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CN-120944352-B - Bismaleimide modified epoxy resin and preparation method thereof

CN120944352BCN 120944352 BCN120944352 BCN 120944352BCN-120944352-B

Abstract

The invention discloses bismaleimide modified epoxy resin and a preparation method thereof, relating to the technical field of epoxy resin, is prepared from bismaleimide, epoxy resin, compound curing agent, compound promoter, modifier and compound solvent. According to the invention, allylated bismaleimide is adopted to modify the molecular structure, so that the compatibility of the bismaleimide and epoxy resin is effectively improved, and the heat resistance is obviously improved. And a composite curing system and a high-efficiency accelerator are selected, so that the process energy consumption is reduced. The modified core-shell rubber particle modifier is introduced into an epoxy resin system, so that the toughness and impact resistance of the composite material can be remarkably improved, and meanwhile, the thermal stability and flame retardance of the resin can be effectively improved by adding the allyl POSS into the modified core-shell rubber particle. The application of the composite solvent can promote dissolution and balance viscosity and volatilization speed. The resin system is particularly suitable for the high-end fields of 5G high-frequency copper-clad plates, aerospace thermal protection coatings and the like.

Inventors

  • ZHU LIMING
  • WU HAIBING
  • WANG XIAOLONG
  • CHEN YINGFENG
  • XIE JIANZHENG

Assignees

  • 江苏耀鸿电子有限公司

Dates

Publication Date
20260512
Application Date
20251011

Claims (8)

  1. 1. The preparation method of the bismaleimide modified epoxy resin is characterized by comprising the following steps: step S1, under the protection of nitrogen, uniformly mixing epoxy resin and a modifier, heating to 110-130 ℃, stirring for 40-60min, adding bismaleimide, heating to 130-150 ℃, and preserving heat for 40-60min to form a homogeneous system; s2, cooling the homogeneous system in the step S1 to 75-85 ℃, adding a composite solvent, stirring and filtering to obtain a glue solution; Step S3, mixing the glue solution, the compound curing agent and the compound accelerating agent in the step S2, preserving heat for 30-60min, and cooling to obtain bismaleimide modified epoxy resin; in the step S1, the homogeneous system comprises the following raw materials, by weight, 15-25 parts of epoxy resin, 15-30 parts of modifier and 40-50 parts of bismaleimide; the modifier is core-shell rubber particles; The core-shell rubber particles are modified core-shell rubber particles, and the preparation method of the modified core-shell rubber particles is as follows: 1) Dispersing the dried core-shell rubber particles in a toluene water solvent, adding gamma-mercaptopropyl trimethoxy silane, stirring at 450-550rpm for 30-50min, and distilling under reduced pressure to obtain core-shell rubber particles with surfaces coated with a silane coupling agent; 2) Dispersing core-shell rubber particles coated with a silane coupling agent on the surface in a mixed solvent, performing ultrasonic dispersion for 30-40min, adding a photoinitiator in a dark place under the protection of nitrogen, stirring for 20-30min, adding allyl POSS, heating to 50-70 ℃, mechanically stirring for 30-40min, transferring to a quartz reactor, irradiating for 4-6min in a UV curing machine under the nitrogen atmosphere, performing centrifugal washing, and performing vacuum drying for 10-12 h to obtain modified core-shell rubber particles; The toluene aqueous solvent is obtained by mixing toluene and water in a volume ratio of 9:1; the bismaleimide is alkene propylated bismaleimides.
  2. 2. The preparation method of the bismaleimide modified epoxy resin according to claim 1 is characterized in that in the step S2, the mass ratio of a homogeneous system to a composite solvent in the glue solution is (3-4) (6-7).
  3. 3. The preparation method of the bismaleimide modified epoxy resin according to claim 1 is characterized in that the mass ratio of the epoxy resin to the compound curing agent to the compound accelerator is (15-25): 8-12): 1-2.
  4. 4. The preparation method of the bismaleimide modified epoxy resin according to claim 1 is characterized in that the epoxy resin is one or more of furan epoxy resin, tetraglycidyl amine type epoxy resin, bisphenol A type epoxy resin and flame retardant type epoxy resin.
  5. 5. The preparation method of the bismaleimide modified epoxy resin is characterized in that the bismaleimide modified epoxy resin is prepared from 10 parts by weight of core-shell rubber particles coated with a silane coupling agent on the surface, 50 parts by weight of toluene water solvent and 0.5 part by weight of gamma-mercaptopropyl trimethoxy silane, 3 parts by weight of allyl POSS, 0.3 part by weight of photoinitiator, 60 parts by weight of mixed solvent and 10 parts by weight of core-shell rubber particles coated with a silane coupling agent on the surface, wherein the mixed solvent is obtained by mixing acetone and N, N-dimethylformamide according to a mass ratio of 7:3.
  6. 6. The preparation method of the bismaleimide modified epoxy resin according to claim 1 is characterized in that the composite solvent is formed by compounding acetone and N, N-dimethylformamide according to a mass ratio of 7:3.
  7. 7. The preparation method of the bismaleimide modified epoxy resin is characterized in that the compound curing agent is formed by compounding one or more of diaminodiphenyl sulfone, phthalic anhydride and methyltetrahydrophthalic anhydride in a mass ratio of 7:3, the viscosity-reducing auxiliary curing agent is methylnadic anhydride, the compound accelerator is formed by compounding one or more of an accelerator and an auxiliary accelerator in a mass ratio of 3:1, and the accelerator is 2-ethyl-4-methyl-imidazole, tertiary amine and dicyandiamide, and the auxiliary accelerator is urea accelerator.
  8. 8. A bismaleimide modified epoxy resin characterized in that the bismaleimide modified epoxy resin is prepared by the preparation method according to any one of claims 1 to 7.

Description

Bismaleimide modified epoxy resin and preparation method thereof Technical Field The invention relates to the technical field of epoxy resin, in particular to bismaleimide modified epoxy resin and a preparation method thereof. Background As a high molecular polymer, the epoxy resin (EP) has the characteristics of convenient curing, strong adhesion, low contractility, good chemical resistance, good electrical insulation and the like, can be used as a coating, an adhesive, a casting material, a mould pressing material, a matrix resin of a fiber reinforced composite material and the like, and is widely applied to various industries such as transportation, aerospace, mechano-electronics, mechanical manufacturing, construction, chemical industry corrosion prevention and the like, and is an indispensable important base material. With the wide application of epoxy resin in various national economy fields, epoxy resin composite materials need to face higher temperature conditions, but epoxy resin is inflammable, hard and brittle in texture, poor in wet heat resistance and accompanied by dense smoke and molten drops during combustion, so that the application of the epoxy resin in high technical fields such as aerospace, electronic and electric fields and the like is limited to a great extent, and the requirements of people on the flame retardance and the heat resistance of the epoxy resin composite materials are higher and higher, and therefore, EP modification has become a current hot research subject. The bismaleimide resin (BMI) which is also widely applied to the fields of aviation, machinery, electronics and the like has the advantages of excellent high temperature resistance, wet heat resistance, electrical insulation, flame retardance and the like, and is commonly used as a resin matrix of an advanced composite material, a high temperature resistant insulating material and the like. However, the process performance is relatively poor, the melting point of the monomer is high, the crosslinking density of the cured product is high, the brittleness is high, and the like, which are important barriers for preventing BMI from adapting to high technical requirements and expanding new application fields. In order to solve the problems, the invention provides bismaleimide modified epoxy resin and a preparation method thereof. BMI is used as an EP modifier, bismaleimide and epoxy resin are copolymerized, and the epoxy resin is modified, so that the preparation method has the advantages of both the bismaleimide and the epoxy resin. Disclosure of Invention The invention aims to provide bismaleimide modified epoxy resin and a preparation method thereof, so as to solve the problems in the prior art. In order to achieve the above purpose, the present invention provides the following technical solutions: A preparation method of bismaleimide modified epoxy resin comprises the following steps: step S1, under the protection of nitrogen, uniformly mixing epoxy resin and a modifier, heating to 110-130 ℃, stirring for 40-60min, adding bismaleimide, heating to 130-150 ℃, and preserving heat for 40-60min to form a homogeneous system; s2, cooling the homogeneous system in the step S1 to 75-85 ℃, adding a composite solvent, stirring and filtering to obtain a glue solution; And step S3, mixing the glue solution, the compound curing agent and the compound accelerating agent in the step S2, preserving heat for 30-60min, and cooling to obtain the bismaleimide modified epoxy resin. More optimally, in the step S1, the homogeneous system comprises the following raw materials, by weight, 15-25 parts of epoxy resin, 15-30 parts of modifier and 40-50 parts of bismaleimide. More optimally, the epoxy resin is one or more of furan epoxy resin, tetraglycidyl amine type epoxy resin, bisphenol A type epoxy resin and flame retardant type epoxy resin, the Bismaleimide (BMI) is replaced by allylated bismaleimide, allyloxy is introduced on an aromatic ring of the BMI, and the modifier is one or more of core-shell rubber particles, carboxyl-terminated nitrile rubber and siloxane modifier. More optimally, the modifier is modified core-shell rubber particles, and the preparation method of the modified core-shell rubber particles is as follows: 1) Dispersing the dried core-shell rubber particles in a toluene water solvent, adding gamma-mercaptopropyl trimethoxy silane, stirring at 450-550rpm for 30-50min, and distilling under reduced pressure to obtain core-shell rubber particles with surfaces coated with a silane coupling agent; 2) Dispersing core-shell rubber particles coated with a silane coupling agent on the surface in a mixed solvent, performing ultrasonic dispersion for 30-40min, adding a photoinitiator in a dark place under the protection of nitrogen, stirring for 20-30min, adding allyl POSS, heating to 50-70 ℃, mechanically stirring for 30-40min at 300rpm, transferring to a quartz reactor, irradiating for 4-6min in a UV curing machine under the nitr