CN117165234A - High-temperature-resistant anti-aging electronic packaging resin and preparation method thereof - Google Patents
High-temperature-resistant anti-aging electronic packaging resin and preparation method thereof Download PDFInfo
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- CN117165234A CN117165234A CN202311188458.XA CN202311188458A CN117165234A CN 117165234 A CN117165234 A CN 117165234A CN 202311188458 A CN202311188458 A CN 202311188458A CN 117165234 A CN117165234 A CN 117165234A
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- 238000004100 electronic packaging Methods 0.000 title claims abstract description 54
- 229920005989 resin Polymers 0.000 title claims abstract description 44
- 239000011347 resin Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 230000003712 anti-aging effect Effects 0.000 title claims abstract description 12
- 239000003822 epoxy resin Substances 0.000 claims abstract description 52
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 52
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 230000032683 aging Effects 0.000 claims abstract description 42
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 28
- 239000004917 carbon fiber Substances 0.000 claims abstract description 28
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 22
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 17
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 13
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 13
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 12
- GJLPUBMCTFOXHD-UPHRSURJSA-N (11z)-1$l^{2},2$l^{2},3$l^{2},4$l^{2},5$l^{2},6$l^{2},7$l^{2},8$l^{2},9$l^{2},10$l^{2}-decaboracyclododec-11-ene Chemical compound [B]1[B][B][B][B][B]\C=C/[B][B][B][B]1 GJLPUBMCTFOXHD-UPHRSURJSA-N 0.000 claims abstract description 8
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 90
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 62
- 239000000203 mixture Substances 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 239000011787 zinc oxide Substances 0.000 claims description 31
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 22
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 238000002390 rotary evaporation Methods 0.000 claims description 15
- 238000005303 weighing Methods 0.000 claims description 15
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- QTKDDPSHNLZGRO-UHFFFAOYSA-N 4-methylcyclohexane-1,3-diamine Chemical compound CC1CCC(N)CC1N QTKDDPSHNLZGRO-UHFFFAOYSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 10
- -1 p-hydroxyphenyl Chemical group 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 5
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
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- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 15
- 239000005022 packaging material Substances 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
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- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation 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
- 238000004519 manufacturing process Methods 0.000 description 1
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Abstract
The invention relates to the technical field of electronic packaging resin, in particular to high-temperature-resistant anti-aging electronic packaging resin and a preparation method thereof, wherein nano titanium dioxide is coated by tetraethoxysilane to prepare silicon-coated titanium dioxide, and then the silicon-coated titanium dioxide is added into epoxy resin to modify the silicon-coated titanium dioxide, so that the modified epoxy resin has stronger ultraviolet absorption and shielding capability, and the epoxy resin has better ultraviolet aging resistance to a certain extent; and secondly, the prepared o-carborane bisphenol glycidyl ether is added into the epoxy resin, so that the high temperature resistance of the epoxy resin can be enhanced, and the added modified high temperature resistant carbon fiber can be uniformly dispersed in a molecular gap of the epoxy resin after being modified by the silane coupling agent, so that the high temperature resistance of the epoxy resin is further enhanced, and the high temperature resistant and ageing resistant electronic packaging resin prepared by the invention has excellent market application value.
Description
Technical Field
The invention relates to the technical field of electronic packaging resins, in particular to a high-temperature-resistant anti-aging electronic packaging resin and a preparation method thereof.
Background
Electronic packaging materials can be divided into three main categories, including metal-based electronic packaging materials, ceramic-based electronic packaging materials, and plastic-based electronic packaging materials. The metal-based electronic packaging material has high mechanical strength, good processability, excellent heat conduction performance, good insulating performance, small linear expansion coefficient, excellent heat conduction performance and good chemical resistance stability, but the two packaging materials are complex in preparation, high in cost and high in price, so that the metal-based electronic packaging material is mainly applied to the fields of aerospace, aviation and military; the plastic-based electronic packaging material is widely applied to the civil field because of low cost. Among plastic-based electronic packaging materials, epoxy resins are widely used with their outstanding advantages of low shrinkage, excellent electrical insulation properties, good adhesion properties, excellent corrosion resistance, low cost, and the like.
The preparation method of the special epoxy resin for LED electronic packaging and the epoxy resin thereof are disclosed in Chinese patent No. CN202110877090.2, the preparation process is safe, the condition is mild, the reaction rate can be well controlled by combining the microreactor with the tubular reactor, the preparation process is safer, the prepared epichlorohydrin solvent and methanol can be fully recovered, and various performance indexes of the epoxy resin also accord with the standard. However, the epoxy resin special for electronic packaging prepared by the invention does not improve the high temperature resistance and the ageing resistance of the epoxy resin, so that the application range of the epoxy resin is limited in use, and if the defects of the epoxy resin can be improved, the market application prospect of the epoxy resin can be greatly expanded.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects existing in the prior art, the invention provides the high-temperature-resistant and ageing-resistant electronic packaging resin and the preparation method thereof, which can effectively solve the problem that the epoxy resin in the prior art is poor in high-temperature resistance and ageing resistance.
Technical proposal
In order to achieve the above purpose, the invention is realized by the following technical scheme:
a preparation method of high-temperature-resistant anti-aging electronic packaging resin comprises the following steps:
s1, weighing 20 parts by weight of nano titanium dioxide and 100 parts by weight of absolute ethyl alcohol, mixing, adding 2-3 parts by weight of polyethylene glycol dispersing agent, rapidly stirring, performing ultrasonic dispersion, adding 40-50 parts by weight of deionized water, heating to 60 ℃ for heat preservation, adding 4-5 parts by weight of tetraethoxysilane and 1-2 parts by weight of ammonia water under the stirring condition of stirring speed of 400-500r/min, aging for 2 hours under the original temperature condition, filtering to remove filtrate, and drying in an oven at 100 ℃ for 3-5 hours to obtain silicon-coated titanium dioxide;
s2, weighing 0.5-0.8 part by weight of silicon-coated titanium dioxide in S1, dispersing in 200 parts by weight of acetone, adding 1-2 parts by weight of silane coupling agent KH560 after full stirring, adding 100 parts by weight of epoxy resin after ultrasonic dispersion, fully stirring, standing at 90 ℃ for 2 hours, removing acetone through reduced pressure rotary evaporation, and obtaining the modified epoxy resin;
s3, adding 6-8 parts by weight of 1, 2-bis (p-hydroxyphenyl) -o-carborane, 68-70 parts by weight of epichlorohydrin and 10-11 parts by weight of benzyl triethyl ammonium chloride into a flask which is provided with a condenser pipe and is filled with nitrogen, heating an oil bath to 85 ℃ for reaction for 3 hours, dropwise adding 60 parts by weight of sodium hydroxide solution, continuing to react for 1 hour, cooling to room temperature, filtering the reaction solution, washing the filtrate with deionized water for 3 times, adding 5-6 parts by weight of anhydrous sodium sulfate, standing for 12 hours, drying in a vacuum oven at 100 ℃ after filtering and spin drying, and obtaining the o-carborane bisphenol glycidyl ether after cooling;
s4, the anti-ultraviolet modified epoxy resin in S2 and the ortho-carborane bisphenol glycidyl ether in S3 are prepared according to the following ratio of 8:1, adding 3-5% of modified high-temperature resistant carbon fiber and 2-3% of aluminum doped zinc oxide whisker into the mixture, mixing and stirring the mixture at 130 ℃, adding 1-2% of 4,4' -diaminodiphenyl sulfone into the mixture under the stirring condition, stirring the mixture for 40min, adding 1-2% of composite curing agent component into the mixture, continuously stirring the mixture for 30min, vacuumizing the mixture, removing bubbles, and curing the mixture in an oven to obtain the high-temperature resistant and ageing resistant electronic packaging resin.
Further, the stirring speed of the rapid stirring in the S1 is 800-1000r/min, the stirring time is 20min, and the frequency of ultrasonic dispersion in the S1 is 23-26kHz.
Further, the stirring speed of the full stirring in the step S2 is 500-800r/min, and the stirring time is 15-20min.
Further, the temperature condition of the reduced pressure rotary evaporation in the step S2 is 35 ℃.
Further, the mass fraction of the sodium hydroxide solution in the S3 is 25%.
Further, the preparation method of the modified high temperature resistant carbon fiber in the S4 comprises the following steps: dispersing 10-12 parts by weight of carbon fiber in 50 parts by weight of absolute ethyl alcohol, stirring at a stirring speed of 600-800r/min for 10min, adding 8-10 parts by weight of silane coupling agent KH560, continuously stirring for 5min, performing ultrasonic dispersion at a frequency of 26-27kHz for 10min, removing ethanol by rotary evaporation, and drying in a drying oven at 55 ℃ for 12h to obtain the modified high-temperature-resistant carbon fiber.
Further, the preparation method of the aluminum-doped zinc oxide whisker in the step S4 comprises the following steps: according to 5:1, weighing zinc oxide whisker and aluminum oxide according to the weight ratio, pouring the zinc oxide whisker and aluminum oxide into a crucible, uniformly mixing, then placing the mixture in a high-temperature furnace at 920 ℃ for 15 hours at constant temperature, naturally cooling the mixture to normal temperature after discharging, grinding the mixture, and sieving the mixture with a 200-mesh sieve to obtain the aluminum-doped zinc oxide whisker.
Further, the composite curing agent in the S4 is prepared by mixing 4,4' -diaminodiphenyl methane and 4-methyl 1, 3-cyclohexanediamine according to the equal weight ratio.
Further, the specific temperature and time for curing in S4 are: pre-curing for 1h at 90 ℃, then for 2h at 130 ℃, then for 3h at 170 ℃ and finally for 2h at 200 ℃.
The raw materials of the high-temperature-resistant anti-aging electronic packaging resin comprise: nanometer titanium dioxide, absolute ethyl alcohol, polyethylene glycol dispersing agent, tetraethoxysilane, ammonia water, acetone, silane coupling agent KH560, epoxy resin, 1, 2-bis (p-hydroxyphenyl) -o-carborane, epichlorohydrin, benzyl triethyl ammonium chloride, sodium hydroxide solution with mass fraction of 25%, anhydrous sodium sulfate, carbon fiber, zinc oxide whisker, alumina, 4 '-diamino diphenyl sulfone, 4' -diamino diphenyl methane and 4-methyl 1, 3-cyclohexanediamine.
Advantageous effects
The invention provides a high-temperature-resistant anti-aging electronic packaging resin and a preparation method thereof, and compared with the prior art, the invention has the following beneficial effects:
according to the invention, the nano titanium dioxide is coated by the tetraethoxysilane to prepare the silicon-coated titanium dioxide, and then the silicon-coated titanium dioxide is added into the epoxy resin to modify the silicon-coated titanium dioxide, so that the modified epoxy resin has stronger ultraviolet absorption and shielding capability, and the epoxy resin has better ultraviolet aging resistance; secondly, the prepared o-carborane bisphenol glycidyl ether is added into the epoxy resin, so that the high temperature resistance of the epoxy resin can be enhanced, and the modified high temperature resistant carbon fiber added into the epoxy resin can be uniformly dispersed in the molecular gaps of the epoxy resin after being modified by the silane coupling agent, so that the high temperature resistance of the epoxy resin is further enhanced; finally, the prepared epoxy resin has stable antistatic performance by adding the aluminum-doped zinc oxide whisker, so that the high-temperature-resistant and ageing-resistant electronic packaging resin prepared by the invention has excellent market application value.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. 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 invention is further described below with reference to examples.
Example 1
The preparation method of the high-temperature-resistant anti-aging electronic packaging resin comprises the following steps:
s1, weighing 20 parts by weight of nano titanium dioxide and 100 parts by weight of absolute ethyl alcohol, mixing, adding 2 parts by weight of polyethylene glycol dispersing agent, rapidly stirring, performing ultrasonic dispersion, adding 40 parts by weight of deionized water, heating to 60 ℃ for heat preservation, adding 4 parts by weight of tetraethoxysilane and 1 part by weight of ammonia water under the stirring condition of stirring speed of 400r/min, aging for 2 hours under the original temperature condition, filtering to remove filtrate, and drying in an oven at 100 ℃ for 3 hours, wherein the obtained product is denoted as silicon-coated titanium dioxide;
s2, weighing 0.5 part by weight of silicon-coated titanium dioxide in the S1, dispersing in 200 parts by weight of acetone, adding 1 part by weight of silane coupling agent KH560 after full stirring, adding 100 parts by weight of epoxy resin after ultrasonic dispersion, fully stirring, standing at 90 ℃ for 2 hours, and removing the acetone by reduced pressure rotary evaporation to obtain the ultraviolet-resistant modified epoxy resin;
s3, adding 6 parts by weight of 1, 2-bis (p-hydroxyphenyl) -o-carborane, 68 parts by weight of epichlorohydrin and 10 parts by weight of benzyl triethyl ammonium chloride into a flask which is provided with a condenser pipe and is filled with nitrogen, heating an oil bath to 85 ℃ for reaction for 3 hours, dropwise adding 60 parts by weight of sodium hydroxide solution, continuing to react for 1 hour, cooling to room temperature, filtering the reaction solution, washing the filtrate with deionized water for 3 times, adding 5 parts by weight of anhydrous sodium sulfate, standing for 12 hours, filtering, spin-drying, and then placing in a vacuum oven at 100 ℃ for drying for 24 hours, and cooling to obtain the o-carborane bisphenol glycidyl ether;
s4, the anti-ultraviolet modified epoxy resin in S2 and the ortho-carborane bisphenol glycidyl ether in S3 are prepared according to the following ratio of 8:1, adding 3% of modified high-temperature resistant carbon fiber and 2% of aluminum doped zinc oxide whisker into the mixture, mixing and stirring the mixture at the temperature of 130 ℃, adding 1% of 4,4' -diaminodiphenyl sulfone into the mixture under the stirring condition, stirring the mixture for 40min, adding 1% of composite curing agent component into the mixture, continuously stirring the mixture for 30min, vacuumizing the mixture, removing bubbles, and curing the mixture in an oven to obtain the high-temperature resistant and ageing-resistant electronic packaging resin.
The stirring speed of the rapid stirring in S1 is 800r/min, the stirring time is 20min, and the frequency of ultrasonic dispersion in S1 is 23kHz.
The stirring speed of the full stirring in the step S2 is 500r/min, and the stirring time is 15min.
The temperature conditions for the reduced pressure rotary evaporation in S2 were 35 ℃.
The mass fraction of the sodium hydroxide solution in S3 is 25%.
The preparation method of the modified high-temperature-resistant carbon fiber in the S4 comprises the following steps: dispersing 10 parts by weight of carbon fiber in 50 parts by weight of absolute ethyl alcohol, stirring at a stirring speed of 600r/min for 10min, adding 8 parts by weight of silane coupling agent KH560, continuously stirring for 5min, performing ultrasonic dispersion at a frequency of 26kHz for 10min, removing ethanol by rotary evaporation, and drying in an oven at 55 ℃ for 12h to obtain the modified high-temperature-resistant carbon fiber.
The preparation method of the aluminum-doped zinc oxide whisker in the S4 comprises the following steps: according to 5:1, weighing zinc oxide whisker and aluminum oxide according to the weight ratio, pouring the zinc oxide whisker and aluminum oxide into a crucible, uniformly mixing, then placing the mixture in a high-temperature furnace at 920 ℃ for 15 hours at constant temperature, naturally cooling the mixture to normal temperature after discharging, grinding the mixture, and sieving the mixture with a 200-mesh sieve to obtain the aluminum-doped zinc oxide whisker.
The composite curing agent in S4 is prepared by mixing 4,4' -diaminodiphenyl methane and 4-methyl 1, 3-cyclohexanediamine according to the equal weight ratio.
The specific temperature and time for curing in S4 are: pre-curing for 1h at 90 ℃, then for 2h at 130 ℃, then for 3h at 170 ℃ and finally for 2h at 200 ℃.
The high temperature-resistant and ageing-resistant electronic packaging resin comprises the following raw materials: nanometer titanium dioxide, absolute ethyl alcohol, polyethylene glycol dispersing agent, tetraethoxysilane, ammonia water, acetone, silane coupling agent KH560, epoxy resin, 1, 2-bis (p-hydroxyphenyl) -o-carborane, epichlorohydrin, benzyl triethyl ammonium chloride, sodium hydroxide solution with mass fraction of 25%, anhydrous sodium sulfate, carbon fiber, zinc oxide whisker, alumina, 4 '-diamino diphenyl sulfone, 4' -diamino diphenyl methane and 4-methyl 1, 3-cyclohexanediamine.
Example 2
The preparation method of the high-temperature-resistant anti-aging electronic packaging resin comprises the following steps:
s1, weighing 20 parts by weight of nano titanium dioxide and 100 parts by weight of absolute ethyl alcohol, mixing, adding 3 parts by weight of polyethylene glycol dispersing agent, rapidly stirring, performing ultrasonic dispersion, adding 50 parts by weight of deionized water, heating to 60 ℃ for heat preservation, adding 5 parts by weight of tetraethoxysilane and 2 parts by weight of ammonia water under the stirring condition of the stirring speed of 500r/min, aging for 2 hours under the original temperature condition, filtering to remove filtrate, and drying in an oven at 100 ℃ for 5 hours, wherein the obtained product is denoted as silicon-coated titanium dioxide;
s2, weighing 0.8 part by weight of silicon-coated titanium dioxide in the S1, dispersing in 200 parts by weight of acetone, adding 2 parts by weight of a silane coupling agent KH560 after full stirring, adding 100 parts by weight of epoxy resin after ultrasonic dispersion, fully stirring, standing at 90 ℃ for 2 hours, and removing the acetone by reduced pressure rotary evaporation to obtain the ultraviolet-resistant modified epoxy resin;
s3, adding 8 parts by weight of 1, 2-bis (p-hydroxyphenyl) -o-carborane, 70 parts by weight of epichlorohydrin and 11 parts by weight of benzyl triethyl ammonium chloride into a flask which is provided with a condenser pipe and is filled with nitrogen, heating an oil bath to 85 ℃ for reaction for 3 hours, dropwise adding 60 parts by weight of sodium hydroxide solution, continuing to react for 1 hour, cooling to room temperature, filtering the reaction solution, washing the filtrate with deionized water for 3 times, adding 6 parts by weight of anhydrous sodium sulfate, standing for 12 hours, filtering, spin-drying, and then placing in a vacuum oven at 100 ℃ for drying for 24 hours, and cooling to obtain the o-carborane bisphenol glycidyl ether;
s4, the anti-ultraviolet modified epoxy resin in S2 and the ortho-carborane bisphenol glycidyl ether in S3 are prepared according to the following ratio of 8:1, adding modified high temperature resistant carbon fiber accounting for 5 percent of the weight of the ultraviolet resistant modified epoxy resin and 3 percent of aluminum doped zinc oxide whisker, then placing the mixture at the temperature of 130 ℃ for mixing and stirring, adding 4,4' -diaminodiphenyl sulfone accounting for 2 percent of the weight of the ultraviolet resistant modified epoxy resin under the stirring condition, stirring for 40min, adding a composite curing agent accounting for 2 percent of the weight of the ultraviolet resistant modified epoxy resin, continuously stirring for 30min, vacuumizing, removing bubbles, and placing the mixture in an oven for curing, thus obtaining the high temperature resistant and ageing resistant electronic packaging resin.
The stirring speed of the rapid stirring in the S1 is 1000r/min, the stirring time is 20min, and the frequency of ultrasonic dispersion in the S1 is 26kHz.
The stirring speed of the full stirring in the step S2 is 800r/min, and the stirring time is 20min.
The temperature conditions for the reduced pressure rotary evaporation in S2 were 35 ℃.
The mass fraction of the sodium hydroxide solution in S3 is 25%.
The preparation method of the modified high-temperature-resistant carbon fiber in the S4 comprises the following steps: dispersing 12 parts by weight of carbon fiber in 50 parts by weight of absolute ethyl alcohol, stirring at a stirring speed of 800r/min for 10min, adding 10 parts by weight of silane coupling agent KH560, continuously stirring for 5min, performing ultrasonic dispersion at a frequency of 27kHz for 10min, removing ethanol by rotary evaporation, and drying in an oven at 55 ℃ for 12h to obtain the modified high-temperature-resistant carbon fiber.
The preparation method of the aluminum-doped zinc oxide whisker in the S4 comprises the following steps: according to 5:1, weighing zinc oxide whisker and aluminum oxide according to the weight ratio, pouring the zinc oxide whisker and aluminum oxide into a crucible, uniformly mixing, then placing the mixture in a high-temperature furnace at 920 ℃ for 15 hours at constant temperature, naturally cooling the mixture to normal temperature after discharging, grinding the mixture, and sieving the mixture with a 200-mesh sieve to obtain the aluminum-doped zinc oxide whisker.
The composite curing agent in S4 is prepared by mixing 4,4' -diaminodiphenyl methane and 4-methyl 1, 3-cyclohexanediamine according to the equal weight ratio.
The specific temperature and time for curing in S4 are: pre-curing for 1h at 90 ℃, then for 2h at 130 ℃, then for 3h at 170 ℃ and finally for 2h at 200 ℃.
The high temperature-resistant and ageing-resistant electronic packaging resin comprises the following raw materials: nanometer titanium dioxide, absolute ethyl alcohol, polyethylene glycol dispersing agent, tetraethoxysilane, ammonia water, acetone, silane coupling agent KH560, epoxy resin, 1, 2-bis (p-hydroxyphenyl) -o-carborane, epichlorohydrin, benzyl triethyl ammonium chloride, sodium hydroxide solution with mass fraction of 25%, anhydrous sodium sulfate, carbon fiber, zinc oxide whisker, alumina, 4 '-diamino diphenyl sulfone, 4' -diamino diphenyl methane and 4-methyl 1, 3-cyclohexanediamine.
Example 3
The preparation method of the high-temperature-resistant anti-aging electronic packaging resin comprises the following steps:
s1, weighing 20 parts by weight of nano titanium dioxide and 100 parts by weight of absolute ethyl alcohol, mixing, adding 3 parts by weight of polyethylene glycol dispersing agent, rapidly stirring, performing ultrasonic dispersion, adding 45 parts by weight of deionized water, heating to 60 ℃ for heat preservation, adding 5 parts by weight of tetraethoxysilane and 2 parts by weight of ammonia water under the stirring condition of the stirring speed of 500r/min, aging for 2 hours under the original temperature condition, filtering to remove filtrate, and drying in an oven at 100 ℃ for 4 hours, wherein the obtained product is denoted as silicon-coated titanium dioxide;
s2, weighing 0.7 part by weight of silicon-coated titanium dioxide in the S1, dispersing in 200 parts by weight of acetone, adding 2 parts by weight of silane coupling agent KH560 after full stirring, adding 100 parts by weight of epoxy resin after ultrasonic dispersion, fully stirring, standing at 90 ℃ for 2 hours, and removing the acetone by reduced pressure rotary evaporation to obtain the ultraviolet-resistant modified epoxy resin;
s3, adding 7 parts by weight of 1, 2-bis (p-hydroxyphenyl) -o-carborane, 69 parts by weight of epichlorohydrin and 10 parts by weight of benzyl triethyl ammonium chloride into a flask which is provided with a condenser pipe and is filled with nitrogen, heating an oil bath to 85 ℃ for reaction for 3 hours, dropwise adding 60 parts by weight of sodium hydroxide solution, continuing to react for 1 hour, cooling to room temperature, filtering the reaction solution, washing the filtrate with deionized water for 3 times, adding 5 parts by weight of anhydrous sodium sulfate, standing for 12 hours, filtering, spin-drying, and then placing in a vacuum oven at 100 ℃ for drying for 24 hours, and cooling to obtain the o-carborane bisphenol glycidyl ether;
s4, the anti-ultraviolet modified epoxy resin in S2 and the ortho-carborane bisphenol glycidyl ether in S3 are prepared according to the following ratio of 8:1, adding modified high temperature resistant carbon fiber accounting for 4 percent of the weight of the ultraviolet resistant modified epoxy resin and 3 percent of aluminum doped zinc oxide whisker, then placing the mixture at the temperature of 130 ℃ for mixing and stirring, adding 4,4' -diaminodiphenyl sulfone accounting for 1 percent of the weight of the ultraviolet resistant modified epoxy resin under the stirring condition, stirring for 40min, adding a composite curing agent accounting for 2 percent of the weight of the ultraviolet resistant modified epoxy resin, continuously stirring for 30min, vacuumizing, removing bubbles, and placing the mixture in an oven for curing, thus obtaining the high temperature resistant and ageing resistant electronic packaging resin.
The stirring speed of the rapid stirring in the S1 is 900r/min, the stirring time is 20min, and the frequency of ultrasonic dispersion in the S1 is 25kHz.
The stirring speed of the full stirring in the step S2 is 600r/min, and the stirring time is 18min.
The temperature conditions for the reduced pressure rotary evaporation in S2 were 35 ℃.
The mass fraction of the sodium hydroxide solution in S3 is 25%.
The preparation method of the modified high-temperature-resistant carbon fiber in the S4 comprises the following steps: dispersing 11 parts by weight of carbon fiber in 50 parts by weight of absolute ethyl alcohol, stirring at a stirring speed of 700r/min for 10min, adding 9 parts by weight of silane coupling agent KH560, continuously stirring for 5min, performing ultrasonic dispersion at a frequency of 27kHz for 10min, removing ethanol by rotary evaporation, and drying in an oven at 55 ℃ for 12h to obtain the modified high-temperature-resistant carbon fiber.
The preparation method of the aluminum-doped zinc oxide whisker in the S4 comprises the following steps: according to 5:1, weighing zinc oxide whisker and aluminum oxide according to the weight ratio, pouring the zinc oxide whisker and aluminum oxide into a crucible, uniformly mixing, then placing the mixture in a high-temperature furnace at 920 ℃ for 15 hours at constant temperature, naturally cooling the mixture to normal temperature after discharging, grinding the mixture, and sieving the mixture with a 200-mesh sieve to obtain the aluminum-doped zinc oxide whisker.
The composite curing agent in S4 is prepared by mixing 4,4' -diaminodiphenyl methane and 4-methyl 1, 3-cyclohexanediamine according to the equal weight ratio.
The specific temperature and time for curing in S4 are: pre-curing for 1h at 90 ℃, then for 2h at 130 ℃, then for 3h at 170 ℃ and finally for 2h at 200 ℃.
The high temperature-resistant and ageing-resistant electronic packaging resin comprises the following raw materials: nanometer titanium dioxide, absolute ethyl alcohol, polyethylene glycol dispersing agent, tetraethoxysilane, ammonia water, acetone, silane coupling agent KH560, epoxy resin, 1, 2-bis (p-hydroxyphenyl) -o-carborane, epichlorohydrin, benzyl triethyl ammonium chloride, sodium hydroxide solution with mass fraction of 25%, anhydrous sodium sulfate, carbon fiber, zinc oxide whisker, alumina, 4 '-diamino diphenyl sulfone, 4' -diamino diphenyl methane and 4-methyl 1, 3-cyclohexanediamine.
Comparative example 1
The preparation method of the high-temperature-resistant and ageing-resistant electronic packaging resin provided by the comparative example is approximately the same as that of the embodiment 1, and the main difference is that: the silicon-coated titanium dioxide in example 1 was replaced with unmodified titanium dioxide in the production method of comparative example 1.
Comparative example 2
The preparation method of the high-temperature-resistant and ageing-resistant electronic packaging resin provided by the comparative example is approximately the same as that of the embodiment 1, and the main difference is that: the preparation of comparative example 2 was carried out without adding the o-carborane bisphenol glycidyl ether of example 1.
Comparative example 3
The preparation method of the high-temperature-resistant and ageing-resistant electronic packaging resin provided by the comparative example is approximately the same as that of the embodiment 1, and the main difference is that: the modified high temperature resistant carbon fiber in example 1 was not added to the preparation method of comparative example 3.
Performance testing
The high temperature resistant and aging resistant electronic packaging resins prepared in examples 1 to 3 were labeled as example 1, example 2 and example 3, respectively, the high temperature resistant and aging resistant electronic packaging resins prepared in comparative examples 1 to 3 were labeled as comparative example 1, comparative example 2 and comparative example 3, respectively, and then the properties of examples 1 to 3 and comparative examples 1 to 3 were examined, and specific examination data are recorded in the following table:
the data in the above table shows that the high temperature and aging resistant electronic packaging resin in the present examples 1 to 3 does not undergo aging yellowing under ultraviolet irradiation, but the high temperature and aging resistant electronic packaging resin in the comparative examples 1 to 3 starts aging yellowing under ultraviolet irradiation, which indicates that the high temperature and aging resistant electronic packaging resin in the present examples 1 to 3 has better aging resistance, and the data in the above table shows that the thermal decomposition temperature of the high temperature and aging resistant electronic packaging resin in the present examples 1 to 3 is higher, and has better high temperature resistance.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the high-temperature-resistant anti-aging electronic packaging resin is characterized by comprising the following steps of:
s1, weighing 20 parts by weight of nano titanium dioxide and 100 parts by weight of absolute ethyl alcohol, mixing, adding 2-3 parts by weight of polyethylene glycol dispersing agent, rapidly stirring, performing ultrasonic dispersion, adding 40-50 parts by weight of deionized water, heating to 60 ℃ for heat preservation, adding 4-5 parts by weight of tetraethoxysilane and 1-2 parts by weight of ammonia water under the stirring condition of stirring speed of 400-500r/min, aging for 2 hours under the original temperature condition, filtering to remove filtrate, and drying in an oven at 100 ℃ for 3-5 hours to obtain silicon-coated titanium dioxide;
s2, weighing 0.5-0.8 part by weight of silicon-coated titanium dioxide in S1, dispersing in 200 parts by weight of acetone, adding 1-2 parts by weight of silane coupling agent KH560 after full stirring, adding 100 parts by weight of epoxy resin after ultrasonic dispersion, fully stirring, standing at 90 ℃ for 2 hours, removing acetone through reduced pressure rotary evaporation, and obtaining the modified epoxy resin;
s3, adding 6-8 parts by weight of 1, 2-bis (p-hydroxyphenyl) -o-carborane, 68-70 parts by weight of epichlorohydrin and 10-11 parts by weight of benzyl triethyl ammonium chloride into a flask which is provided with a condenser pipe and is filled with nitrogen, heating an oil bath to 85 ℃ for reaction for 3 hours, dropwise adding 60 parts by weight of sodium hydroxide solution, continuing to react for 1 hour, cooling to room temperature, filtering the reaction solution, washing the filtrate with deionized water for 3 times, adding 5-6 parts by weight of anhydrous sodium sulfate, standing for 12 hours, drying in a vacuum oven at 100 ℃ after filtering and spin drying, and obtaining the o-carborane bisphenol glycidyl ether after cooling;
s4, the anti-ultraviolet modified epoxy resin in S2 and the ortho-carborane bisphenol glycidyl ether in S3 are prepared according to the following ratio of 8:1, adding 3-5% of modified high-temperature resistant carbon fiber and 2-3% of aluminum doped zinc oxide whisker into the mixture, mixing and stirring the mixture at 130 ℃, adding 1-2% of 4,4' -diaminodiphenyl sulfone into the mixture under the stirring condition, stirring the mixture for 40min, adding 1-2% of composite curing agent component into the mixture, continuously stirring the mixture for 30min, vacuumizing the mixture, removing bubbles, and curing the mixture in an oven to obtain the high-temperature resistant and ageing resistant electronic packaging resin.
2. The method for preparing the high-temperature-resistant and anti-aging electronic packaging resin according to claim 1, wherein the stirring speed of the rapid stirring in the step S1 is 800-1000r/min, the stirring time is 20min, and the ultrasonic dispersion frequency in the step S1 is 23-26kHz.
3. The method for preparing the high-temperature-resistant and aging-resistant electronic packaging resin according to claim 1, wherein the stirring speed of the sufficient stirring in the step S2 is 500-800r/min, and the stirring time is 15-20min.
4. The method for preparing the high-temperature-resistant and aging-resistant electronic packaging resin according to claim 1, wherein the temperature condition of reduced pressure rotary evaporation in the step S2 is 35 ℃.
5. The method for preparing the high-temperature-resistant and aging-resistant electronic packaging resin according to claim 1, wherein the mass fraction of the sodium hydroxide solution in the S3 is 25%.
6. The method for preparing the high-temperature-resistant and aging-resistant electronic packaging resin according to claim 1, wherein the method for preparing the modified high-temperature-resistant carbon fiber in the step S4 is as follows: dispersing 10-12 parts by weight of carbon fiber in 50 parts by weight of absolute ethyl alcohol, stirring at a stirring speed of 600-800r/min for 10min, adding 8-10 parts by weight of silane coupling agent KH560, continuously stirring for 5min, performing ultrasonic dispersion at a frequency of 26-27kHz for 10min, removing ethanol by rotary evaporation, and drying in a drying oven at 55 ℃ for 12h to obtain the modified high-temperature-resistant carbon fiber.
7. The method for preparing the high-temperature-resistant and aging-resistant electronic packaging resin according to claim 1, wherein the method for preparing the aluminum-doped zinc oxide whisker in the step S4 is as follows: according to 5:1, weighing zinc oxide whisker and aluminum oxide according to the weight ratio, pouring the zinc oxide whisker and aluminum oxide into a crucible, uniformly mixing, then placing the mixture in a high-temperature furnace at 920 ℃ for 15 hours at constant temperature, naturally cooling the mixture to normal temperature after discharging, grinding the mixture, and sieving the mixture with a 200-mesh sieve to obtain the aluminum-doped zinc oxide whisker.
8. The method for preparing the high-temperature-resistant and ageing-resistant electronic packaging resin is characterized in that the S4 composite curing agent is prepared by mixing 4,4' -diaminodiphenyl methane and 4-methyl-1, 3-cyclohexanediamine according to the equal weight ratio.
9. The method for preparing the high-temperature-resistant and aging-resistant electronic packaging resin according to claim 1, wherein the specific temperature and time for curing in the step S4 are as follows: pre-curing for 1h at 90 ℃, then for 2h at 130 ℃, then for 3h at 170 ℃ and finally for 2h at 200 ℃.
10. The high temperature and aging resistant electronic packaging resin prepared by the method for preparing the high temperature and aging resistant electronic packaging resin according to any one of claims 1 to 9, wherein the raw materials of the high temperature and aging resistant electronic packaging resin comprise: nanometer titanium dioxide, absolute ethyl alcohol, polyethylene glycol dispersing agent, tetraethoxysilane, ammonia water, acetone, silane coupling agent KH560, epoxy resin, 1, 2-bis (p-hydroxyphenyl) -o-carborane, epichlorohydrin, benzyl triethyl ammonium chloride, sodium hydroxide solution with mass fraction of 25%, anhydrous sodium sulfate, carbon fiber, zinc oxide whisker, alumina, 4 '-diamino diphenyl sulfone, 4' -diamino diphenyl methane and 4-methyl 1, 3-cyclohexanediamine.
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