CN-122011341-A - Epoxy resin material with low curing stress and high insulating property, and preparation method and application thereof

Abstract

The application belongs to the technical field of epoxy insulating materials, and particularly relates to an epoxy resin material with low curing stress and high insulating property, and a preparation method and application thereof; the epoxy resin material provided by the application is characterized in that 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester, 4-aminobenzoic acid and sebacic acid are introduced in the epoxy resin curing process, and are matched with three-section curing to activate dynamic transesterification reaction, so that a chain segment rearrangement and stress relaxation reaction-relaxation platform is constructed, the internal stress caused by uneven shrinkage at high temperature is balanced, fluorine-containing hyperbranched epoxy resin molecules absorb crack expansion energy and dissipate impact stress through a hyperbranched structure, in addition, nitrogen and fluorine in a compact epoxy crosslinking curing network constructed by a dual curing agent system can be used as charge traps to capture carriers, thereby improving the mechanical property and insulation property of the epoxy resin material, and solving the technical problem that the high-performance epoxy resin material is difficult to prepare in the prior art.

Inventors

• ZHENG YAO
• YAN LE
• YU JIAHE
• ZHOU FUSHENG
• GAO CHAO
• HUANG RUODONG
• XIONG JIAMING
• YUE YANGJING
• WANG GUOLI
• JIN HU
• ZHANG YI

Assignees

• 南方电网科学研究院有限责任公司

Dates

Publication Date

20260512

Application Date

20260309

Claims (10)

1. 1. The preparation method of the epoxy resin material with low curing stress and high insulating property is characterized by comprising the following steps: performing nucleophilic epoxy ring-opening reaction on fluorine-containing bisphenol compound and branched multifunctional glycidyl ether to obtain fluorine-containing hyperbranched epoxy resin molecules; Mixing fluorine-containing hyperbranched epoxy resin molecules, 4, 5-epoxycyclohexane-1, 2-diglycidyl ester, 4-aminobenzoic acid, sebacic acid and epoxy resin, and stirring and degassing to obtain an epoxy resin material precursor; Sequentially solidifying the precursor of the epoxy resin material at a first temperature, a second temperature and a third temperature, and cooling to obtain the epoxy resin material with low solidifying stress and high insulating property, wherein the first temperature is lower than the second temperature, and the second temperature is lower than the third temperature; and the curing temperature of the third temperature curing is 105-135 ℃.
2. 2. The method for preparing the epoxy resin material with low curing stress and high insulating property according to claim 1, wherein the fluorine-containing hyperbranched epoxy resin molecules are at least one selected from bisphenol AF, fluorine-substituted bisphenol AP and trifluoromethyl-substituted bisphenol AP; The branched multifunctional glycidyl ether is at least one selected from trimethylolpropane triglycidyl ether, triphenyl glycidyl ether and 1,3, 4-benzene triethyl ketone group glycidyl ether.
3. 3. The method for preparing the epoxy resin material with low curing stress and high insulating property according to claim 1, wherein the epoxy resin material precursor comprises, by mass, 5-45 parts of fluorine-containing hyperbranched epoxy resin molecules, 20-60 parts of 4, 5-epoxycyclohexane-1, 2-diglycidyl phthalate, 10-25 parts of 4-aminobenzoic acid, 25-45 parts of sebacic acid and 80-120 parts of epoxy resin.
4. 4. The method for preparing the epoxy resin material with low curing stress and high insulating property according to claim 1, wherein the epoxy resin is at least one selected from the group consisting of E51 epoxy resin, E44 epoxy resin, E20 epoxy resin, E12 epoxy resin, E06 epoxy resin and E03 epoxy resin.
5. 5. The method for preparing the epoxy resin material with low curing stress and high insulating property according to claim 1, wherein the temperature of stirring and degassing is 60-100 ℃, the time is 0.5-2 h, and the rotating speed is 200-500 rad/s.
6. 6. The method for preparing the epoxy resin material with low curing stress and high insulating property according to claim 1, wherein the curing temperature at the first temperature is 70-85 ℃ and the curing time is 0.5-2.5 h; the second temperature is 85-105 ℃ and the curing time is 1-5 h; and the curing time at the third temperature is 6-12 hours.
7. 7. The method for preparing the epoxy resin material with low curing stress and high insulating property according to claim 1, wherein the cooling rate is 2-10 ℃ per hour.
8. 8. An epoxy resin material with low curing stress and high insulating property, which is characterized by being prepared by the preparation method of any one of claims 1-7.
9. 9. Use of an epoxy resin material of low curing stress and high insulation properties as claimed in claim 8 for insulation of electrical equipment.
10. 10. The use of claim 9, wherein the electrical device comprises a high voltage electrical device, an ultra high voltage electrical device, or an extra high voltage electrical device.

Description

Epoxy resin material with low curing stress and high insulating property, and preparation method and application thereof Technical Field The application belongs to the technical field of epoxy insulating materials, and particularly relates to an epoxy resin material with low curing stress and high insulating property, and a preparation method and application thereof. Background Epoxy resin is widely applied to the fields of electronic component packaging, power equipment insulation, composite material matrix and the like due to excellent adhesive property, mechanical strength, chemical corrosion resistance and good electrical insulation property, however, with the continuous improvement of the requirements of modern industry on miniaturization, integration and high reliability of devices, the inherent defects of the traditional epoxy resin material are increasingly prominent, and two key technical problems are that the higher curing internal stress and the insulation property under a high electric field are insufficient. The curing internal stress of the epoxy resin material mainly originates from the fact that when the epoxy resin is converted from a liquid state to a solid state in the curing process, the curing process is regulated by the aid of non-uniform crosslinking density, volume shrinkage and the like, particularly in a fast-curing or thick-wall workpiece, stress concentration is caused by difference of internal and external temperature differences and curing speed, microcracks and buckling deformation are generated on the product, mechanical properties are reduced, meanwhile, microcracks of the epoxy resin material can accelerate deterioration of insulating properties in a high-electric field environment, even package device failure is caused, the yield, service life and long-term operation reliability of the product are seriously influenced, in order to reduce the curing stress, the prior art generally adopts the curing process regulation of adding a flexible chain segment toughening agent, using an aliphatic epoxy compound, slowly heating up and the like, however, the rigidity, heat resistance and insulating properties of the material are always sacrificed by adding the toughening agent, and simple process regulation is limited in reducing the stress effect caused by intrinsic properties of a crosslinked network, the production period is remarkably prolonged, and the efficiency is reduced. The traditional epoxy resin material has irreversible and non-dynamic epoxy cross-linked network structure in the curing process, if a novel epoxy resin material preparation method can be developed, the preparation method can activate rearrangement of epoxy cross-linked chain segments in the high-temperature rapid curing process, fully relax the internal stress of a cross-linked system, effectively reduce the curing internal stress generated by the high-temperature rapid curing, optimize the cross-linked network structure, avoid microcracks generated in the curing process of the epoxy resin material and improve the mechanical property and the insulating property of the epoxy resin material, however, the research on the existing epoxy resin material preparation process is not deep enough, and the epoxy resin material with low curing stress and high insulating property is difficult to prepare. Disclosure of Invention In view of the above, the application provides an epoxy resin material with low curing stress and high insulating property, and a preparation method and application thereof, which are used for solving the technical problem that the high-performance epoxy resin material is difficult to prepare in the prior art. The first aspect of the present application provides a method for preparing an epoxy resin material having low curing stress and high insulation properties, comprising the steps of: The preparation method of fluorine-containing hyperbranched epoxy resin molecules comprises the steps of carrying out nucleophilic epoxy ring-opening reaction on fluorine-containing bisphenol compound and branched multifunctional glycidyl ether to obtain fluorine-containing hyperbranched epoxy resin molecules; Mixing fluorine-containing hyperbranched epoxy resin molecules, 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester, 4-aminobenzoic acid, sebacic acid and epoxy resin, and stirring and degassing to obtain an epoxy resin material precursor; And (3) sequentially carrying out low-temperature (first temperature), medium-temperature (second temperature) and high-temperature curing (third temperature) on the epoxy resin material precursor, and cooling to obtain the epoxy resin material with low curing stress and high insulating property, wherein the curing temperature of the high-temperature (third temperature) curing is 105-135 ℃. Preferably, in the preparation step of the fluorine-containing hyperbranched epoxy resin molecule, the fluorine-containing hyperbranched epoxy resin molecule is selected from