An anti-falling and fall-resistant epoxy glass fiber composite electronic product plate and a preparation process thereof

Abstract

The present application relates to the technical field of composite board, in particular to an epoxy glass fiber composite electronic product board resistant to falling and dropping and a preparation process.The polyurethane prepolymer is added dropwise into the silicone seed emulsion, and the polyurethane-silicone emulsion is obtained by initiation.The reaction monomer is added dropwise into the polyurethane-silicone emulsion, and a core-shell rubber particle with a three-layer structure is obtained by initiation.The bisphenol A epoxy resin, the curing agent, the accelerator, the core-shell rubber particle, the foaming agent and the surfactant are mixed and heated to obtain an epoxy resin glue solution;the glass fiber cloth is cut and dried, and then is laid on the glass plate;the epoxy resin glue solution is uniformly coated on the glass fiber cloth, and the finished product is obtained by sufficient impregnation, drying, lamination and curing.The finished product prepared by the present application has good toughness and hydrophobic corrosion resistance, and therefore has a wide application prospect in the technical field of epoxy resin.

Description

Technical Field

[0001] This invention relates to the field of composite board technology, specifically to a drop-resistant and impact-resistant epoxy fiberglass composite electronic product board and its preparation process. Background Technology

[0002] In the booming development of the modern electronics industry, epoxy fiberglass composite electronic product boards have demonstrated irreplaceable modern value due to their superior performance, but some issues still need improvement. Epoxy fiberglass composite boards possess numerous advantages. They have excellent mechanical properties; high strength and good rigidity provide a stable support structure for electronic components, ensuring that electronic products maintain their physical form in various complex environments, are less prone to deformation or damage, and thus extend their lifespan. Simultaneously, they possess excellent electrical insulation properties, effectively preventing current leakage and short circuits, ensuring the safe and stable operation of electronic products. Furthermore, these boards have good processing performance; they can be precisely manufactured into circuit boards of various shapes and sizes through cutting, drilling, stamping, and other processing methods to meet the design requirements of different electronic products. Moreover, their processing is relatively simple, improving production efficiency and reducing production costs, bringing significant economic benefits to electronics manufacturing companies.

[0003] However, electronic products inevitably suffer from various external impacts and vibrations during production, transportation, and use. If the board material lacks sufficient toughness, cracks or even breakage can easily occur, affecting the normal operation of internal electronic components and significantly shortening the product's lifespan. Furthermore, moisture can easily penetrate the board material, causing short circuits and rusting of electronic components, similarly shortening the product's lifespan. Therefore, improving the hydrophobic properties of the board material can effectively prevent moisture intrusion, protect the stable operation of internal circuits, and reduce the failure rate. Simultaneously, electronic products may come into contact with various chemicals in different environments, such as acids, alkalis, and salt solutions. Board materials with poor corrosion resistance will be corroded by these chemicals, causing structural damage, decreased insulation performance, and potential safety hazards.

[0004] In order to overcome the shortcomings of the prior art, the present invention provides a drop-resistant and impact-resistant epoxy fiberglass composite electronic product board and its preparation process. Summary of the Invention

[0005] The purpose of this invention is to provide a drop-resistant and impact-resistant epoxy fiberglass composite electronic product board and its manufacturing process, so as to solve the problems in the prior art.

[0006] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0007] A process for preparing a drop-resistant and impact-resistant epoxy fiberglass composite electronic product board includes the following steps:

[0008] Step 1: Mix deionized water, sodium dodecyl sulfonate, octamethylcyclotetrasiloxane, tetraethyl orthosilicate, and methacryloyloxypropylmethyldimethoxysilane. Stir at 25-30℃ for 30-40 minutes, then add an emulsifier and emulsify for another 30-40 minutes to obtain an organosilicon emulsion. Under nitrogen atmosphere, stir and heat the organosilicon emulsion to 85-95℃, then add p-toluenesulfonic acid and continue the reaction for 8-10 hours to obtain an organosilicon seed emulsion.

[0009] Polypropylene glycol, hexamethylene diisocyanate, and butyl acrylate are mixed and stirred at 25-30℃ for 1.5-2.0 h. Then, hydroxyethyl acrylate is added and stirring is continued for 30-40 min to obtain a polyurethane prepolymer. The polyurethane prepolymer is added dropwise to an organosilicon seed emulsion at a rate of 30-40 drops / min, and ammonium persulfate is added to continue the reaction for 2-3 h to obtain a polyurethane-organosilicon emulsion.

[0010] Step 2: Add the reactant monomers to the polyurethane-silicone emulsion at a rate of 30-40 drops / min, and add ammonium persulfate to continue the reaction for 2-3 hours. After the reaction is completed, cool, demulsify, and dry to obtain a core-shell rubber particle with a three-layer structure.

[0011] Step 3: Mix and heat bisphenol A epoxy resin, curing agent, accelerator, core-shell rubber particles, foaming agent and surfactant to obtain an epoxy resin liquid; cut and dry 10-15 layers of glass fiber cloth and lay them flat on a glass plate, then evenly coat the epoxy resin liquid onto the glass fiber cloth, and after full impregnation, drying and lamination curing, obtain the finished product.

[0012] In a more optimized manner, in step one, the content of each component of the organosilicon seed emulsion is as follows (by mass): 100-120 parts deionized water, 0.4-0.5 parts sodium dodecyl sulfonate, 30-35 parts octamethylcyclotetrasiloxane, 3-5 parts tetraethyl orthosilicate, 2-3 parts methacryloxypropylmethyldimethoxysilane, 0.2-0.3 parts emulsifier, and 2-3 parts p-toluenesulfonic acid; wherein the emulsifier is emulsifier OP-10.

[0013] In a more optimized manner, in step one, the content of each component of the polyurethane prepolymer is as follows: by mass parts, 8-10 parts of polypropylene glycol, 5-6 parts of hexamethylene diisocyanate, 20-25 parts of butyl acrylate, and 1-2 parts of hydroxyethyl acrylate; the reaction mass ratio of polyurethane prepolymer, organosilicon seed emulsion and ammonium persulfate is 2:(5-6):0.01.

[0014] In a more optimized manner, in step two, the reaction monomers include modified propylene monomers, acrylamide, hexafluoropropylene, perfluoromethyl vinyl ether, and allyl alcohol glycidyl ether, wherein the reaction molar ratio of modified propylene monomers, acrylamide, hexafluoropropylene, perfluoromethyl vinyl ether, and allyl alcohol glycidyl ether is (3-4):1:2:(2-3):1; and the reaction mass ratio of reaction monomers, polyurethane-silicone emulsion, and ammonium persulfate is (2-3):15:0.02.

[0015] A more optimized preparation process for the modified propylene monomer is as follows: 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, ethylene glycol monomethyl ether, propylene glycol methyl ether, polymerization inhibitor methylhydroquinone, triethylamine and tetrahydrofuran are mixed and stirred at 65-75℃ until dissolved. Then, a tetrahydrofuran solution of acryloyl chloride is added dropwise, and the reaction is continued with stirring for 12-14 hours. After the reaction is completed, the mixture is separated, washed, filtered, rotary evaporated, and recrystallized to obtain the modified propylene monomer.

[0016] In a more optimized manner, the molar ratio of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, ethylene glycol monomethyl ether, propylene glycol methyl ether and acryloyl chloride in the preparation of the modified propylene monomer is 2:(1.5-2.0):1:6.

[0017] In a more optimized manner, the specific preparation process of the epoxy resin solution in step three is as follows: Bisphenol A epoxy resin, curing agent, and accelerator are mixed and heated at 85-95℃ for 40-60 minutes, then heated to 140-150℃ and core-shell rubber particles are added and heated for 50-60 minutes, then cooled to 60-70℃ and foaming agent and surfactant are added and heated for 40-60 minutes. After heating, the epoxy resin solution is discharged.

[0018] In a more optimized manner, the content of each component in the epoxy resin adhesive is as follows: by mass parts, 40-60 parts bisphenol A epoxy resin, 5-10 parts curing agent, 2-3 parts accelerator, 5-10 parts core-shell rubber particles, 5-10 parts foaming agent, and 2-5 parts surfactant; wherein the curing agent is polyetheramine D230, the accelerator is triethanolamine, the foaming agent is benzenesulfonyl hydrazine, and the surfactant is Tween 20.

[0019] In a more optimized manner, the lamination and curing process parameters in step three are as follows: lamination temperature is 100-180℃, lamination pressure is 5-50MPa, and lamination time is 3-20min.

[0020] The beneficial effects of this invention are:

[0021] The invention is characterized in that, in step one, an organosilicon seed emulsion is prepared by adding deionized water, sodium dodecyl sulfonate, octamethylcyclotetrasiloxane, tetraethyl orthosilicate, methacryloyloxypropylmethyldimethoxysilane, an emulsifier, and p-toluenesulfonic acid. A polyurethane prepolymer is prepared by adding polypropylene glycol, hexamethylene diisocyanate, butyl acrylate, and hydroxyethyl acrylate. The polyurethane prepolymer is then added dropwise to the organosilicon seed emulsion, and an ammonium sulfate initiation process yields a polyurethane-organosilicon emulsion. In this step, several organosilicon monomers are first added, and an organosilicon seed emulsion is obtained through hydrolysis and condensation. Then, a polyurethane prepolymer is prepared by reacting isocyanate groups and hydroxyl groups. Finally, ammonium persulfate is used as an initiator to decompose and generate free radicals, which initiate a free radical polymerization reaction between the unsaturated double bonds present in the polyurethane prepolymer and the organosilicon seed emulsion, causing the polyurethane and organosilicon to be chemically bonded together to form a stable polyurethane-organosilicon composite emulsion.

[0022] The present invention is characterized in that, in step two, a modified propylene monomer is obtained by adding 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, ethylene glycol monomethyl ether, propylene glycol methyl ether, the polymerization inhibitor methylhydroquinone, triethylamine, tetrahydrofuran, and acryloyl chloride. The modified propylene monomer, acrylamide, hexafluoropropylene, perfluoromethyl vinyl ether, and allyl glycidyl ether are added dropwise to a polyurethane-silicone emulsion, and the molar ratio of the modified propylene monomer, acrylamide, hexafluoropropylene, perfluoromethyl vinyl ether, and allyl glycidyl ether is set to (3-4):1:2:(2-3):1, thereby initiating the reaction to obtain a core-shell rubber particle with a three-layer structure.

[0023] The modified propylene monomer contains a large number of polyether segments with good flexibility and benzotriazole structures with good aging resistance. Therefore, adding it to polyurethane-silicone emulsions can effectively improve the flexibility and aging resistance of core-shell rubber particles. Perfluoromethyl vinyl ether and allyl glycidyl ether monomers also contain a large number of polyether chains with good flexibility. Therefore, adding them to polyurethane-silicone emulsions can effectively improve the flexibility of core-shell rubber particles. Hexafluoropropylene and perfluoromethyl vinyl ether monomers contain a large number of fluorine groups with hydrophobic and corrosion-resistant properties. Therefore, adding them to polyurethane-silicone emulsions can effectively improve the hydrophobicity of core-shell rubber particles and their resistance to acids, alkalis, organic solvents, and other chemicals, extending the service life of the material. Acrylamide monomers contain active amino groups. Therefore, by grafting amino-containing compounds onto acrylic polymers through chemical reactions, the amino groups can undergo a curing reaction with the main resin, epoxy resin, allowing the core-shell rubber particles to better participate in the epoxy resin curing network and improving the toughening effect.

[0024] The invention is characterized in that, in step three, bisphenol A epoxy resin, curing agent, accelerator, core-shell rubber particles, foaming agent, and surfactant are mixed and heated to obtain an epoxy resin solution; glass fiber cloth is cut, dried, and laid flat on a glass plate, and then the epoxy resin solution is evenly coated onto the glass fiber cloth. After thorough impregnation, drying, lamination, and curing, the finished product is obtained. The finished product prepared by this invention has good toughness and hydrophobic corrosion resistance, and therefore has broad application prospects in the field of epoxy resin technology. Detailed Implementation

[0025] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0026] Raw material source:

[0027] Polypropylene glycol, molecular weight 400; Bisphenol A epoxy resin, provided by Jinan Yanglan New Material Technology Co., Ltd., viscosity 12000; Tween 20, provided by Jinan Xinshuangyue Chemical Co., Ltd., model 20; Fiberglass cloth, provided by Langfang Deyuan Energy Saving Technology Co., Ltd., thickness 0.18mm; by mass parts, one part is 1g.

[0028] Example 1: Step 1: Mix 100g deionized water, 0.4g sodium dodecyl sulfonate, 30g octamethylcyclotetrasiloxane, 3g tetraethyl orthosilicate, and 2g methacryloxypropylmethyldimethoxysilane. Stir at 30°C for 40 min, then add 0.2g emulsifier OP-10 and emulsify for 40 min to obtain an organosilicon emulsion. Under nitrogen atmosphere, stir and heat the organosilicon emulsion to 95°C, then add 2g p-toluenesulfonic acid and continue the reaction for 10 h to obtain an organosilicon seed emulsion.

[0029] 8g of polypropylene glycol, 5g of hexamethylene diisocyanate, and 20g of butyl acrylate were mixed and stirred at 30℃ for 2.0h. Then, 1g of hydroxyethyl acrylate was added and stirring was continued for 40min to obtain a polyurethane prepolymer. The polyurethane prepolymer was added dropwise to an organosilicon seed emulsion at a rate of 40 drops / min, and ammonium persulfate was added and the reaction was continued for 3h to obtain a polyurethane-organosilicon emulsion. The mass ratio of polyurethane prepolymer, organosilicon seed emulsion, and ammonium persulfate was 2:5.5:0.01.

[0030] Step 2: Mix 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, ethylene glycol monomethyl ether, propylene glycol methyl ether, polymerization inhibitor methylhydroquinone, triethylamine, and tetrahydrofuran, and stir at 75°C until dissolved. Then add a tetrahydrofuran solution of acryloyl chloride dropwise, and continue stirring for 14 hours. After the reaction is complete, separate the contents, wash, filter, rotary evaporate, and recrystallize to obtain the modified propylene monomer. The molar ratio of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, ethylene glycol monomethyl ether, propylene glycol methyl ether, and acryloyl chloride is 2:1.8:1:6.

[0031] Modified propylene monomers, acrylamide, hexafluoropropylene, perfluoromethyl vinyl ether, and allyl glycidyl ether were added dropwise to a polyurethane-silicone emulsion at a rate of 40 drops / min. Ammonium persulfate was added and the reaction continued for 3 hours. After the reaction was completed, the mixture was cooled, demulsified, and dried to obtain a core-shell rubber particle with a three-layer structure. The molar ratio of the modified propylene monomers, acrylamide, hexafluoropropylene, perfluoromethyl vinyl ether, and allyl glycidyl ether was 3.5:1:2:2.5:1; the mass ratio of the reactants, polyurethane-silicone emulsion, and ammonium persulfate was 2.5:15:0.02.

[0032] Step 3: Mix 50g of bisphenol A epoxy resin, 7g of polyetheramine D230, and 2g of triethanolamine, heat at 95℃ for 60min, then raise the temperature to 150℃ and add 8g of core-shell rubber particles, heat for 60min, then lower the temperature to 70℃ and add 7g of benzenesulfonyl hydrazine and 3g of Tween 20, heat for 60min. After heating, discharge the material to obtain epoxy resin solution; cut and dry 15 layers of glass fiber cloth and lay them flat on a glass plate, then evenly coat the epoxy resin solution onto the glass fiber cloth, and after full impregnation, drying, lamination and curing, obtain the finished product; the lamination and curing process parameters are: lamination temperature 180℃, lamination pressure 50MPa, lamination time 20min.

[0033] Example 2: Step 1: Mix 100g deionized water, 0.4g sodium dodecyl sulfonate, 30g octamethylcyclotetrasiloxane, 3g tetraethyl orthosilicate, and 2g methacryloxypropylmethyldimethoxysilane. Stir at 27°C for 35 min, then add 0.2g emulsifier OP-10 and emulsify for 35 min to obtain an organosilicon emulsion. Under nitrogen atmosphere, stir and heat the organosilicon emulsion to 90°C, then add 2g p-toluenesulfonic acid and continue the reaction for 9 h to obtain an organosilicon seed emulsion.

[0034] 8g of polypropylene glycol, 5g of hexamethylene diisocyanate, and 20g of butyl acrylate were mixed and stirred at 27°C for 1.7h. Then, 1g of hydroxyethyl acrylate was added and stirring was continued for 35min to obtain a polyurethane prepolymer. The polyurethane prepolymer was added dropwise to an organosilicon seed emulsion at a rate of 40 drops / min, and ammonium persulfate was added to continue the reaction for 2.5h to obtain a polyurethane-organosilicon emulsion. The mass ratio of polyurethane prepolymer, organosilicon seed emulsion, and ammonium persulfate was 2:5.5:0.01.

[0035] Step 2: Mix 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, ethylene glycol monomethyl ether, propylene glycol methyl ether, polymerization inhibitor methylhydroquinone, triethylamine, and tetrahydrofuran, and stir at 70°C until dissolved. Then add a tetrahydrofuran solution of acryloyl chloride dropwise, and continue stirring for 13 hours. After the reaction is complete, separate the contents, wash, filter, rotary evaporate, and recrystallize to obtain the modified propylene monomer. The molar ratio of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, ethylene glycol monomethyl ether, propylene glycol methyl ether, and acryloyl chloride is 2:1.8:1:6.

[0036] Modified propylene monomers, acrylamide, hexafluoropropylene, perfluoromethyl vinyl ether, and allyl glycidyl ether were added dropwise to a polyurethane-silicone emulsion at a rate of 40 drops / min. Ammonium persulfate was then added, and the reaction continued for 2.5 hours. After the reaction was completed, the mixture was cooled, demulsified, and dried to obtain a core-shell rubber particle with a three-layer structure. The molar ratio of the modified propylene monomers, acrylamide, hexafluoropropylene, perfluoromethyl vinyl ether, and allyl glycidyl ether was 3.5:1:2:2.5:1; the mass ratio of the reactants, polyurethane-silicone emulsion, and ammonium persulfate was 2.5:15:0.02.

[0037] Step 3: Mix 50g of bisphenol A epoxy resin, 7g of polyetheramine D230, and 2g of triethanolamine, heat at 90℃ for 50min, then raise the temperature to 145℃ and add 8g of core-shell rubber particles, heat for 55min, then lower the temperature to 65℃ and add 7g of benzenesulfonyl hydrazine and 3g of Tween 20, heat for 50min. After heating, discharge the material to obtain epoxy resin solution; cut and dry 15 layers of fiberglass cloth and lay them flat on a glass plate, then evenly coat the fiberglass cloth with epoxy resin solution, and after full impregnation, drying, and lamination curing, obtain the finished product; the lamination curing process parameters are: lamination temperature 170℃, lamination pressure 45MPa, and lamination time 15min.

[0038] Example 3: Step 1: Mix 100g deionized water, 0.4g sodium dodecyl sulfonate, 30g octamethylcyclotetrasiloxane, 3g tetraethyl orthosilicate, and 2g methacryloxypropylmethyldimethoxysilane. Stir at 25°C for 30 min, then add 0.2g emulsifier OP-10 and emulsify for 30 min to obtain an organosilicon emulsion. Under nitrogen atmosphere, stir and heat the organosilicon emulsion to 85°C, then add 2g p-toluenesulfonic acid and continue the reaction for 8 h to obtain an organosilicon seed emulsion.

[0039] 8g of polypropylene glycol, 5g of hexamethylene diisocyanate, and 20g of butyl acrylate were mixed and stirred at 25°C for 1.5h. Then, 1g of hydroxyethyl acrylate was added and stirring was continued for 30min to obtain a polyurethane prepolymer. The polyurethane prepolymer was added dropwise to an organosilicon seed emulsion at a rate of 40 drops / min, and ammonium persulfate was added to continue the reaction for 2h to obtain a polyurethane-organosilicon emulsion. The mass ratio of polyurethane prepolymer, organosilicon seed emulsion, and ammonium persulfate was 2:5.5:0.01.

[0040] Step 2: Mix 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, ethylene glycol monomethyl ether, propylene glycol methyl ether, polymerization inhibitor methylhydroquinone, triethylamine, and tetrahydrofuran, and stir at 65°C until dissolved. Then add a tetrahydrofuran solution of acryloyl chloride dropwise, and continue stirring for 12 hours. After the reaction is complete, separate the contents, wash, filter, rotary evaporate, and recrystallize to obtain the modified propylene monomer. The molar ratio of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, ethylene glycol monomethyl ether, propylene glycol methyl ether, and acryloyl chloride is 2:1.8:1:6.

[0041] Modified propylene monomers, acrylamide, hexafluoropropylene, perfluoromethyl vinyl ether, and allyl glycidyl ether were added dropwise to a polyurethane-silicone emulsion at a rate of 40 drops / min. Ammonium persulfate was then added, and the reaction continued for 2 hours. After the reaction was completed, the mixture was cooled, demulsified, and dried to obtain a core-shell rubber particle with a three-layer structure. The molar ratio of the modified propylene monomers, acrylamide, hexafluoropropylene, perfluoromethyl vinyl ether, and allyl glycidyl ether was 3.5:1:2:2.5:1; the mass ratio of the reactants, polyurethane-silicone emulsion, and ammonium persulfate was 2.5:15:0.02.

[0042] Step 3: Mix 50g of bisphenol A epoxy resin, 7g of polyetheramine D230, and 2g of triethanolamine, heat at 85℃ for 40min, then raise the temperature to 140℃ and add 8g of core-shell rubber particles, heat for 50min, then lower the temperature to 60℃ and add 7g of benzenesulfonyl hydrazine and 3g of Tween 20, heat for 40min. After heating, discharge the material to obtain epoxy resin solution; cut and dry 15 layers of glass fiber cloth and lay them flat on a glass plate, then evenly coat the epoxy resin solution onto the glass fiber cloth, and after full impregnation, drying, lamination and curing, obtain the finished product; the lamination and curing process parameters are: lamination temperature 160℃, lamination pressure 40MPa, lamination time 10min.

[0043] Comparative Example 1: When preparing core-shell rubber particles, the modified propylene monomer in the reaction monomer was removed, and the rest was the same as in Example 1. The specific steps are as follows: Step 1: 100g of deionized water, 0.4g of sodium dodecyl sulfonate, 30g of octamethylcyclotetrasiloxane, 3g of tetraethyl orthosilicate, and 2g of methacryloyloxypropylmethyldimethoxysilane were mixed and stirred at 30°C for 40min. Then, 0.2g of emulsifier OP-10 was added and emulsified for 40min to obtain an organosilicon emulsion. Under nitrogen atmosphere, the organosilicon emulsion was stirred and heated to 95°C. Then, 2g of p-toluenesulfonic acid was added and the reaction was continued for 10h to obtain an organosilicon seed emulsion.

[0044] 8g of polypropylene glycol, 5g of hexamethylene diisocyanate, and 20g of butyl acrylate were mixed and stirred at 30℃ for 2.0h. Then, 1g of hydroxyethyl acrylate was added and stirring was continued for 40min to obtain a polyurethane prepolymer. The polyurethane prepolymer was added dropwise to an organosilicon seed emulsion at a rate of 40 drops / min, and ammonium persulfate was added and the reaction was continued for 3h to obtain a polyurethane-organosilicon emulsion. The mass ratio of polyurethane prepolymer, organosilicon seed emulsion, and ammonium persulfate was 2:5.5:0.01.

[0045] Step 2: Acrylamide, hexafluoropropylene, perfluoromethyl vinyl ether, and allyl alcohol glycidyl ether were added dropwise to the polyurethane-silicone emulsion at a rate of 40 drops / min, and ammonium persulfate was added to continue the reaction for 3 hours. After the reaction was completed, the mixture was cooled, demulsified, and dried to obtain a core-shell rubber particle with a three-layer structure. The molar ratio of acrylamide, hexafluoropropylene, perfluoromethyl vinyl ether, and allyl alcohol glycidyl ether was 1:2:2.5:1; the mass ratio of the reactants, polyurethane-silicone emulsion, and ammonium persulfate was 2.5:15:0.02.

[0046] Step 3: Mix 50g of bisphenol A epoxy resin, 7g of polyetheramine D230, and 2g of triethanolamine, heat at 95℃ for 60min, then raise the temperature to 150℃ and add 8g of core-shell rubber particles, heat for 60min, then lower the temperature to 70℃ and add 7g of benzenesulfonyl hydrazine and 3g of Tween 20, heat for 60min. After heating, discharge the material to obtain epoxy resin solution; cut and dry 15 layers of glass fiber cloth and lay them flat on a glass plate, then evenly coat the epoxy resin solution onto the glass fiber cloth, and after full impregnation, drying, lamination and curing, obtain the finished product; the lamination and curing process parameters are: lamination temperature 180℃, lamination pressure 50MPa, lamination time 20min.

[0047] Comparative Example 2: When preparing core-shell rubber particles, the modified propylene monomer, perfluoromethyl vinyl ether, and allyl alcohol glycidyl ether in the reaction monomers were removed, and the rest were the same as in Example 1. The specific steps are as follows: Step 1: 100g of deionized water, 0.4g of sodium dodecyl sulfonate, 30g of octamethylcyclotetrasiloxane, 3g of tetraethyl orthosilicate, and 2g of methacryloyloxypropylmethyldimethoxysilane were mixed and stirred at 30°C for 40min. Then, 0.2g of emulsifier OP-10 was added and emulsified for 40min to obtain an organosilicon emulsion. Under nitrogen atmosphere, the organosilicon emulsion was stirred and heated to 95°C. Then, 2g of p-toluenesulfonic acid was added and the reaction was continued for 10h to obtain an organosilicon seed emulsion.

[0048] 8g of polypropylene glycol, 5g of hexamethylene diisocyanate, and 20g of butyl acrylate were mixed and stirred at 30℃ for 2.0h. Then, 1g of hydroxyethyl acrylate was added and stirring was continued for 40min to obtain a polyurethane prepolymer. The polyurethane prepolymer was added dropwise to an organosilicon seed emulsion at a rate of 40 drops / min, and ammonium persulfate was added and the reaction was continued for 3h to obtain a polyurethane-organosilicon emulsion. The mass ratio of polyurethane prepolymer, organosilicon seed emulsion, and ammonium persulfate was 2:5.5:0.01.

[0049] Step 2: Acrylamide and hexafluoropropylene were added dropwise to the polyurethane-silicone emulsion at a rate of 40 drops / min, and ammonium persulfate was added to continue the reaction for 3 hours. After the reaction was completed, the mixture was cooled, demulsified, and dried to obtain a core-shell rubber particle with a three-layer structure. The molar ratio of acrylamide to hexafluoropropylene was 1:2; the mass ratio of the reactant monomers, polyurethane-silicone emulsion, and ammonium persulfate was 2.5:15:0.02.

[0050] Step 3: Mix 50g of bisphenol A epoxy resin, 7g of polyetheramine D230, and 2g of triethanolamine, heat at 95℃ for 60min, then raise the temperature to 150℃ and add 8g of core-shell rubber particles, heat for 60min, then lower the temperature to 70℃ and add 7g of benzenesulfonyl hydrazine and 3g of Tween 20, heat for 60min. After heating, discharge the material to obtain epoxy resin solution; cut and dry 15 layers of glass fiber cloth and lay them flat on a glass plate, then evenly coat the epoxy resin solution onto the glass fiber cloth, and after full impregnation, drying, lamination and curing, obtain the finished product; the lamination and curing process parameters are: lamination temperature 180℃, lamination pressure 50MPa, lamination time 20min.

[0051] Comparative Example 3: When preparing core-shell rubber particles, hexafluoropropylene and perfluoromethyl vinyl ether were removed from the reactant monomers, and the rest were the same as in Example 1. The specific steps are as follows: Step 1: 100g of deionized water, 0.4g of sodium dodecyl sulfonate, 30g of octamethylcyclotetrasiloxane, 3g of tetraethyl orthosilicate, and 2g of methacryloxypropylmethyldimethoxysilane were mixed and stirred at 30°C for 40min. Then, 0.2g of emulsifier OP-10 was added and emulsified for 40min to obtain an organosilicon emulsion. Under nitrogen atmosphere, the organosilicon emulsion was stirred and heated to 95°C. Then, 2g of p-toluenesulfonic acid was added and the reaction was continued for 10h to obtain an organosilicon seed emulsion.

[0052] 8g of polypropylene glycol, 5g of hexamethylene diisocyanate, and 20g of butyl acrylate were mixed and stirred at 30℃ for 2.0h. Then, 1g of hydroxyethyl acrylate was added and stirring was continued for 40min to obtain a polyurethane prepolymer. The polyurethane prepolymer was added dropwise to an organosilicon seed emulsion at a rate of 40 drops / min, and ammonium persulfate was added and the reaction was continued for 3h to obtain a polyurethane-organosilicon emulsion. The mass ratio of polyurethane prepolymer, organosilicon seed emulsion, and ammonium persulfate was 2:5.5:0.01.

[0053] Step 2: Mix 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, ethylene glycol monomethyl ether, propylene glycol methyl ether, polymerization inhibitor methylhydroquinone, triethylamine, and tetrahydrofuran, and stir at 75°C until dissolved. Then add a tetrahydrofuran solution of acryloyl chloride dropwise, and continue stirring for 14 hours. After the reaction is complete, separate the contents, wash, filter, rotary evaporate, and recrystallize to obtain the modified propylene monomer. The molar ratio of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, ethylene glycol monomethyl ether, propylene glycol methyl ether, and acryloyl chloride is 2:1.8:1:6.

[0054] Modified propylene monomer, acrylamide, and allyl alcohol glycidyl ether were added dropwise to a polyurethane-silicone emulsion at a rate of 40 drops / min, and ammonium persulfate was added to continue the reaction for 3 hours. After the reaction was completed, the mixture was cooled, demulsified, and dried to obtain a core-shell rubber particle with a three-layer structure. The molar ratio of modified propylene monomer, acrylamide, and allyl alcohol glycidyl ether was 3.5:1:1; the mass ratio of reactant monomer, polyurethane-silicone emulsion, and ammonium persulfate was 2.5:15:0.02.

[0055] Step 3: Mix 50g of bisphenol A epoxy resin, 7g of polyetheramine D230, and 2g of triethanolamine, heat at 95℃ for 60min, then raise the temperature to 150℃ and add 8g of core-shell rubber particles, heat for 60min, then lower the temperature to 70℃ and add 7g of benzenesulfonyl hydrazine and 3g of Tween 20, heat for 60min. After heating, discharge the material to obtain epoxy resin solution; cut and dry 15 layers of glass fiber cloth and lay them flat on a glass plate, then evenly coat the epoxy resin solution onto the glass fiber cloth, and after full impregnation, drying, lamination and curing, obtain the finished product; the lamination and curing process parameters are: lamination temperature 180℃, lamination pressure 50MPa, lamination time 20min.

[0056] Comparative Example 4: The core-shell rubber particles were removed, and the rest was the same as in Example 1. The specific steps are as follows: Step 1: 50g of bisphenol A epoxy resin, 7g of polyetheramine D230, and 2g of triethanolamine were mixed and heated at 95°C for 60min, then heated to 150°C for 60min, then cooled to 70°C and 7g of benzenesulfonyl hydrazine and 3g of Tween 20 were added and heated for 60min. After heating, the epoxy resin solution was discharged. 15 layers of glass fiber cloth were cut, dried, and laid flat on a glass plate. The epoxy resin solution was then evenly coated onto the glass fiber cloth. After thorough impregnation, drying, and lamination curing, the finished product was obtained. The lamination curing process parameters were: lamination temperature of 180°C, lamination pressure of 50MPa, and lamination time of 20min.

[0057] Testing and experimentation:

[0058] Impact resistance test: The epoxy resin liquid prepared in this invention was cured at 130℃ for 5 hours and cut to obtain a sample of 80×10×4mm; the sample was then tested using the XJU22 cantilever beam impact tester of Shandong Oubet Test Equipment Co., Ltd.

[0059] Elongation at break test: The epoxy resin solution prepared in this invention was cured at 130℃ for 5 hours and cut to obtain a sample of 150×10×4mm; then the sample was tested using an electronic universal testing machine according to the standard GB / T 1040.1-2018, with a loading speed of 20mm / min, and the elongation at break was calculated according to the formula based on the reading.

[0060] Hydrophobicity test: The finished product prepared according to this invention was used as a sample, and the water contact angle was measured using a water contact angle meter from DataPhysics, Germany. The results are shown in the table below:

[0061]

[0062] Conclusion: The dosages in Examples 1-3 remained unchanged, with only some reaction parameters modified. Experimental data show that the various properties of the samples did not exhibit significant fluctuations.

[0063] Comparative Example 1: In the preparation of core-shell rubber particles, the modified propylene monomer in the reactant monomer was removed, while the rest was the same as in Example 1. Experimental data showed that, compared to Example 1, the impact strength decreased to 29.2 KJ / m. 2 The elongation at break decreased to 15.3%. The reason for this is that the modified propylene monomer contains a large number of polyether segments with good flexibility. Therefore, adding it to the polyurethane-silicone emulsion to prepare epoxy resin can effectively improve the flexibility of the material. Removing it reduces the impact strength and elongation at break.

[0064] Comparative Example 2: In the preparation of core-shell rubber particles, the modified propylene monomer, perfluoromethyl vinyl ether, and allyl alcohol glycidyl ether were removed from the reaction monomers, while the rest remained the same as in Example 1. The impact strength was reduced to 25.7 KJ / m. 2 The elongation at break decreased to 13.3%. The reason for this is that the modified propylene monomer, perfluoromethyl vinyl ether, and allyl alcohol glycidyl ether contain a large number of polyether segments with good flexibility. Therefore, adding them to the polyurethane-silicone emulsion to prepare epoxy resin can effectively improve the flexibility of the material. Removing them reduces the impact strength and elongation at break.

[0065] Comparative Example 3: In the preparation of core-shell rubber particles, hexafluoropropylene and perfluoromethyl vinyl ether were removed from the reactant monomers, while the rest remained the same as in Example 1. The impact strength was reduced to 30.9 KJ / m. 2 The elongation at break decreased to 16.4%, and the water contact angle decreased to 86°. The reason for this is that hexafluoropropylene and perfluoromethyl vinyl ether contain a large number of fluorine groups with hydrophobic and corrosion-resistant properties. Therefore, adding them to polyurethane-silicone emulsion to prepare epoxy resin can effectively improve the hydrophobic properties of the material. Removing them reduces the water contact angle.

[0066] Comparative Example 4: The core-shell rubber particles were removed, and the rest remained the same as in Example 1. The impact strength was reduced to 11.5 KJ / m. 2The elongation at break decreased to 9.2%, and the water contact angle decreased to 75°. The reason for this is that, according to Comparative Examples 1-3, the core-shell rubber particles prepared by this invention have good flexibility and hydrophobicity. Therefore, after removing the core-shell rubber particles, the impact strength, elongation at break, and water contact angle decreased.

[0067] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process method article or apparatus.

[0068] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A process for preparing a drop-resistant and impact-resistant epoxy fiberglass composite electronic product board, characterized in that: Includes the following steps: Step 1: Mix deionized water, sodium dodecyl sulfonate, octamethylcyclotetrasiloxane, tetraethyl orthosilicate, and methacryloyloxypropylmethyldimethoxysilane. Stir at 25-30℃ for 30-40 minutes, then add an emulsifier and emulsify for another 30-40 minutes to obtain an organosilicon emulsion. Under nitrogen atmosphere, stir and heat the organosilicon emulsion to 85-95℃, then add p-toluenesulfonic acid and continue the reaction for 8-10 hours to obtain an organosilicon seed emulsion. Polypropylene glycol, hexamethylene diisocyanate, and butyl acrylate are mixed and stirred at 25-30℃ for 1.5-2.0 h. Then, hydroxyethyl acrylate is added and stirring is continued for 30-40 min to obtain a polyurethane prepolymer. The polyurethane prepolymer is added dropwise to an organosilicon seed emulsion at a rate of 30-40 drops / min, and ammonium persulfate is added to continue the reaction for 2-3 h to obtain a polyurethane-organosilicon emulsion. Step 2: Add the reactant monomers to the polyurethane-silicone emulsion at a rate of 30-40 drops / min, and add ammonium persulfate to continue the reaction for 2-3 hours. After the reaction is completed, cool, demulsify, and dry to obtain a core-shell rubber particle with a three-layer structure. The reacting monomers include modified propylene monomers, acrylamide, hexafluoropropylene, perfluoromethyl vinyl ether, and allyl glycidyl ether. The molar ratio of the reacting monomers, acrylamide, hexafluoropropylene, perfluoromethyl vinyl ether, and allyl glycidyl ether is (3-4):1:2:(2-3):1; the mass ratio of the reacting monomers, polyurethane-silicone emulsion, and ammonium persulfate is (2-3):15:0.

02. The preparation process of the modified propylene monomer is as follows: 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, ethylene glycol monomethyl ether, propylene glycol methyl ether, polymerization inhibitor methylhydroquinone, triethylamine and tetrahydrofuran are mixed and stirred at 65-75℃ until dissolved. Then, a tetrahydrofuran solution of acryloyl chloride is added dropwise, and the reaction is continued to be stirred for 12-14 hours. After the reaction is completed, the mixture is separated, washed, filtered, rotary evaporated, and recrystallized to obtain the modified propylene monomer. The molar ratio of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, ethylene glycol monomethyl ether, propylene glycol methyl ether and acryloyl chloride is 2:(1.5-2.0):1:

6. Step 3: Mix and heat bisphenol A epoxy resin, curing agent, accelerator, core-shell rubber particles, foaming agent and surfactant to obtain an epoxy resin liquid; cut and dry 10-15 layers of glass fiber cloth and lay them flat on a glass plate, then evenly coat the epoxy resin liquid onto the glass fiber cloth, and after full impregnation, drying and lamination curing, obtain the finished product.

2. The preparation process of a drop-resistant and impact-resistant epoxy fiberglass composite electronic product board according to claim 1, characterized in that: In step one, the content of each component of the organosilicon seed emulsion is as follows (by mass): 100-120 parts deionized water, 0.4-0.5 parts sodium dodecyl sulfonate, 30-35 parts octamethylcyclotetrasiloxane, 3-5 parts tetraethyl orthosilicate, 2-3 parts methacryloxypropylmethyldimethoxysilane, 0.2-0.3 parts emulsifier, and 2-3 parts p-toluenesulfonic acid; the emulsifier is emulsifier OP-10.

3. The preparation process of a drop-resistant and impact-resistant epoxy fiberglass composite electronic product board according to claim 1, characterized in that: In step one, the content of each component of the polyurethane prepolymer is as follows: by mass parts, 8-10 parts polypropylene glycol, 5-6 parts hexamethylene diisocyanate, 20-25 parts butyl acrylate, and 1-2 parts hydroxyethyl acrylate; the reaction mass ratio of polyurethane prepolymer, organosilicon seed emulsion and ammonium persulfate is 2:(5-6):0.

01.

4. The preparation process of a drop-resistant and impact-resistant epoxy fiberglass composite electronic product board according to claim 1, characterized in that: In step three, the specific preparation process of the epoxy resin solution is as follows: Bisphenol A epoxy resin, curing agent, and accelerator are mixed and heated at 85-95℃ for 40-60 minutes, then heated to 140-150℃ and core-shell rubber particles are added and heated for 50-60 minutes, then cooled to 60-70℃ and foaming agent and surfactant are added and heated for 40-60 minutes. After heating, the epoxy resin solution is discharged.

5. The preparation process of a drop-resistant and impact-resistant epoxy fiberglass composite electronic product board according to claim 4, characterized in that: The epoxy resin adhesive contains the following components by mass: 40-60 parts bisphenol A epoxy resin, 5-10 parts curing agent, 2-3 parts accelerator, 5-10 parts core-shell rubber particles, 5-10 parts foaming agent, and 2-5 parts surfactant; the curing agent is polyetheramine D230, the accelerator is triethanolamine, the foaming agent is benzenesulfonyl hydrazine, and the surfactant is Tween 20.

6. The preparation process of a drop-resistant and impact-resistant epoxy fiberglass composite electronic product board according to claim 1, characterized in that: In step three, the lamination curing process parameters are as follows: lamination temperature is 100-180℃, lamination pressure is 5-50MPa, and lamination time is 3-20min.

7. A drop-resistant and impact-resistant epoxy fiberglass composite electronic product board, characterized in that, Prepared according to any one of the preparation processes described in claims 1-6.

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