High-temperature-resistant, high-frequency and high-speed BT resin-based copper-clad plate and preparation method thereof
By combining core-shell structured boron fluorinated nitride and low-dielectric dispersion modified silicon carbide with cross-linked coating of graphene oxide and ammonium polyphosphate, the problems of low dielectric and high thermal conductivity of copper clad laminates under high temperature and high frequency environments are solved, thereby improving the stability of signal transmission and mechanical strength.
Patent Information
- Application Number
- CN202511824149.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-05
- Publication Date
- 2026-01-20
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
Existing technologies cannot meet the requirements of low dielectric constant and low dielectric loss of copper clad laminates in high temperature and high frequency environments, resulting in severe signal attenuation and loss during transmission, and insufficient thermal stability of materials in high temperature processing and working environments.
The first and second fillers, which adopt a core-shell structure, are combined with boron fluoride and silicon carbide modified with low dielectric dispersion, and then cross-linked with graphene oxide and ammonium polyphosphate to form a copper-clad laminate material that is resistant to high temperature and high frequency.
This achieves low dielectric properties and high thermal conductivity in copper-clad laminates under high temperature and high frequency environments, reducing signal transmission delay and loss, while improving mechanical strength and thermal stability.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of copper-clad plate, and particularly relates to a high-temperature-resistant high-frequency high-speed BT resin-based copper-clad plate and a preparation method thereof. BACKGROUND
[0002] In the 5G fast-developing technological era, due to the fact that 5G high-frequency signals are prone to attenuation and loss in the signal transmission process, in order to guarantee the integrity and stability in the signal transmission process, electronic device materials are required to have low dielectric constant and low dielectric loss; as the material of printed circuit boards, copper-clad plates need to have high-frequency high-speed performance. Modern electronic industry adopts lead-free solder, and the high-temperature environment in the processing process requires that the material itself has high thermal stability, is resistant to high temperature, and is suitable for processing environment and high-temperature working environment.
[0003] To solve the above problems and manufacture high-temperature-resistant high-frequency high-speed copper-clad plates, the present application provides a high-temperature-resistant high-frequency high-speed BT resin-based copper-clad plate and a preparation method thereof. SUMMARY
[0004] The present application aims to provide a high-temperature-resistant high-frequency high-speed BT resin-based copper-clad plate and a preparation method thereof to solve the problems in the prior art.
[0005] To achieve the above-mentioned purpose, the present application provides the following technical scheme: Step one: propylene amine is taken and added into toluene, and mixed uniformly to obtain a propylene amine solution; phenol and polyformaldehyde are taken and added into toluene, and magnetically stirred; heating is performed, and the propylene amine solution is added; heating is performed, and reaction is carried out; cooling is performed, extraction is carried out, and suction filtration is carried out to obtain a benzoxazine monomer; Step two: graphene oxide is taken, ground, and sieved; the benzoxazine monomer, graphene oxide, and ammonium polyphosphate are taken and added into dimethyl silicone oil, and stirred, heated, and reacted; heating is performed, reaction is carried out, cooling is performed, washing is performed, suction filtration is carried out, and drying is carried out to obtain microcapsules; Step three: sodium hydroxide is taken and added into deionized water, and mixed uniformly to obtain a sodium hydroxide solution; corn cob lignin is taken and added into the sodium hydroxide solution, and mixed uniformly; epichlorohydrin and tetrabutylammonium bromide are added, and reaction is carried out; cooling is performed, tetrabutylammonium bromide and sodium hydroxide are added, and reaction is carried out; precipitation is carried out, and drying is carried out to obtain an epoxy resin monomer; Step four: the epoxy resin monomer and the microcapsules are taken and added into acetone, and ultrasonic treatment, stirring, and suction filtration are carried out; heating is performed, and the first filler, the second filler, bisphenol A diglycidyl ether, and polyether amine are added, and ultrasonic treatment is carried out to obtain a copper-clad plate resin glue solution; glass fiber cloth is taken, burned, placed in the copper-clad plate resin glue solution, immersed, solidified, and laminated to obtain a prepreg; the prepreg is loaded into a copper-clad plate, hot-pressed, unloaded, cut, and a high-temperature-resistant high-frequency high-speed BT resin-based copper-clad plate is obtained.
[0006] More optimized, the preparation method of the first filler is: taking hexadecyl trimethyl ammonium bromide into ultrapure water, mixing uniformly to obtain a template solution; taking fluorinated boron nitride into the template solution, ultrasonicating and stirring for 85-95 min under the condition of temperature 15-25℃; slowly adding anhydrous ethanol, ultrasonicating and stirring for 55-65 min; adjusting pH using ammonia water under the condition of temperature 35-45℃, stirring for 9-11 min; adding tetraethyl orthosilicate, stirring for 25-35 min, aging for 3-5 h, centrifuging, washing, vacuum drying, baking for 55-65 min under the condition of temperature 470-490℃ to obtain the first filler.
[0007] More optimized, the preparation method of the second filler is: taking silicon carbide into deionized water, adding grinding balls, adding perfluorodecyl triethoxysilane under the condition of rotation speed 290-310 rpm, reacting for 1.5-2.5 h; centrifuging, drying for 7-9 h under the condition of temperature 70-80℃, grinding to obtain the second filler.
[0008] More optimized, the copper-clad plate resin glue solution comprises the following components, in terms of weight parts: 79-80 parts by weight of epoxy resin monomer, 4-6 parts by weight of microcapsule, 85-105 parts by weight of acetone, 3-5 parts by weight of the first filler, 3-5 parts by weight of the second filler, 15-16 parts by weight of bisphenol A diglycidyl ether, and 5-6 parts by weight of polyether amine.
[0009] More optimized, the microcapsule comprises the following components, in terms of weight parts: 0.5-1.5 parts by weight of benzoxazine monomer, 4-5 parts by weight of graphene oxide, 4-5 parts by weight of ammonium polyphosphate, and 9-11 parts by weight of dimethyl silicone oil.
[0010] More optimized, the preparation method of fluorinated boron nitride is: taking hexagonal boron nitride, vacuumizing, introducing carbon tetrafluoride and nitrogen to adjust the pressure to (-2100)-(-1900) kPa, vacuumizing, introducing carbon tetrafluoride and nitrogen to adjust the pressure to (-1600)-(-1400) kPa, vacuumizing; pressurizing, performing plasma discharge under the condition of voltage 27-29 kV and frequency 8-10 kHz for 14-16 min to obtain fluorinated boron nitride.
[0011] More optimized, the pH value is adjusted to 8.5-9.5.
[0012] More optimized, the second filler comprises the following components, in terms of weight parts: 95-105 parts by weight of silicon carbide, 95-105 parts by weight of deionized water, 195-205 parts by weight of grinding balls, and 0.3-0.5 parts by weight of perfluorodecyl triethoxysilane.
[0013] More optimized, the volume ratio of carbon tetrafluoride to nitrogen is (0.9-1.1):(24-26).
[0014] Compared with the prior art, the present application has the following advantages: 1. The present application provides a high-temperature-resistant, high-frequency-resistant and high-speed-resistant BT resin-based copper-clad plate, which is prepared by using epoxidized corn cob lignin as an epoxy resin monomer, fluorinated boron nitride with a core-shell structure as a first filler, low-dielectric-dispersed modified silicon carbide as a second filler, bisphenol A diglycidyl ether and polyether amine as a curing agent, and epoxy resin monomer cross-linking to coat microcapsules to obtain a high-temperature-resistant, high-frequency-resistant and high-speed-resistant BT resin-based copper-clad plate; wherein benzoxazine monomers are used as coating materials to cross-link and coat graphene oxide and ammonium polyphosphate to form polybenzoxazine, which is resistant to high temperature and has a low dielectric constant, thereby reducing the delay and loss of signals in the transmission process and being suitable for high-frequency and high-speed environments. On the one hand, ammonium polyphosphate is used as a flame retardant and graphene oxide is used as a carbon source, and the ammonium polyphosphate decomposes under heat to form a strong water-absorbing substance, which promotes the carbonization of the carbon source graphene oxide to form a dense carbonized layer to insulate heat and oxygen and play a flame-retardant role; on the other hand, the addition of graphene oxide improves the thermal conductivity and mechanical strength of the copper-clad plate substrate.
[0015] 2. The present application provides a method for preparing a first filler, which is prepared by using fluorinated boron nitride as a core layer and silicon dioxide as a shell layer to obtain a core-shell structure first filler; wherein carbon tetrafluoride is used as a fluorine source gas, and hexagonal boron nitride is modified by plasma fluorination to obtain fluorinated boron nitride; the hexagonal boron nitride has high thermal conductivity, low dielectric constant and low dielectric loss, thereby improving the thermal conduction rate and low dielectric properties of the copper-clad plate and being suitable for high-temperature, high-frequency and high-speed environments. The silicon dioxide shell layer, on the one hand, inhibits the agglomeration of fluorinated boron nitride particles; on the other hand, the hydroxyl groups on the surface of the silicon dioxide chemically interact with the polar functional groups of the organic resin matrix to improve the compatibility and interfacial bonding strength of the filler and the matrix.
[0016] 3. The present application provides a method for preparing a second filler, which is prepared by using perfluorodecyl triethoxysilane to modify silicon carbide for low dielectric and dispersion; silicon carbide has high hardness, excellent thermal stability and high thermal conductivity, and is resistant to high temperature; through modification by perfluorodecyl triethoxysilane, on the one hand, the silane groups of perfluorodecyl triethoxysilane chemically bond with the hydroxyl groups on the surface of silicon carbide to introduce perfluorodecyl groups on the surface of silicon carbide, and the perfluorodecyl groups have a high proportion of fluorine atoms to reduce the dielectric constant; on the other hand, the perfluorodecyl long chains on the surface of silicon carbide inhibit agglomeration through steric hindrance to improve the dispersibility of silicon carbide particles. DETAILED DESCRIPTION
[0017] The technical solutions in the embodiments of the present application will be described below in a clear and complete manner. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.
[0018] The source and model of the substance involved in the present application are not specially limited, and exemplarily include: 100nm hexagonal boron nitride with the product number XH-BN-100 is provided by Shanghai Xiaohuan Nanometer Technology Co., Ltd.; Tetraethyl orthosilicate with the product number T110593-1L is provided by Shanghai Aladdin Biochemical Technology Co., Ltd.; 100nm silicon carbide with the product number XH-SiC-100 is provided by Shanghai Xiaohuan Nanometer Technology Co., Ltd.; The grinding ball with the product number GL-200 is provided by Pingxiang Guanlin Environmental Protection Technology Co., Ltd.; Perfluorodecyltriethoxysilane with the product number S40230-25g is provided by Shanghai Yuan Ye Biological Technology Co., Ltd.; Paraformaldehyde with the product number 410 is provided by Jinan Shidada Chemical Co., Ltd.; Graphene oxide with the product number M33420 is provided by Shanghai Mai Rui Biological Technology Co., Ltd.; Ammonium polyphosphate with the product number S67475-100g is provided by Shanghai Yuan Ye Biological Technology Co., Ltd.; Dimethyl silicone oil with the product number DY-201 is provided by Shandong Dayi Chemical Co., Ltd.; LIG-1 type corncob lignin is provided by Shandong Longli Biological Technology Co., Ltd.; Epichlorohydrin with the product number N02418 is provided by Shanghai Mai Rui Biological Technology Co., Ltd.; Tetrabutylammonium bromide with the product number HC3354 is provided by Tianmen Hengchang Chemical Co., Ltd.; Bisphenol A diglycidyl ether with the product number JS0452 is provided by Hubei Jusheng Technology Co., Ltd.; Polyetheramine with the product number HC1775 is provided by Tianmen Hengchang Chemical Co., Ltd.; Example 1: A preparation method of a high-temperature-resistant, high-frequency-resistant and high-speed-resistant BT resin-based copper-clad plate; Step one: preparation of the first filler S1: Take hexagonal boron nitride, vacuumize, and pass in carbon tetrafluoride and nitrogen according to the volume ratio of 0.9:26 to adjust the pressure to-2100kPa, vacuumize, and pass in carbon tetrafluoride and nitrogen according to the volume ratio of 0.9:26 to adjust the pressure to-1600kPa, vacuumize; pressurize, and under the conditions of voltage 27kV and frequency 8kHz, carry out plasma discharge for 14min to obtain fluorinated boron nitride; S2: Take 1.44 g of cetyl trimethyl ammonium bromide and add it to 110 mL of ultrapure water, mix well to obtain a template solution; take 0.3 g of nitrogen fluorinated boron oxide and add it to the template solution, ultrasonic at a temperature of 15℃, stir for 85 min; slowly add 60 mL of anhydrous ethanol, ultrasonic, stir for 55 min; adjust the pH value to 8.5 using ammonia water at a temperature of 35℃, stir for 9 min; add 0.06 g of tetraethyl orthosilicate, stir for 25 min, age for 3 h, centrifuge, wash, vacuum dry, bake at a temperature of 470℃ for 55 min to obtain a first filler; Step two: preparation of a second filler Take 95 g of silicon carbide and add it to 95 mL of deionized water, add 195 g of grinding balls, add 0.3 g of perfluorodecyl triethoxysilane at a rotation speed of 290 rpm, react for 1.5 h; centrifuge, dry at a temperature of 70℃ for 7 h, grind to obtain a second filler; Step three: preparation of microcapsules S1: Take 2.85 g of propylene amine and add it to 5 mL of toluene, mix well to obtain a propylene amine solution; take 4.7 g of phenol, 3.3 g of polyformaldehyde and add them to 20 mL of toluene, magnetically stir at a temperature of 15℃ for 25 min; heat, add the propylene amine solution at a temperature of 40℃; heat, react at a temperature of 95℃ for 9 h; cool, extract, suction filter to obtain a benzoxazine monomer; S2: Take graphene oxide, grind, sieve; take 1 g of benzoxazine monomer, 4 g of graphene oxide, 4 g of ammonium polyphosphate and add them to 10 g of dimethyl silicone oil, stir at a temperature of 15℃ for 15 min, heat, react at a temperature of 140℃ for 3 h; heat, react at a temperature of 170℃ for 0.5 h, cool, wash, suction filter, dry to obtain microcapsules; Step four: preparation of high-temperature, high-frequency and high-speed BT resin-based copper-clad plate S1: Take 0.004 g of sodium hydroxide and add it to 1 L of deionized water, mix well to obtain a sodium hydroxide solution; take 4 g of corn cob lignin and add it to 10 mL of sodium hydroxide solution, mix well, add 40 g of epoxy chloropropane, 0.4 g of tetrabutyl ammonium bromide, react at a temperature of 55℃ for 2 h; cool, add 0.4 g of tetrabutyl ammonium bromide, 0.4 g of sodium hydroxide, react for 7 h; precipitate, dry to obtain an epoxy resin monomer; S2: Take 79 g of epoxy resin monomer, 5 g of microcapsules and add them to 85 mL of acetone, ultrasonic, stir, suction filter; heat, add 3 g of the first filler, 3 g of the second filler, 15 g of bisphenol A diglycidyl ether, 5 g of polyether amine at a temperature of 90℃, ultrasonic to obtain a copper-clad plate resin glue solution; S3: Take the glass fiber cloth, burn, and place it in the copper-clad plate resin glue solution, immerse for 9 minutes, and cure for 9 minutes at a temperature of 175 DEG C to obtain a prepreg; stack, plate, hot press, disassemble the plate, and cut to obtain a high-temperature, high-frequency, and high-speed BT resin-based copper-clad plate.
[0019] Embodiment 2: A method for preparing a high-temperature, high-frequency, and high-speed BT resin-based copper-clad plate; Step one: preparing a first filler S1: Take the hexagonal boron nitride, vacuumize, and pass in carbon tetrafluoride and nitrogen at a volume ratio of 1:25 to adjust the pressure to -2000 kPa, vacuumize, and pass in carbon tetrafluoride and nitrogen at a volume ratio of 1:25 to adjust the pressure to -1500 kPa, vacuumize; pressurize, and perform plasma discharge at a voltage of 28 kV and a frequency of 9 kHz for 15 minutes to obtain fluorinated boron nitride; S2: Take 1.44 g of cetyltrimethylammonium bromide and add it to 120 mL of ultrapure water, mix well to obtain a template solution; take 0.4 g of fluorinated boron nitride and add it to the template solution, ultrasonic stir for 90 minutes at a temperature of 20 DEG C; slowly add 60 mL of anhydrous ethanol, ultrasonic stir for 60 minutes; adjust the pH value to 9 using ammonia water at a temperature of 40 DEG C, stir for 10 minutes; add 0.08 g of tetraethyl orthosilicate, stir for 30 minutes, age for 4 hours, centrifuge, wash, vacuum dry, and bake at a temperature of 480 DEG C for 60 minutes to obtain a first filler; Step two: preparing a second filler Take 100 g of silicon carbide and add it to 100 mL of deionized water, add 200 g of grinding balls, and add 0.4 g of perfluorodecyltriethoxysilane at a rotation speed of 300 rpm, and react for 2 hours; centrifuge, dry at a temperature of 75 DEG C for 8 hours, and grind to obtain a second filler; Step three: preparing a microcapsule S1: Take 2.85 g of propylene amine and add it to 5 mL of toluene, mix well to obtain a propylene amine solution; take 4.7 g of phenol and 3.3 g of paraformaldehyde and add them to 20 mL of toluene, magnetically stir for 30 minutes at a temperature of 20 DEG C; heat, add the propylene amine solution at a temperature of 45 DEG C; heat, and react for 10 hours at a temperature of 100 DEG C; cool, extract, and filter to obtain a benzoxazine monomer; S2: Take graphene oxide, grind, and sieve; take 1 g of benzoxazine monomer, 4.5 g of graphene oxide, and 4.5 g of ammonium polyphosphate and add them to 10 g of dimethyl silicone oil, stir for 20 minutes at a temperature of 20 DEG C, heat, and react for 4 hours at a temperature of 150 DEG C; heat, and react for 1 hour at a temperature of 180 DEG C, cool, wash, filter, and dry to obtain a microcapsule; Step four: preparation of high temperature resistant high frequency high speed BT resin based copper clad plate S1: take 0.004g sodium hydroxide into 1L deionized water, mix well, get sodium hydroxide solution; take 4g corn cob lignin into 55mL sodium hydroxide solution, mix well, add 40g epichlorohydrin, 0.4g tetrabutylammonium bromide, under the condition of temperature 60℃, reaction for 3h; cooling, add 1.2g tetrabutylammonium bromide, 1.2g sodium hydroxide, reaction for 8h; precipitation, drying, get epoxy resin monomer; S2: take 79.5g epoxy resin monomer, 5g microcapsule into 95mL acetone, ultrasonic, stirring, suction filtration; heating, under the condition of temperature 100℃, add 4g first filler, 4g second filler, 15.5g bisphenol A diglycidyl ether, 5.5g polyether amine, ultrasonic, get copper clad plate resin glue solution; S3: take glass fiber cloth, burning, put into copper clad plate resin glue solution, immerse for 10min, under the condition of temperature 185℃, curing for 10min, get prepreg; laminating, plate, hot pressing, dismounting, cutting, get high temperature resistant high frequency high speed BT resin based copper clad plate.
[0020] Example 3: a preparation method of high temperature resistant high frequency high speed BT resin based copper clad plate; Step one: preparation of first filler S1: take hexagonal boron nitride, vacuum, according to volume ratio 1.1:24, pass into carbon tetrafluoride, nitrogen to adjust pressure to-1900kPa, vacuum, according to volume ratio 1.1:24, pass into carbon tetrafluoride, nitrogen to adjust pressure to-1400kPa, vacuum; pressurize, under the condition of voltage 29kV, frequency 10kHz, carry out plasma discharge, fluorination for 16min, get fluorinated boron nitride; S2: take 1.44g cetyl trimethyl ammonium bromide into 130mL ultrapure water, mix well, get template solution; take 0.5g fluorinated boron nitride into template solution, under the condition of temperature 25℃, ultrasonic, stirring for 95min; slowly add 60mL anhydrous ethanol, ultrasonic, stirring for 65min; under the condition of temperature 45℃, use ammonia water to adjust pH value to 9.5, stirring for 11min; add 0.1g tetraethyl orthosilicate, stirring for 35min, aging for 5h, centrifugal, washing, vacuum drying, under the condition of temperature 490℃, baking for 65min, get first filler; Step two: preparation of second filler Take 105g silicon carbide into 105mL deionized water, add 205g grinding ball, under the condition of rotation speed 310rpm, add 0.5g perfluorodecyl triethoxysilane, reaction for 2.5h; centrifugal, drying for 9h under the condition of temperature 80℃, grinding, get second filler; Step three: preparing microcapsules S1: 2.85g of acrylamide was taken into 5mL of toluene and mixed uniformly to obtain an acrylamide solution; 4.7g of phenol and 3.3g of paraformaldehyde were taken into 20mL of toluene, and under the condition of a temperature of 25℃, magnetic stirring was conducted for 35min; the temperature was raised, and under the condition of a temperature of 50℃, the acrylamide solution was added; the temperature was raised, and under the condition of a temperature of 105℃, reaction was conducted for 11h; cooling, extraction, and suction filtration were conducted to obtain a benzoxazine monomer; S2: graphene oxide was taken, ground, and sieved; 1g of the benzoxazine monomer, 5g of graphene oxide, and 5g of ammonium polyphosphate were taken into 10g of dimethyl silicone oil, and under the condition of a temperature of 25℃, stirring was conducted for 25min; the temperature was raised, and under the condition of a temperature of 160℃, reaction was conducted for 5h; the temperature was raised, and under the condition of a temperature of 190℃, reaction was conducted for 1.5h; cooling, washing, suction filtration, and drying were conducted to obtain microcapsules; Step four: preparing a high-temperature-resistant, high-frequency-resistant, and high-speed-resistant BT resin-based copper-clad plate S1: 0.004g of sodium hydroxide was taken into 1L of deionized water and mixed uniformly to obtain a sodium hydroxide solution; 4g of corncob lignin was taken into 100mL of the sodium hydroxide solution and mixed uniformly, and 40g of epichlorohydrin and 0.4g of tetrabutylammonium bromide were added, and under the condition of a temperature of 65℃, reaction was conducted for 4h; cooling, 2g of tetrabutylammonium bromide and 2g of sodium hydroxide were added, and reaction was conducted for 9h; precipitation and drying were conducted to obtain an epoxy resin monomer; S2: 80g of the epoxy resin monomer and 5g of the microcapsules were taken into 105mL of acetone, and ultrasonic treatment and stirring were conducted, and suction filtration was conducted; 5g of the first filler, 5g of the second filler, 16g of bisphenol A diglycidyl ether, and 6g of polyetheramine were added under the condition of a temperature of 110℃, and ultrasonic treatment was conducted to obtain a copper-clad plate resin sizing liquid; S3: glass fiber cloth was taken, burned, and placed in the copper-clad plate resin sizing liquid, and impregnation was conducted for 11min, and under the condition of a temperature of 195℃, curing was conducted for 11min to obtain a prepreg; lamination, plate loading, hot pressing, plate unloading, and cutting were conducted to obtain a high-temperature-resistant, high-frequency-resistant, and high-speed-resistant BT resin-based copper-clad plate.
[0021] Comparative Example 1: no first filler was added, and the rest was according to Example 2; Step one: preparing the second filler 100g of silicon carbide was taken into 100mL of deionized water, 200g of grinding balls were added, and under the condition of a rotation speed of 300rpm, 0.4g of perfluorodecyltriethoxysilane was added, and reaction was conducted for 2h; centrifugation was conducted, and under the condition of a temperature of 75℃, drying was conducted for 8h, and grinding was conducted to obtain the second filler; Step two: preparing microcapsules S1: take 2.85g acrylamide into 5mL toluene, mix well, get acrylamide solution; take 4.7g phenol, 3.3g polyformaldehyde into 20mL toluene, under the condition of temperature 20℃, magnetic stirring for 30min; heating, under the condition of temperature 45℃, add acrylamide solution; heating, under the condition of temperature 100℃, reaction for 10h; cooling, extraction, suction filtration, get benzoxazine monomer; S2: take graphene oxide, grind, sieve; take 1g benzoxazine monomer, 4.5g graphene oxide, 4.5g ammonium polyphosphate into 10g dimethyl silicone oil, under the condition of temperature 20℃, stirring for 20min, heating, under the condition of temperature 150℃, reaction for 4h; heating, under the condition of temperature 180℃, reaction for 1h, cooling, washing, suction filtration, drying, get microcapsule; Step three: preparation of high temperature resistant, high frequency resistant and high speed resistant BT resin based copper clad plate S1: take 0.004g sodium hydroxide into 1L deionized water, mix well, get sodium hydroxide solution; take 4g corn cob lignin into 55mL sodium hydroxide solution, mix well, add 40g epichlorohydrin, 0.4g tetrabutylammonium bromide, under the condition of temperature 60℃, reaction for 3h; cooling, add 1.2g tetrabutylammonium bromide, 1.2g sodium hydroxide, reaction for 8h; precipitation, drying, get epoxy resin monomer; S2: take 79.5g epoxy resin monomer, 5g microcapsule into 95mL acetone, ultrasonic, stirring, suction filtration; heating, under the condition of temperature 100℃, add 4g second filler, 15.5g bisphenol A diglycidyl ether, 5.5g polyetheramine, ultrasonic, get copper clad plate resin glue solution; S3: take glass fiber cloth, burn, put into copper clad plate resin glue solution, immerse for 10min, under the condition of temperature 185℃, curing for 10min, get prepreg; laminating, plate, hot pressing, dismounting, cutting, get high temperature resistant, high frequency resistant and high speed resistant BT resin based copper clad plate.
[0022] Comparative example 2: no second filler is added, the rest refers to example 2; Step one: preparation of first filler S1: take hexagonal boron nitride, vacuumize, according to volume ratio 1:25, pass in carbon tetrafluoride, nitrogen to adjust pressure to-2000kPa, vacuumize, according to volume ratio 1:25, pass in carbon tetrafluoride, nitrogen to adjust pressure to-1500kPa, vacuumize; pressurize, under the condition of voltage 28kV, frequency 9kHz, carry out plasma discharge, fluorination for 15min, get fluorinated boron nitride; S2: Take 1.44 g of cetyl trimethyl ammonium bromide and add it to 120 mL of ultrapure water, mix well to obtain a template solution; take 0.4 g of boron nitride fluoride and add it to the template solution, ultrasonic at a temperature of 20℃, stir for 90 min; slowly add 60 mL of anhydrous ethanol, ultrasonic, stir for 60 min; adjust the pH value to 9 using ammonia water at a temperature of 40℃, stir for 10 min; add 0.08 g of tetraethyl orthosilicate, stir for 30 min, age for 4 h, centrifuge, wash, vacuum dry, bake at a temperature of 480℃ for 60 min to obtain a first filler; Step two: preparation of microcapsules S1: Take 2.85 g of propylene amine and add it to 5 mL of toluene, mix well to obtain a propylene amine solution; take 4.7 g of phenol and 3.3 g of polyformaldehyde and add them to 20 mL of toluene, magnetic stirring at a temperature of 20℃ for 30 min; heat, add the propylene amine solution at a temperature of 45℃; heat, react at a temperature of 100℃ for 10 h; cool, extract, suction filter to obtain a benzoxazine monomer; S2: Take graphene oxide, grind, sieve; take 1 g of benzoxazine monomer, 4.5 g of graphene oxide, 4.5 g of ammonium polyphosphate and add them to 10 g of dimethyl silicone oil, stir at a temperature of 20℃ for 20 min, heat, react at a temperature of 150℃ for 4 h; heat, react at a temperature of 180℃ for 1 h, cool, wash, suction filter, dry to obtain microcapsules; Step three: preparation of high-temperature, high-frequency and high-speed BT resin-based copper-clad plate S1: Take 0.004 g of sodium hydroxide and add it to 1 L of deionized water, mix well to obtain a sodium hydroxide solution; take 4 g of corn core lignin and add it to 55 mL of sodium hydroxide solution, mix well, add 40 g of epoxy chloropropane and 0.4 g of tetrabutyl ammonium bromide, react at a temperature of 60℃ for 3 h; cool, add 1.2 g of tetrabutyl ammonium bromide and 1.2 g of sodium hydroxide, react for 8 h; precipitate, dry to obtain an epoxy resin monomer; S2: Take 79.5 g of epoxy resin monomer and 5 g of microcapsules and add them to 95 mL of acetone, ultrasonic, stir, suction filter; heat, add 4 g of the first filler, 15.5 g of bisphenol A diglycidyl ether and 5.5 g of polyether amine at a temperature of 100℃, ultrasonic to obtain a copper-clad plate resin glue solution; S3: Take glass fiber cloth, burn, place in the copper-clad plate resin glue solution, immerse for 10 min, cure at a temperature of 185℃ for 10 min to obtain a prepreg; laminate, plate, hot press, unplate, cut to obtain a high-temperature, high-frequency and high-speed BT resin-based copper-clad plate.
[0023] Comparative example 3: no graphene oxide is added, the rest refers to example 2; Step one: preparation of the first filler S1: take the hexagonal boron nitride, vacuum, according to the volume ratio of 1:25 into carbon tetrafluoride, nitrogen to adjust the pressure to-2000kPa, vacuum, according to the volume ratio of 1:25 into carbon tetrafluoride, nitrogen to adjust the pressure to-1500kPa, vacuum; pressurized, under the condition of voltage 28kV, frequency 9kHz, plasma discharge, fluorination 15min, get fluorinated boron nitride; S2: take 1.44g cetyl trimethyl ammonium bromide into 120mL ultrapure water, mix evenly, get template solution; take 0.4g fluorinated boron nitride into the template solution, under the condition of temperature 20℃, ultrasonic, stirring 90min; slowly add 60mL anhydrous ethanol, ultrasonic, stirring 60min; under the condition of temperature 40℃, using ammonia water to adjust the pH value to 9, stirring 10min; add 0.08g tetraethyl orthosilicate, stirring 30min, aging 4h, centrifugal, washing, vacuum drying, under the condition of temperature 480℃, baking 60min, get the first filler; Step two: preparation of the second filler Take 100g silicon carbide into 100mL deionized water, add 200g grinding ball, under the condition of rotation speed 300rpm, add 0.4g perfluorodecyl triethoxysilane, reaction 2h; centrifugal, drying 8h under the condition of temperature 75℃, grinding, get the second filler; Step three: preparation of microcapsule S1: take 2.85g acrylamide into 5mL toluene, mix evenly, get acrylamide solution; take 4.7g phenol, 3.3g polyformaldehyde into 20mL toluene, under the condition of temperature 20℃, magnetic stirring 30min; heating, under the condition of temperature 45℃, add acrylamide solution; heating, under the condition of temperature 100℃, reaction 10h; cooling, extraction, suction filtration, get benzoxazine monomer; S2: take graphene oxide, grinding, sieving; take 1g benzoxazine monomer, 4.5g ammonium polyphosphate into 10g dimethyl silicone oil, under the condition of temperature 20℃, stirring 20min, heating, under the condition of temperature 150℃, reaction 4h; heating, under the condition of temperature 180℃, reaction 1h, cooling, washing, suction filtration, drying, get microcapsule; Step four: preparation of high temperature resistant, high frequency resistant and high speed resistant BT resin based copper clad plate S1: take 0.004 g of sodium hydroxide into 1 L of deionized water, mix well to obtain a sodium hydroxide solution; take 4 g of corncob lignin and add it into 55 mL of the sodium hydroxide solution, mix well, add 40 g of epichlorohydrin, 0.4 g of tetrabutylammonium bromide, and react at a temperature of 60℃ for 3 h; cool down, add 1.2 g of tetrabutylammonium bromide and 1.2 g of sodium hydroxide, and react for 8 h; precipitate, dry, and obtain an epoxy resin monomer; S2: take 79.5 g of the epoxy resin monomer and 5 g of microcapsules, add them into 95 mL of acetone, ultrasonic, stir, and suction filter; heat up, add 4 g of the first filler, 4 g of the second filler, 15.5 g of bisphenol A diglycidyl ether, and 5.5 g of polyetheramine at a temperature of 100℃, ultrasonic, and obtain a copper-clad plate resin glue solution; S3: take a glass fiber cloth, burn it, put it into the copper-clad plate resin glue solution, immerse for 10 min, cure at a temperature of 185℃ for 10 min, and obtain a prepreg; stack, plate, hot press, unplate, cut, and obtain a high-temperature, high-frequency, and high-speed BT resin-based copper-clad plate.
[0024] Comparative Example 4: no ammonium polyphosphate is added, and the rest is according to Example 2; Step one: preparation of the first filler S1: take hexagonal boron nitride, vacuumize, introduce carbon tetrafluoride and nitrogen according to a volume ratio of 1:25 to adjust the pressure to-2000 kPa, vacuumize, introduce carbon tetrafluoride and nitrogen according to a volume ratio of 1:25 to adjust the pressure to-1500 kPa, and vacuumize; fluorinate boron nitride by plasma discharge at a voltage of 28 kV and a frequency of 9 kHz for 15 min to obtain fluorinated boron nitride; S2: take 1.44 g of cetyltrimethylammonium bromide and add it into 120 mL of ultrapure water, mix well to obtain a template solution; take 0.4 g of fluorinated boron nitride and add it into the template solution, ultrasonic at a temperature of 20℃, stir for 90 min; slowly add 60 mL of anhydrous ethanol, ultrasonic, stir for 60 min; adjust the pH value to 9 using ammonia water at a temperature of 40℃, stir for 10 min; add 0.08 g of tetraethyl orthosilicate, stir for 30 min, age for 4 h, centrifuge, wash, vacuum dry, bake at a temperature of 480℃ for 60 min, and obtain the first filler; Step two: preparation of the second filler Take 100 g of silicon carbide and add it into 100 mL of deionized water, add 200 g of grinding balls, add 0.4 g of perfluorodecyltriethoxysilane at a rotation speed of 300 rpm, and react for 2 h; centrifuge, dry at a temperature of 75℃ for 8 h, grind, and obtain the second filler; Step three: preparation of the microcapsule S1: 2.85 g of acrylamide was taken into 5 mL of toluene, mixed uniformly to obtain an acrylamide solution; 4.7 g of phenol and 3.3 g of paraformaldehyde were taken into 20 mL of toluene, and stirred magnetically at a temperature of 20℃ for 30 min; the temperature was raised, and the acrylamide solution was added at a temperature of 45℃; the temperature was raised, and the reaction was carried out at a temperature of 100℃ for 10 h; cooling, extraction, and suction filtration were performed to obtain a benzoxazine monomer; S2: The graphene oxide was ground and sieved; 1 g of the benzoxazine monomer and 4.5 g of the graphene oxide were taken into 10 g of dimethyl silicone oil, stirred at a temperature of 20℃ for 20 min, the temperature was raised, and the reaction was carried out at a temperature of 150℃ for 4 h; the temperature was raised, and the reaction was carried out at a temperature of 180℃ for 1 h; cooling, washing, suction filtration, and drying were performed to obtain microcapsules; Step four: preparation of a high-temperature-resistant, high-frequency-resistant, and high-speed-resistant BT resin-based copper-clad plate S1: 0.004 g of sodium hydroxide was taken into 1 L of deionized water, mixed uniformly to obtain a sodium hydroxide solution; 4 g of corn cob lignin was taken into 55 mL of the sodium hydroxide solution, mixed uniformly, 40 g of epichlorohydrin and 0.4 g of tetrabutylammonium bromide were added, and the reaction was carried out at a temperature of 60℃ for 3 h; cooling, 1.2 g of tetrabutylammonium bromide and 1.2 g of sodium hydroxide were added, and the reaction was carried out for 8 h; precipitation and drying were performed to obtain an epoxy resin monomer; S2: 79.5 g of the epoxy resin monomer and 5 g of the microcapsules were taken into 95 mL of acetone, ultrasonically treated, stirred, and suction filtered; 4 g of the first filler, 4 g of the second filler, 15.5 g of bisphenol A diglycidyl ether, and 5.5 g of polyetheramine were added at a temperature of 100℃, ultrasonically treated to obtain a copper-clad plate resin sizing agent; S3: A glass fiber cloth was taken, burned, placed in the copper-clad plate resin sizing agent, immersed for 10 min, and cured at a temperature of 185℃ for 10 min to obtain a prepreg; lamination, plate loading, hot pressing, plate unloading, and cutting were performed to obtain a high-temperature-resistant, high-frequency-resistant, and high-speed-resistant BT resin-based copper-clad plate.
[0025] Experiment: The high-temperature-resistant, high-frequency-resistant, and high-speed-resistant BT resin-based copper-clad plates prepared in Examples 1-3 and Comparative Examples 1-4 were subjected to performance determination; High-temperature-resistant performance determination: (1) The glass transition temperature was determined by using an HCT-1 type differential thermal gravimetric combined instrument, and the temperature was raised to 300℃ at a temperature rise rate of 10℃ / min; (2) The temperature at which 5% of the thermal weight loss was determined by using a TG / DTA6300 type synchronous thermal analyzer, under a nitrogen atmosphere with a nitrogen flow rate of 200 mL / min, and the temperature was raised to 800℃ at a temperature rise rate of 10℃ / min; After the above experiment was completed, the obtained data are shown in Table 1: Table 1
[0026] Conclusion: By analyzing the experimental data, the high-temperature, high-frequency and high-speed BT resin-based copper-clad plate prepared in Examples 1-3 has a higher glass transition temperature and thermal weight loss temperature, indicating that it is more stable in a high-temperature environment and more resistant to high temperatures; the high-temperature, high-frequency and high-speed BT resin-based copper-clad plate prepared in Comparative Examples 1-4 has a lower glass transition temperature and thermal weight loss temperature, indicating that it is easily affected in a high-temperature environment and difficult to maintain normal form and performance.
[0027] Comparative analysis of Comparative Example 1 without adding the first filler and Example 2 shows that fluorinated boron nitride is used as the core layer and silicon dioxide is used as the shell layer to obtain a core-shell structure first filler; wherein carbon tetrafluoride is used as the fluorine source gas and hexagonal boron nitride is modified by plasma fluorination to obtain fluorinated boron nitride; hexagonal boron nitride has high thermal conductivity, which improves the heat conduction rate of the copper-clad plate and is suitable for high-temperature environments.
[0028] Comparative analysis of Comparative Example 2 without adding the second filler and Example 2 shows that the second filler is prepared and full-fluorodecyl triethoxysilane is used to modify silicon carbide for low dielectric and dispersion; silicon carbide has high hardness, excellent thermal stability and high thermal conductivity, and is resistant to high temperatures.
[0029] Comparative analysis of Comparative Example 3 without adding graphene oxide and Example 2 shows that the two-dimensional layered structure of graphene oxide forms a dense carbonized layer in a high-temperature environment, which insulates heat and oxygen and slows down the combustion rate, and cooperates with ammonium polyphosphate to retard flame.
[0030] Comparative analysis of Comparative Example 4 without adding ammonium polyphosphate and Example 2 shows that ammonium polyphosphate is used as a flame retardant and graphene oxide is used as a carbon source; ammonium polyphosphate decomposes under heat to form a strong water-absorbing substance, which promotes the carbonization of the carbon source substance graphene oxide to form a dense carbonized layer that insulates heat and oxygen, thereby playing a flame-retardant role.
[0031] It is apparent for those skilled in the art that the present application is not limited to the details of the foregoing exemplary embodiments, but can be implemented in other particular forms without departing from the spirit or essential characteristics of the present application. Therefore, the embodiments should be considered in all respects as illustrative and not restrictive, the scope of the present application being defined by the appended claims rather than the foregoing description, and all changes coming within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims
1. A method for preparing a high-temperature, high-frequency, and high-speed BT resin-based copper-clad laminate, characterized in that: Includes the following steps: Step 1: Add acrylamine to toluene and mix well to obtain an acrylamine solution; add phenol and paraformaldehyde to toluene and stir magnetically; heat and add the acrylamine solution; heat and react. Cooling, extraction, and filtration yielded the benzoxazine monomer; Step 2: Take graphene oxide, grind it, and sieve it; add benzoxazine monomer, graphene oxide, and ammonium polyphosphate to dimethyl silicone oil, stir, heat, and react; Heating, reaction, cooling, washing, filtration, drying, to obtain microcapsules; Step 3: Add sodium hydroxide to deionized water and mix well to obtain a sodium hydroxide solution; add corn cob lignin to the sodium hydroxide solution and mix well; add epichlorohydrin and tetrabutylammonium bromide and react; cool, add tetrabutylammonium bromide and sodium hydroxide and react; precipitate, dry and obtain epoxy resin monomer; Step 4: Add epoxy resin monomer and microcapsules to acetone, sonicate, stir, and filter. Heating is performed, and the first filler, the second filler, bisphenol A diglycidyl ether, and polyetheramine are added. The mixture is then sonicated to obtain a copper-clad laminate resin solution. Fiberglass cloth is taken, ignited, placed in the copper-clad laminate resin solution, impregnated, and cured to obtain a prepreg. The prepreg is then stacked, mounted, hot-pressed, disassembled, and cut to obtain a high-temperature, high-frequency, and high-speed BT resin-based copper-clad laminate.
2. The method for preparing a high-temperature, high-frequency, high-speed BT resin-based copper-clad laminate according to claim 1, characterized in that: The preparation method of the first packing material is as follows: hexadecyltrimethylammonium bromide is added to ultrapure water and mixed evenly to obtain a template solution; boron fluoride nitride is added to the template solution and ultrasonically stirred for 85-95 minutes at a temperature of 15-25℃; anhydrous ethanol is slowly added and ultrasonically stirred for 55-65 minutes; the pH is adjusted with ammonia water at a temperature of 35-45℃ and stirred for 9-11 minutes; tetraethyl orthosilicate is added and stirred for 25-35 minutes, aged for 3-5 hours, centrifuged, washed, vacuum dried, and baked at a temperature of 470-490℃ for 55-65 minutes to obtain the first packing material.
3. The method for preparing a high-temperature, high-frequency, high-speed BT resin-based copper-clad laminate according to claim 1, characterized in that: The preparation method of the second filler is as follows: silicon carbide is added to deionized water, grinding balls are added, and perfluorodecyltriethoxysilane is added at a speed of 290-310 rpm. The reaction is carried out for 1.5-2.5 h. After centrifugation, the mixture is dried at a temperature of 70-80℃ for 7-9 h and then ground to obtain the second filler.
4. The method for preparing a high-temperature, high-frequency, high-speed BT resin-based copper-clad laminate according to claim 1, characterized in that: The copper-clad laminate resin solution comprises the following components, in parts by weight: 79-80 parts by weight of epoxy resin monomer, 4-6 parts by weight of microcapsules, 85-105 parts by weight of acetone, 3-5 parts by weight of first filler, 3-5 parts by weight of second filler, 15-16 parts by weight of bisphenol A diglycidyl ether, and 5-6 parts by weight of polyetheramine.
5. The method for preparing a high-temperature, high-frequency, high-speed BT resin-based copper-clad laminate according to claim 1, characterized in that: The microcapsules comprise the following components, in parts by weight: 0.5-1.5 parts by weight of benzoxazine monomer, 4-5 parts by weight of graphene oxide, 4-5 parts by weight of ammonium polyphosphate, and 9-11 parts by weight of dimethyl silicone oil.
6. The method for preparing a high-temperature, high-frequency, high-speed BT resin-based copper-clad laminate according to claim 2, characterized in that: The preparation method of the boron nitride fluoride is as follows: take hexagonal boron nitride, evacuate, introduce carbon tetrafluoride and nitrogen to adjust the pressure to (-2100)-(-1900) kPa, evacuate again, introduce carbon tetrafluoride and nitrogen to adjust the pressure to (-1600)-(-1400) kPa, evacuate again; pressurize, and perform plasma discharge under the conditions of voltage 27-29 kV and frequency 8-10 kHz, fluorinate for 14-16 min to obtain boron nitride fluoride.
7. The method for preparing a high-temperature, high-frequency, high-speed BT resin-based copper-clad laminate according to claim 2, characterized in that: The pH value is adjusted to 8.5-9.
5.
8. The method for preparing a high-temperature, high-frequency, high-speed BT resin-based copper-clad laminate according to claim 3, characterized in that: The second filler comprises the following components, in parts by weight: 95-105 parts silicon carbide, 95-105 parts deionized water, 195-205 parts grinding balls, and 0.3-0.5 parts perfluorodecyltriethoxysilane.
9. The method for preparing a high-temperature, high-frequency, high-speed BT resin-based copper-clad laminate according to claim 6, characterized in that: The volume ratio of carbon tetrafluoride to nitrogen is (0.9-1.1):(24-26).
10. A high-temperature resistant, high-frequency, high-speed BT resin-based copper clad laminate prepared by the preparation method of a high-temperature resistant, high-frequency, high-speed BT resin-based copper clad laminate according to any one of claims 1-9.