioxide to obtain the epoxy resin for the high-frequency high-speed copper-clad plate.
More optimally, the epoxy resin for the high-frequency high-speed copper-clad plate comprises the following components: 140-150 parts of epoxy resin, 50-62 parts of solvent, 2-15 parts of curing agent and 35-40 parts of modified hexagonal boron nitride-silicon dioxide.
More optimally, the preparation method of the hexagonal boron nitride-silicon dioxide comprises the following steps: taking absolute ethyl alcohol, deionized water and ethyl orthosilicate, and uniformly stirring to obtain an ethyl orthosilicate mixed solution; taking fluorine-containing hexagonal boron nitride nanosheets and ionized water, performing ultrasonic dispersion, adding ammonia water, performing ultrasonic dispersion for 20-30min, adding tetraethoxysilane mixed solution, stirring for 5-7h at 55-65 ℃, filtering, washing and drying to obtain hexagonal boron nitride-silicon dioxide.
More optimally, the preparation method of the fluorine-containing hexagonal boron nitride nano-sheet comprises the following steps: taking hexagonal boron nitride nanosheets and tetrahydrofuran, performing ultrasonic dispersion, adding 1H, 2H-tridecafluoron-octyl triethoxysilane and tetrabutylammonium fluoride solution, stirring for 4-5d, adding anhydrous calcium chloride, stirring for 22-26h, filtering, performing rotary evaporation until solid is separated out, dripping the rest liquid into glacial methanol, recrystallizing, standing, and drying to obtain the fluorine-containing hexagonal boron nitride nanosheets.
More optimally, the mass ratio of the fluorine-containing hexagonal boron nitride nano-sheet to the tetraethoxysilane is (0.1-0.2): (5-6).
More optimally, the preparation method of the hexagonal boron nitride nanosheets comprises the following steps: uniformly stirring hexagonal boron nitride and isopropanol, performing ultrasonic treatment for 6-7 hours, standing for 44-50 hours, taking supernatant, centrifuging, taking supernatant, filtering, washing and drying to obtain the hexagonal boron nitride nanosheets.
More preferably, the curing agent is any one or more of 2-methylimidazole and dicyandiamide.
More preferably, the solvent is any one or more of butanone and toluene.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides an epoxy resin for a high-frequency high-speed copper-clad plate and a preparation method thereof.
According to the invention, firstly, the hexagonal boron nitride is peeled into the hexagonal boron nitride nano-sheet, the hexagonal boron nitride nano-sheet has good heat resistance and dielectric property, and can improve the service performance of the copper-clad plate.
(2) The invention further combines the hexagonal boron nitride nano-sheet and silicon dioxide together, and controls the mass ratio of the fluorine-containing hexagonal boron nitride nano-sheet to the tetraethoxysilane to be (0.15-0.2): (5-6), the silicon dioxide has good fluidity and excellent dielectric property, the silicon dioxide can reduce the thermal expansion coefficient of the copper-clad plate, and the heat resistance of the copper-clad plate is improved. However, the hexagonal boron nitride-silicon dioxide is difficult to disperse in the resin and is easy to agglomerate. Firstly, maleic anhydride provides anhydride groups, and the anhydride groups have good compatibility with epoxy resin, so that the modified hexagonal boron nitride-silicon dioxide has better dispersibility in the epoxy resin, and simultaneously, the modified hexagonal boron nitride-silicon dioxide can promote crosslinking and solidification with the epoxy resin, enhance the dielectric property of the copper-clad plate and reduce the dielectric constant.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The manufacturers of all the raw materials involved in the present invention are not particularly limited, and include, by way of example: hexagonal boron nitride: particle size: 1-2 μm, supplied by Shanghai Ala Biochemical technology Co., ltd; 2-methylimidazole is supplied by basf corporation; 1H, 2H-tridecafluoron-octyltriethoxysilane is available from Shanghai Ala Biochemical technologies Co., ltd; epoxy resin: CYD-128 is provided by Baling petrochemical division of China petrochemical group.
Example 1: the preparation method of the epoxy resin for the high-frequency high-speed copper-clad plate comprises the following steps:
step one: preparing hexagonal boron nitride nano-sheets:
taking 2g of hexagonal boron nitride and 500mL of isopropanol, uniformly stirring, carrying out ultrasonic treatment for 6.5 hours, standing for 46 hours, taking supernatant, centrifuging, taking supernatant, filtering, washing and drying to obtain hexagonal boron nitride nanosheets;
step two: preparing fluorine-containing hexagonal boron nitride nano-sheets:
taking 0.2g of hexagonal boron nitride nanosheets and 100mL of tetrahydrofuran, performing ultrasonic dispersion, adding 1.5g of 1H, 2H-tridecafluoron-octyl triethoxysilane and 0.7mL of tetrabutylammonium fluoride solution, stirring for 4.5d, adding 1.5g of anhydrous calcium chloride, stirring for 24h, filtering, steaming until solid is separated out, dripping the rest liquid into 150mL of glacial methanol, recrystallizing, standing and drying to obtain the fluorine-containing hexagonal boron nitride nanosheets;
step three: preparation of hexagonal boron nitride-silicon dioxide:
taking 80mL of absolute ethyl alcohol, 15mL of deionized water and 5.58g of ethyl orthosilicate, and uniformly stirring to obtain an ethyl orthosilicate mixed solution; taking 0.15g of fluorine-containing hexagonal boron nitride nano-sheet and 100mL of deionized water, performing ultrasonic dispersion, adding 6mL of ammonia water, performing ultrasonic dispersion for 25min, adding tetraethoxysilane mixed solution, stirring at 60 ℃ for 6h, filtering, washing and drying to obtain hexagonal boron nitride-silicon dioxide;
step four: preparation of modified hexagonal boron nitride-silicon dioxide:
taking 5g of hexagonal boron nitride-silicon dioxide and 500mL of deionized water, and uniformly stirring to obtain a hexagonal boron nitride-silicon dioxide solution; uniformly stirring 10g of maleic anhydride and 100mL of toluene solution, adding the mixture into the hexagonal boron nitride-silicon dioxide solution, uniformly stirring, reacting for 7 hours at 97 ℃, and drying to obtain modified hexagonal boron nitride-silicon dioxide;
step five: preparation of epoxy resin for high-frequency high-speed copper-clad plate:
uniformly stirring epoxy resin, butanone, 2-methylimidazole, dicyandiamide and modified hexagonal boron nitride-silicon dioxide to obtain the epoxy resin for the high-frequency high-speed copper-clad plate;
the epoxy resin for the high-frequency high-speed copper-clad plate comprises the following components: 145 parts of epoxy resin, 55 parts of butanone, 0.5 part of 2-methylimidazole, 3.5 parts of dicyandiamide and 37 parts of modified hexagonal boron nitride-silicon dioxide.
Example 2: the preparation method of the epoxy resin for the high-frequency high-speed copper-clad plate comprises the following steps:
step one: preparing hexagonal boron nitride nano-sheets:
taking 2g of hexagonal boron nitride and 500mL of isopropanol, uniformly stirring, carrying out ultrasonic treatment for 6 hours, standing for 44 hours, taking supernatant, centrifuging, taking supernatant, filtering, washing and drying to obtain hexagonal boron nitride nanosheets;
step two: preparing fluorine-containing hexagonal boron nitride nano-sheets:
taking 0.2g of hexagonal boron nitride nanosheets and 100mL of tetrahydrofuran, performing ultrasonic dispersion, adding 1.5g of 1H, 2H-tridecafluoron-octyl triethoxysilane and 0.7mL of tetrabutylammonium fluoride solution, stirring for 4d, adding 1.5g of anhydrous calcium chloride, stirring for 22h, filtering, steaming until solid is separated out, dripping the rest liquid into 150mL of glacial methanol, recrystallizing, standing and drying to obtain fluorine-containing hexagonal boron nitride nanosheets;
step three: preparation of hexagonal boron nitride-silicon dioxide:
taking 80mL of absolute ethyl alcohol, 15mL of deionized water and 5.58g of ethyl orthosilicate, and uniformly stirring to obtain an ethyl orthosilicate mixed solution; taking 0.15g of fluorine-containing hexagonal boron nitride nano-sheet and 100mL of deionized water, performing ultrasonic dispersion, adding 6mL of ammonia water, performing ultrasonic dispersion for 20min, adding tetraethoxysilane mixed solution, stirring for 5h at 55 ℃, filtering, washing and drying to obtain hexagonal boron nitride-silicon dioxide;
step four: preparation of modified hexagonal boron nitride-silicon dioxide:
taking 5g of hexagonal boron nitride-silicon dioxide and 500mL of deionized water, and uniformly stirring to obtain a hexagonal boron nitride-silicon dioxide solution; uniformly stirring 10g of maleic anhydride and 100mL of toluene solution, adding the mixture into the hexagonal boron nitride-silicon dioxide solution, uniformly stirring, reacting for 6 hours at 95 ℃, and drying to obtain modified hexagonal boron nitride-silicon dioxide;
step five: preparation of epoxy resin for high-frequency high-speed copper-clad plate:
uniformly stirring epoxy resin, butanone, 2-methylimidazole, dicyandiamide and modified hexagonal boron nitride-silicon dioxide to obtain the epoxy resin for the high-frequency high-speed copper-clad plate;
the epoxy resin for the high-frequency high-speed copper-clad plate comprises the following components: 140 parts of epoxy resin, 50 parts of butanone, 0.5 part of 2-methylimidazole, 3 parts of dicyandiamide and 35 parts of modified hexagonal boron nitride-silicon dioxide.
Example 3: the preparation method of the epoxy resin for the high-frequency high-speed copper-clad plate comprises the following steps:
step one: preparing hexagonal boron nitride nano-sheets:
taking 2g of hexagonal boron nitride and 500mL of isopropanol, uniformly stirring, carrying out ultrasonic treatment for 7 hours, standing for 50 hours, taking supernatant, centrifuging, taking supernatant, filtering, washing and drying to obtain hexagonal boron nitride nanosheets;
step two: preparing fluorine-containing hexagonal boron nitride nano-sheets:
taking 0.2g of hexagonal boron nitride nanosheets and 100mL of tetrahydrofuran, performing ultrasonic dispersion, adding 1.5g of 1H, 2H-tridecafluoron-octyl triethoxysilane and 0.7mL of tetrabutylammonium fluoride solution, stirring for 4-5d, adding 1.5g of anhydrous calcium chloride, stirring for 26h, filtering, steaming until solid is separated out, dripping the rest liquid into 150mL of glacial methanol, recrystallizing, standing and drying to obtain the fluorine-containing hexagonal boron nitride nanosheets;
step three: preparation of hexagonal boron nitride-silicon dioxide:
taking 80mL of absolute ethyl alcohol, 15mL of deionized water and 5.58g of ethyl orthosilicate, and uniformly stirring to obtain an ethyl orthosilicate mixed solution; taking 0.15g of fluorine-containing hexagonal boron nitride nano-sheet and 100mL of deionized water, performing ultrasonic dispersion, adding 6mL of ammonia water, performing ultrasonic dispersion for 30min, adding tetraethoxysilane mixed solution, stirring for 7h at 65 ℃, filtering, washing and drying to obtain hexagonal boron nitride-silicon dioxide;
step four: preparation of modified hexagonal boron nitride-silicon dioxide:
taking 5g of hexagonal boron nitride-silicon dioxide and 500mL of deionized water, and uniformly stirring to obtain a hexagonal boron nitride-silicon dioxide solution; uniformly stirring 10g of maleic anhydride and 100mL of toluene solution, adding the mixture into the hexagonal boron nitride-silicon dioxide solution, uniformly stirring, reacting for 8 hours at 100 ℃, and drying to obtain modified hexagonal boron nitride-silicon dioxide;
step five: preparation of epoxy resin for high-frequency high-speed copper-clad plate:
uniformly stirring epoxy resin, butanone, 2-methylimidazole, dicyandiamide and modified hexagonal boron nitride-silicon dioxide to obtain the epoxy resin for the high-frequency high-speed copper-clad plate;
the epoxy resin for the high-frequency high-speed copper-clad plate comprises the following components: 150 parts of epoxy resin, 62 parts of butanone, 1 part of 2-methylimidazole, 4 parts of dicyandiamide and 40 parts of modified hexagonal boron nitride-silicon dioxide.
Comparative example 1: the preparation method of the epoxy resin for the high-frequency high-speed copper-clad plate does not use 1H, 2H-tridecafluoron-octyl triethoxysilane to modify the hexagonal boron nitride nano-sheet, and the rest is the same as the example 1.
Step one: preparing hexagonal boron nitride nano-sheets:
taking 2g of hexagonal boron nitride and 500mL of isopropanol, uniformly stirring, carrying out ultrasonic treatment for 6.5 hours, standing for 46 hours, taking supernatant, centrifuging, taking supernatant, filtering, washing and drying to obtain hexagonal boron nitride nanosheets;
step two: preparation of hexagonal boron nitride-silicon dioxide:
taking 80mL of absolute ethyl alcohol, 15mL of deionized water and 5.58g of ethyl orthosilicate, and uniformly stirring to obtain an ethyl orthosilicate mixed solution; taking 0.15g of hexagonal boron nitride nanosheets and 100mL of deionized water, performing ultrasonic dispersion, adding 6mL of ammonia water, performing ultrasonic dispersion for 25min, adding tetraethoxysilane mixed solution, stirring for 6h at 60 ℃, filtering, washing and drying to obtain hexagonal boron nitride-silicon dioxide;
step three: preparation of modified hexagonal boron nitride-silicon dioxide:
taking 5g of hexagonal boron nitride-silicon dioxide and 500mL of deionized water, and uniformly stirring to obtain a hexagonal boron nitride-silicon dioxide solution; uniformly stirring 10g of maleic anhydride and 100mL of toluene solution, adding the mixture into the hexagonal boron nitride-silicon dioxide solution, uniformly stirring, reacting for 7 hours at 97 ℃, and drying to obtain modified hexagonal boron nitride-silicon dioxide;
step four: preparation of epoxy resin for high-frequency high-speed copper-clad plate:
uniformly stirring epoxy resin, butanone, 2-methylimidazole, dicyandiamide and modified hexagonal boron nitride-silicon dioxide to obtain the epoxy resin for the high-frequency high-speed copper-clad plate;
the epoxy resin for the high-frequency high-speed copper-clad plate comprises the following components: 145 parts of epoxy resin, 55 parts of butanone, 0.5 part of 2-methylimidazole, 3.5 parts of dicyandiamide and 37 parts of modified hexagonal boron nitride-silicon dioxide.
Comparative example 2: the preparation method of the epoxy resin for the high-frequency high-speed copper-clad plate does not use maleic anhydride to modify hexagonal boron nitride-silicon dioxide, and the rest is the same as in example 1.
Step one: preparing hexagonal boron nitride nano-sheets:
taking 2g of hexagonal boron nitride and 500mL of isopropanol, uniformly stirring, carrying out ultrasonic treatment for 6.5 hours, standing for 46 hours, taking supernatant, centrifuging, taking supernatant, filtering, washing and drying to obtain hexagonal boron nitride nanosheets;
step two: preparing fluorine-containing hexagonal boron nitride nano-sheets:
taking 0.2g of hexagonal boron nitride nanosheets and 100mL of tetrahydrofuran, performing ultrasonic dispersion, adding 1.5g of 1H, 2H-tridecafluoron-octyl triethoxysilane and 0.7mL of tetrabutylammonium fluoride solution, stirring for 4.5d, adding 1.5g of anhydrous calcium chloride, stirring for 24h, filtering, steaming until solid is separated out, dripping the rest liquid into 150mL of glacial methanol, recrystallizing, standing and drying to obtain the fluorine-containing hexagonal boron nitride nanosheets;
step three: preparation of hexagonal boron nitride-silicon dioxide:
taking 80mL of absolute ethyl alcohol, 15mL of deionized water and 5.58g of ethyl orthosilicate, and uniformly stirring to obtain an ethyl orthosilicate mixed solution; taking 0.15g of fluorine-containing hexagonal boron nitride nano-sheet and 100mL of deionized water, performing ultrasonic dispersion, adding 6mL of ammonia water, performing ultrasonic dispersion for 25min, adding tetraethoxysilane mixed solution, stirring at 60 ℃ for 6h, filtering, washing and drying to obtain hexagonal boron nitride-silicon dioxide;
step four: preparation of epoxy resin for high-frequency high-speed copper-clad plate:
uniformly stirring epoxy resin, butanone, 2-methylimidazole, dicyandiamide and hexagonal boron nitride-silicon dioxide to obtain the epoxy resin for the high-frequency high-speed copper-clad plate;
the epoxy resin for the high-frequency high-speed copper-clad plate comprises the following components: 145 parts of epoxy resin, 55 parts of butanone, 0.5 part of 2-methylimidazole, 3.5 parts of dicyandiamide and 37 parts of hexagonal boron nitride-silicon dioxide.
Comparative example 3: the preparation method of the epoxy resin for the high-frequency high-speed copper-clad plate comprises the following steps of: 5.58, the remainder being the same as in example 1.
Step one: preparing hexagonal boron nitride nano-sheets:
taking 2g of hexagonal boron nitride and 500mL of isopropanol, uniformly stirring, carrying out ultrasonic treatment for 6.5 hours, standing for 46 hours, taking supernatant, centrifuging, taking supernatant, filtering, washing and drying to obtain hexagonal boron nitride nanosheets;
step two: preparing fluorine-containing hexagonal boron nitride nano-sheets:
taking 0.2g of hexagonal boron nitride nanosheets and 100mL of tetrahydrofuran, performing ultrasonic dispersion, adding 1.5g of 1H, 2H-tridecafluoron-octyl triethoxysilane and 0.7mL of tetrabutylammonium fluoride solution, stirring for 4.5d, adding 1.5g of anhydrous calcium chloride, stirring for 24h, filtering, steaming until solid is separated out, dripping the rest liquid into 150mL of glacial methanol, recrystallizing, standing and drying to obtain the fluorine-containing hexagonal boron nitride nanosheets;
step three: preparation of hexagonal boron nitride-silicon dioxide:
taking 80mL of absolute ethyl alcohol, 15mL of deionized water and 5.58g of ethyl orthosilicate, and uniformly stirring to obtain an ethyl orthosilicate mixed solution; taking 0.1g of fluorine-containing hexagonal boron nitride nano-sheet and 100mL of deionized water, performing ultrasonic dispersion, adding 6mL of ammonia water, performing ultrasonic dispersion for 25min, adding tetraethoxysilane mixed solution, stirring at 60 ℃ for 6h, filtering, washing and drying to obtain hexagonal boron nitride-silicon dioxide;
step four: preparation of modified hexagonal boron nitride-silicon dioxide:
taking 5g of hexagonal boron nitride-silicon dioxide and 500mL of deionized water, and uniformly stirring to obtain a hexagonal boron nitride-silicon dioxide solution; uniformly stirring 10g of maleic anhydride and 100mL of toluene solution, adding the mixture into the hexagonal boron nitride-silicon dioxide solution, uniformly stirring, reacting for 7 hours at 97 ℃, and drying to obtain modified hexagonal boron nitride-silicon dioxide;
step five: preparation of epoxy resin for high-frequency high-speed copper-clad plate:
uniformly stirring epoxy resin, butanone, 2-methylimidazole, dicyandiamide and modified hexagonal boron nitride-silicon dioxide to obtain the epoxy resin for the high-frequency high-speed copper-clad plate;
the epoxy resin for the high-frequency high-speed copper-clad plate comprises the following components: 145 parts of epoxy resin, 55 parts of butanone, 0.5 part of 2-methylimidazole, 3.5 parts of dicyandiamide and 37 parts of modified hexagonal boron nitride-silicon dioxide.
Experiment:
will 211 (211)Respectively soaking 6-type glass fiber cloth in epoxy resin for the high-frequency high-speed copper-clad plate prepared in the examples 1-3 and the comparative examples 1-3, taking out, and drying at 110 ℃ for 2min to obtain a prepreg; and (3) overlapping 3 prepregs, covering electrolytic copper foil with the thickness of 40 mu m on the upper and lower surfaces, and hot-pressing for 2.5 hours at the temperature of 190 ℃ under the pressure of 35MPa to obtain the copper-clad plate. The substrate comprises the following components: 80% of glass fiber cloth and 20% of PPO resin adhesive by weight, wherein the gram weight of the glass fiber cloth is 25g/m 2 The thickness was 0.03mm. Each copper-clad plate was subjected to performance test, and the copper-clad plate was cut into 50mm×50mm×1mm samples, and the dielectric constant and dielectric dissipation factor of the copper-clad plate were tested at 25 ℃ and 10GHz frequency. Testing heat-resistant cycle times of copper-clad plate by using universal material testing machine
Conclusion: comparative example 1 the hexagonal boron nitride nanosheets were modified without using 1h,2 h-tridecafluoron-octyltriethoxysilane, fluorine atoms were not introduced into the hexagonal boron nitride nanosheets, the number of heat resistant cycles of the copper clad laminate was reduced, the thermal stability was deteriorated, and the dielectric constant was increased. Comparative example 2 does not use maleic anhydride to modify hexagonal boron nitride-silica, the dispersibility of the modified hexagonal boron nitride-silica in epoxy resin becomes poor, the dielectric properties of the copper clad laminate become poor, and the thermal stability is poor. Comparative example 3 the mass ratio of fluorine-containing hexagonal boron nitride nanoplatelets to ethyl orthosilicate was 0.1:5.58, dielectric properties are degraded.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A preparation method of epoxy resin for a high-frequency high-speed copper-clad plate is characterized by comprising the following steps: the method comprises the following steps:
step one: taking hexagonal boron nitride-silicon dioxide and deionized water, and uniformly stirring to obtain hexagonal boron nitride-silicon dioxide solution; uniformly stirring maleic anhydride and toluene solution, adding the mixture into hexagonal boron nitride-silicon dioxide solution, uniformly stirring, reacting at 95-100 ℃ for 6-8 hours, and drying to obtain modified hexagonal boron nitride-silicon dioxide;
step two: uniformly stirring epoxy resin, a solvent, a curing agent and modified hexagonal boron nitride-silicon dioxide to obtain epoxy resin for a high-frequency high-speed copper-clad plate;
the epoxy resin for the high-frequency high-speed copper-clad plate comprises the following components: 140-150 parts by weight of epoxy resin, 50-62 parts by weight of solvent, 2-15 parts by weight of curing agent and 35-40 parts by weight of modified hexagonal boron nitride-silicon dioxide;
the preparation method of the hexagonal boron nitride-silicon dioxide comprises the following steps: taking absolute ethyl alcohol, deionized water and ethyl orthosilicate, and uniformly stirring to obtain an ethyl orthosilicate mixed solution; taking fluorine-containing hexagonal boron nitride nanosheets and ionized water, performing ultrasonic dispersion, adding ammonia water, performing ultrasonic dispersion for 20-30min, adding tetraethoxysilane mixed solution, stirring for 5-7h at 55-65 ℃, filtering, washing and drying to obtain hexagonal boron nitride-silicon dioxide;
the preparation method of the fluorine-containing hexagonal boron nitride nanosheets comprises the following steps: taking hexagonal boron nitride nanosheets and tetrahydrofuran, performing ultrasonic dispersion, adding 1H, 2H-tridecafluoron-octyl triethoxysilane and tetrabutylammonium fluoride solution, stirring for 4-5d, adding anhydrous calcium chloride, stirring for 22-26h, filtering, performing rotary evaporation until solid is separated out, dripping the rest liquid into glacial methanol, recrystallizing, standing, and drying to obtain the fluorine-containing hexagonal boron nitride nanosheets.
2. The method for preparing the epoxy resin for the high-frequency and high-speed copper-clad plate, which is disclosed in claim 1, is characterized in that: the mass ratio of the fluorine-containing hexagonal boron nitride nano-sheet to the tetraethoxysilane is (0.15-0.2): (5-6).
3. The method for preparing the epoxy resin for the high-frequency and high-speed copper-clad plate, which is disclosed in claim 1, is characterized in that: the preparation method of the hexagonal boron nitride nanosheets comprises the following steps: uniformly stirring hexagonal boron nitride and isopropanol, performing ultrasonic treatment for 6-7 hours, standing for 44-50 hours, taking supernatant, centrifuging, taking supernatant, filtering, washing and drying to obtain the hexagonal boron nitride nanosheets.
4. The method for preparing the epoxy resin for the high-frequency and high-speed copper-clad plate, which is disclosed in claim 1, is characterized in that: the curing agent is one or more of 2-methylimidazole and dicyandiamide.
5. The method for preparing the epoxy resin for the high-frequency and high-speed copper-clad plate, which is disclosed in claim 1, is characterized in that: the solvent is any one or more of butanone and toluene.
6. The epoxy resin for a high-frequency and high-speed copper-clad plate prepared by the method for preparing the epoxy resin for the high-frequency and high-speed copper-clad plate according to any one of claims 1 to 5.
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