CN113278179A

CN113278179A - High-temperature-resistance epoxy glass fiber insulating layer, molded part and preparation method thereof

Info

Publication number: CN113278179A
Application number: CN202110555194.1A
Authority: CN
Inventors: 杜旻; 黄洪驰; 师强
Original assignee: Sichuan Dongcai Technology Group Co Ltd
Current assignee: Sichuan Dongcai Technology Group Co Ltd
Priority date: 2021-05-21
Filing date: 2021-05-21
Publication date: 2021-08-20
Anticipated expiration: 2041-05-21
Also published as: CN113278179B

Abstract

The invention discloses a high-temperature-resistant epoxy glass fiber insulating layer, a molded part and a preparation method thereof, and is characterized in that: the insulating layer and the molded part are made of composite materials by hot-press molding one or more layers of overlapped high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg; the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg is formed by impregnating alkali-free glass fiber-fabric with a high-temperature-resistant epoxy adhesive and then baking the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg with a semi-cured product on the alkali-free glass fiber-fabric; the high-temperature-resistant epoxy adhesive consists of epoxy resin, modified epoxy resin, a curing agent, a filler, a solvent and an accelerant. The invention is suitable for insulating layers and molded parts for high-voltage/extra-high voltage power transmission and transformation, high-voltage motors, large-scale generator sets, power transformers and other fields which are used for a long time in high-temperature and high-humidity environments, and has the characteristics of high temperature resistance, high humidity resistance and the like, good performance and strong practicability.

Description

High-temperature-resistance epoxy glass fiber insulating layer, molded part and preparation method thereof

Technical Field

The invention belongs to an insulating layer, a molded part and preparation thereof, and relates to a high-temperature-resistance epoxy glass fiber insulating layer, a molded part and preparation methods thereof. The high-temperature-resistant epoxy glass fiber insulating layer and the molded part prepared by the invention are particularly suitable for insulating layers and molded parts for high-voltage/extra-high voltage power transmission and transformation, which have higher requirements on temperature resistance and need to be used for a long time in high-temperature and high-humidity environments, and are applied to the fields of high-voltage motors, large-scale generator sets, power transformers and the like.

Background

With the national accelerated start of high-voltage power grid construction work and the vigorous demands of markets such as 'western electricity and east electricity transmission', the voltage grade of the whole line from power generation, power transmission to power transformation is continuously improved, so that the high requirements on the mechanical strength, the pressure resistance and the like of an insulating material are provided, and the high-voltage power grid is extended to a new region with sparser personnel and more complex environment along with the construction of the power grid, so that the challenging new requirements on the comprehensive performances such as long-term extreme temperature resistance, humidity resistance, chemical corrosion resistance and the like of an insulating product used in a matching way are provided. In the existing fiber reinforced composite material base material used for insulating layers and molded parts of high-voltage/extra-high voltage power transmission and transformation and the like, the epoxy resin is unique in excellent comprehensive performance. However, the traditional epoxy resin generally has the problems and defects of poor temperature resistance (less than or equal to 180 ℃), strong water absorption of the whole epoxy fiber composite material due to a large amount of free hydroxyl groups, poor humidity resistance, easy foaming and delamination during pressing and use, strength failure and the like.

Therefore, how to solve the existing technical problems is the goal of related research workers' efforts, and how to realize the high temperature resistance of the epoxy fiber insulating layer and the molded part (namely, when the bending strength at 23 ℃ is 450MPa, the mechanical strength at 230 ℃ is more than 225MPa), and the high humidity resistance (the strength retention rate at 121 ℃ and 100% humidity for 96h is more than 50% at normal temperature, namely, the bending strength is more than 225MPa, the shear strength is more than or equal to 15MPa, and the water absorption rate is less than or equal to 2%). However, in the prior art, no literature report is available that can simultaneously meet the above use requirements.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provides a high-temperature-resistance epoxy glass fiber insulating layer, a molded part and a preparation method thereof. Therefore, the high temperature resistant epoxy glass fiber insulating layer, the die-pressed part and the preparation method thereof can realize that the mechanical strength of the part is more than 225MPa at 230 ℃, the bending strength of the part is more than 225MPa at 121 ℃ for 96h in an environment with 100% of humidity, the shear strength is more than or equal to 15MPa, and the water absorption rate is less than or equal to 2%, and meet the use requirements in the fields of high voltage/extra-high voltage power transmission and transformation, high voltage motors, large-scale generator sets, power transformers and the like.

The content of the invention is as follows: a high temperature resistant epoxy glass fiber insulating layer, mould pressing finished piece, its characteristic is: the insulating layer and the molded part are made of one or more layers of overlapped high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg which is subjected to hot press molding to obtain a composite material (namely the high-temperature-resistant epoxy glass fiber insulating layer and the molded part);

the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg is formed by impregnating alkali-free glass fiber-fabric with a high-temperature-resistant epoxy adhesive and then baking (removing part of solvent in the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg) the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg with a semi-cured material on the alkali-free glass fiber-fabric;

the alkali-free glass fiber-woven fabric is alkali-free glass fiber cloth (the product production providing enterprise and trade mark can be EW140 of New material of Haoyang of Taian city, EW60 of great autumn Shuo chemical company, EW200 of Kyowa Delhong glass fiber material company, etc.), 7628 electronic grade alkali-free glass fiber cloth (the product production providing enterprise and trade mark can be EW25 of China giant Stone company, EW120 of Chongzhou International composite Material company, EW250 of Kunshan Shenhao Industrial Material company, etc.), high-strength alkali-free glass fiber cloth (the product production providing enterprise and trade mark can be high-strength cloth of middle Material science and technology company, enhanced alkali-free glass fiber cloth of Sichuan glass fiber group, high-strength glass fiber cloth of Shanghai composite Material company, etc.), alkali-free glass fiber square cloth (the product production providing enterprise and trade mark can be EW100 of China giant Stone Material company, etc.), EW180 of chongqing international composite material corporation, EW210 of Shandong Taian glass fiber corporation, and the like), glass fiber smoldering treatment cloth (product production providing enterprises and brands may be: EW210 of german glass fiber limited, EW160 of sichuan glass fiber limited, and the like);

the high-temperature-resistant epoxy adhesive comprises the following components in parts by weight: 12-45 parts of epoxy resin, 5-35 parts of modified epoxy resin, 6-34 parts of curing agent, 1-61 parts of filler, 9.5-201 parts of solvent and 0.01-0.18 part of accelerator;

the epoxy resin is one or a mixture of more than two of bisphenol fluorene epoxy resin (DGEBF for short), bis-o-cresol fluorene epoxy resin (DGEMBF for short) and bis-di-o-cresol fluorene epoxy resin (DGEDMFF for short), and the chemical structural formulas of the epoxy resin are respectively shown as the following formulas:

bisphenol fluorene epoxy resin (DGEBF for short) molecular structural formula

Molecular structural formula of bis-o-cresol fluorene epoxy resin (DGEMBF for short)

Molecular structural formula of bis-di-o-cresol fluorene epoxy resin (DGEDMFF for short)

The modified epoxy resin is bisphenol A type epoxy resin (product production providing company and brand may be DER-383 of Dow, DER-331 of Dow, E-51 of Baling, CYD-128 of Baling, etc.), bisphenol F type epoxy resin (product production providing company and brand may be EPON-862 of Hansen Miji, NPEF-170 of Nanya epoxy resin (Kunshan), etc.), alicyclic epoxy resin (product production providing company and brand may be TDE-85 of Hubei Xinrunder chemical Co., Ltd., CEL2021P of DAICEL, UVR-6110 of DOW, CY-179 of Hunan, etc.), glycidyl amine type epoxy resin (product production providing company and brand may be AG: Shanghai synthetic resin research institute, etc.), (product production providing company and brand may be DE-383 of Shanghai, etc.), Biphenyl type epoxy resin (product manufacturing and providing enterprises and brands may be BPNE3501LL/9781 of Jiangshan materials science and technology Limited in Hunan), phenol type novolac epoxy resin (product manufacturing and providing enterprises and brands may be NPPN-638S of Nanasia epoxy resin (Kunshan) Limited, EPON 154 of Hansen Mitsukuji materials group in USA, DPNH9501 of Jiangshan materials science and technology Limited in Hunan, etc.), o-cresol type novolac epoxy resin (product manufacturing and providing enterprises and brands may be N-XP of Japan ink corporation, CNE202 of Taiwan Changchun resin factory, NPCN-704/703 of Nanasia epoxy resin (Kunshan) Limited, etc.), bisphenol A novolac type epoxy resin (product manufacturing and providing enterprises and brands may be BNE200 of Taiwan Changchun resin factory, F-51 of Shanghai Satsu chemical technology Limited in China, etc.), bisphenol A novolac type epoxy resin (product manufacturing and brands may be BNE200 of Taiwan China, F-51 of Shanghai Katsu technology Limited in China, etc.), One or a mixture of two or more of resorcinol type epoxy resin (product production providing company and brand may be ERISYS RDGE-H of Jia Dida chemical Co., Ltd., YF-554 of Guangzhou Yifu chemical materials Co., Ltd.), epoxy resin of dicyclopentadiene or dicycladiene and phenol-formaldehyde polycondensation resin (product production providing company and brand may be NPNE1501 of Hunan Jiasheng Material science and technology Co., Ltd., DNE260 of Jinninghuaka resin Co., Ltd., DNE280A75 of Tiangao New technology Co., Ltd.), isocyanate modified epoxy resin (product production providing company and brand may be A-IME AER4152 of Jiangsai chemical Co., Ltd., SEB-350 of SHIN-A T & C, etc.), and hydantoin type epoxy resin (product production providing company and brand may be Whitman electronic material Co., Whitman, HY-070, etc.) An agent;

the curing agent is a mixture of two or more of 4, 4-diaminodiphenylmethane, 4-diaminodiphenylsulfone and diamine fluorene, wherein the chemical structural formula of the diamine fluorene is shown as the following formula:

the filler is one or a mixture of more than two of aluminum hydroxide, aluminum oxide, boehmite, magnesium hydroxide, silicon micropowder, montmorillonite, kaolin, fumed silica, silicon dioxide micropowder, graphene, hydrotalcite and talcum powder;

the accelerant is one or a mixture of more than two of 2-methylimidazole, 2-ethyl-4-methylimidazole, N-dimethylbenzylamine, boron trifluoride ethylamine, triethylamine, hexamethyltetramine and aluminum acetylacetonate;

the solvent is one or a mixture of more than two of toluene, xylene, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, propylene glycol methyl ether, methyl ethyl ketone, cyclohexanone, methyl acetate, butanone, acetone, N-dimethylformamide and ethanol.

The invention comprises the following steps: in the high temperature resistant epoxy alkali-free glass fiber-fabric prepreg: the weight percentage of the semi-cured material is 15-55 percent, and the weight percentage of the alkali-free glass fiber-fabric is 45-85 percent.

The invention comprises the following steps: the high temperature resistant epoxy glass fiber insulating layer and the molded part (namely the prepared composite material) have the mechanical strength of more than 225MPa at the temperature of 230 ℃, the bending strength of more than 225MPa at the temperature of 121 ℃ for 96 hours in the environment with the humidity of 100 percent, the shear strength of more than or equal to 15MPa, and the water absorption of less than or equal to 2 percent.

Another aspect of the invention is: a preparation method of a high temperature resistant epoxy glass fiber insulating layer and a molded part is characterized by comprising the following steps:

a. preparing a high-temperature-resistant epoxy adhesive:

(a) preparing materials: taking raw materials of the components according to the weight ratio of 12-45 parts of epoxy resin, 5-35 parts of modified epoxy resin, 6-34 parts of curing agent, 1-61 parts of filler, 9.5-201 parts of solvent and 0.01-0.18 part of accelerator;

bisphenol fluorene epoxy resin (DGEBF for short) molecular structural formula

the solvent is one or a mixture of more than two of toluene, xylene, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, propylene glycol methyl ether, methyl ethyl ketone, cyclohexanone, methyl acetate, butanone, acetone, N-dimethylformamide and ethanol;

(b) adding the epoxy resin, the modified epoxy resin and the filler in the formula amount in the step (a) into a glue preparation tank at room temperature, stirring for 0.5-2 hours at the temperature of 55-115 ℃, adding a curing agent, stirring for 1-4 hours at the temperature of 100-145 ℃, adding a solvent, fully and uniformly dispersing, adding an accelerator to adjust the forming time of the glue solution, sampling, testing the forming time of the glue solution by using a knife method, and completing preparation of the high-temperature-resistant epoxy adhesive when the forming time is 440-530 seconds under the condition of a 210 ℃ hot plate to obtain the high-temperature-resistant epoxy adhesive;

b. preparing high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg:

b, dipping the alkali-free glass fiber-fabric into the high-temperature-resistant epoxy adhesive in the step a through a gluing machine (which can be a horizontal or vertical gluing machine), and baking the high-temperature-resistant epoxy adhesive through a baking channel of the gluing machine, wherein the baking channel of the gluing machine is 24m long and is divided into 4 sections and 6m in each section, the baking temperature range is 70-175 ℃, the speed of the gluing machine is 8-21 m/min, and the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg is prepared after baking;

c. and (3) pressing the high-temperature-resistant epoxy glass fiber insulating layer and a molded part:

cutting the high temperature resistant epoxy alkali-free glass fiber-fabric prepreg prepared in the step b into a required shape and size according to the drawing (process) requirements of the high temperature resistant epoxy glass fiber insulating layer and a molded part, placing one or more layers of the cut high temperature resistant epoxy alkali-free glass fiber-fabric prepreg on a smooth stainless steel mold (coated with a release agent on two surfaces), sending the high temperature resistant epoxy alkali-free glass fiber-fabric prepreg into a hot press (a common hot press or a vacuum hot press), controlling the temperature to be between 130 and 250 ℃ and the pressure to be between 5 and 30MPa for hot press molding, and determining the hot press molding time to be between 0.5 and 30 hours according to the thickness of a molded structural part to be between 0.2 and 150mm, thus obtaining the high temperature resistant epoxy glass fiber insulating layer and the molded part.

In another aspect of the invention: the high temperature resistant epoxy alkali-free glass fiber-fabric prepreg prepared in the step b is a high temperature resistant epoxy alkali-free glass fiber-fabric prepreg with a semi-cured product on the alkali-free glass fiber-fabric, wherein the high temperature resistant epoxy alkali-free glass fiber-fabric prepreg comprises the following components in percentage by weight: the weight percentage of the semi-cured material is 15-55 percent, and the weight percentage of the alkali-free glass fiber-fabric is 45-85 percent.

In another aspect of the invention: the shape of the stainless steel mold in step c can be a flat plate shape, a U-shaped or similar shape, and other special shapes.

In another aspect of the invention: the high temperature resistant epoxy glass fiber insulation layer and the molded part prepared in the step c have the mechanical strength of more than 225MPa at the temperature of 230 ℃, the bending strength of more than 225MPa at the temperature of 121 ℃ for 96 hours in the environment with the humidity of 100 percent, the shear strength of more than or equal to 15MPa and the water absorption of less than or equal to 2 percent.

Compared with the prior art, the invention has the following characteristics and beneficial effects:

(1) by adopting the invention, the matrix resin and all raw materials are long-term high-temperature resistant products, and the requirement of high mechanical strength can be strictly met when the resin is used at the temperature of more than 230 ℃ for a long time; the bending strength is 585-618 MPa in a normal state, the bending strength is 378-393 MPa at 230 ℃, especially the strength retention rate is higher at high temperature and high humidity, the bending strength is 378-393 MPa (the retention rate is more than or equal to 60%) at 230 ℃, the bending strength is 446-479 MPa (the retention rate is more than or equal to 75%) after 96h at 121 ℃ and 100% humidity, and the shear strength is 29-35 MPa; the technical problem that the bending strength retention rate of the epoxy carbon fiber composite material at the temperature of over 230 ℃ is more than or equal to 50 percent due to the self strength difference of the epoxy carbon fiber composite material is solved;

(2) the invention adopts the synergistic technology of the modified resin and the epoxy resin, so that the resin system of the modified resin and the epoxy resin simultaneously meets better toughness on the basis of resisting the use temperature of more than 230 ℃ for a long time, and particularly solves the technical problem that the bending strength retention rate is more than 75 percent at the temperature of 121 ℃ and the humidity of 100 percent after 96 hours, which cannot be achieved by the performance of the resin, in the aspects of moisture and heat resistance, and also greatly reduces the production cost of the product;

(3) by adopting the invention, the preparation process is simple, the operation is easy, the product quality is excellent, and the cost is reduced; the high-temperature-resistance epoxy glass fiber insulating layer and the die-pressed part prepared by the invention are particularly suitable for the insulating layer and the die-pressed part for high-voltage/extra-high voltage power transmission and transformation, which have higher requirements on temperature resistance and need to be used for a long time in high-temperature and high-humidity environments, and the fields of high-voltage motors, large-scale generating sets, power transformers and the like, and have the advantages of reliable use and strong practicability.

Detailed Description

The following examples are intended to further illustrate the present invention and should not be construed as limiting the scope of the invention, which is intended to be covered by the claims appended hereto.

In the following examples, the amounts of each ingredient component material indicated as "parts" are parts by weight (e.g., both grams or kilograms).

Preparation of first part high-temperature-resistant epoxy adhesive

Example 1-1:

respectively adding 35 parts of bisphenol fluorene epoxy resin (DGEBF for short), 15 parts of alicyclic epoxy resin, 11 parts of bisphenol A type epoxy resin and 45 parts of talcum powder into a glue preparation tank at room temperature, stirring for 0.75 hour at the temperature of 85 ℃, adding 11 parts of curing agent 4, 4-diaminodiphenyl sulfone and 16 parts of diamine fluorene, stirring for 1 hour at the temperature of 100 ℃, adding 156 parts of N, N-dimethylformamide to fully and uniformly disperse the N, N-dimethylformamide, adding 0.11 part of accelerator 2-methylimidazole to adjust the forming time of glue solution, sampling, testing the forming time of the glue solution by a knife method (210 ℃ hot plate) for 467 seconds, and finishing the preparation of the glue solution.

Examples 1 to 2:

at room temperature, 45 parts of bis-o-cresol fluorene epoxy resin (DGEMBF for short), 19 parts of glycidyl amine epoxy resin, 12 parts of bisphenol A epoxy resin and 51 parts of silicon powder are respectively added into a glue preparation tank, stirred for 0.5 hour at the temperature of 75 ℃, then added with 5 parts of curing agent 4, 4-diaminodiphenylmethane and 29 parts of diamine fluorene, stirred for 2.5 hours at the temperature of 115 ℃, added with 181 parts of xylene to be fully and uniformly dispersed, then added with 0.13 part of accelerant 2-ethyl-4-methylimidazole to adjust the molding time of glue solution, sampled, tested by a knife method for 461 seconds at the molding time (210 ℃ hot plate), and the glue solution is prepared.

Examples 1 to 3:

at room temperature, 40 parts of bis-o-cresol fluorene epoxy resin (DGEDMFF for short), 16 parts of biphenyl epoxy resin, 9 parts of glycidyl amine epoxy resin and 32 parts of montmorillonite are respectively added into a glue preparation tank, after stirring for 0.75 hour at the temperature of 55 ℃,4 parts of curing agent, 4-diaminodiphenylmethane and 14 parts of bisaminofluorene are added, stirring for 1.25 hours at the temperature of 125 ℃, 41 parts of butanone is added, after the materials are fully and uniformly dispersed, 0.054 part of accelerator boron trifluoride ethylamine fluoride is added to adjust the forming time of glue solution, sampling is carried out, the forming time of the glue solution (210 ℃ hot plate) is tested by a knife method for 515 seconds, and the glue solution is prepared.

Examples 1 to 4:

at room temperature, 12 parts of bis-o-cresol fluorene epoxy resin (DGEMBF for short), 7 parts of epoxy resin of dicyclopentadiene or dicyclo-diene and phenolic aldehyde polycondensation resin, 2 parts of o-cresol novolac epoxy resin and 1 part of fumed silica are respectively added into a glue preparation tank, stirred for 1.25 hours at the temperature of 85 ℃, added with 4 parts of curing agent, 4-diaminodiphenyl sulfone and 2 parts of diamine fluorene, stirred for 1.25 hours at the temperature of 135 ℃, added with 15 parts of methyl acetate, fully dispersed and uniform, added with 0.01 part of accelerant aluminum acetylacetonate to adjust the forming time of the glue solution, sampled, tested by a knife method for the forming time (210 ℃) of the glue solution for 526 seconds, and the glue solution is prepared.

Examples 1 to 5:

at room temperature, 27 parts of bis-o-cresol fluorene epoxy resin (DGEDMBF for short), 21 parts of isocyanate modified epoxy resin, 6 parts of bisphenol A novolac epoxy resin and 29 parts of silica micropowder are respectively added into a glue preparation tank, after stirring for 1 hour at the temperature of 90 ℃, 12 parts of curing agent 4, 4-diaminodiphenyl sulfone and 10 parts of diamine fluorene are added, stirring is carried out for 3 hours at the temperature of 115 ℃, 61 parts of toluene is added, after the toluene is fully and uniformly dispersed, 0.075 part of accelerant N, N-dimethylbenzylamine is added to adjust the forming time of glue solution, sampling is carried out, the forming time of the glue solution (210 ℃ hot plate) is tested by a knife method for 493 seconds, and the glue solution is prepared.

Examples 1 to 6:

at room temperature, 19 parts of bis-o-cresol fluorene epoxy resin (DGEDMFF for short), 3 parts of biphenyl epoxy resin, 2 parts of epoxy resin of dicyclopentadiene or dicyclo diene and phenolic aldehyde polycondensation resin and 12 parts of graphene are respectively added into a glue preparation tank, stirred for 0.75 hour at the temperature of 105 ℃, added with 2 parts of curing agent 4, 4-diaminodiphenylmethane and 4 parts of diamine fluorene, stirred for 1 hour at the temperature of 125 ℃, added with 9.5 parts of acetone to be fully and uniformly dispersed, added with 0.012 parts of accelerator boron trifluoride ethylamine trifluoride to adjust the forming time of the glue solution, sampled, tested by a knife method for the forming time (210 ℃ hot plate) of the glue solution for 530 seconds, and the glue solution is prepared.

Examples 1 to 7:

respectively adding 14 parts of bis-o-cresol fluorene epoxy resin (DGEMBF), 14 parts of bisphenol fluorene epoxy resin (DGEBF), 10 parts of phenol novolac epoxy resin, 12 parts of biphenyl epoxy resin and 38 parts of silicon micro powder into a glue preparation tank at room temperature, stirring for 1.25 hours at the temperature of 100 ℃, adding 12 parts of curing agent 4, 4-diaminodiphenyl sulfone and 4 parts of bisamine fluorene, stirring for 1.75 hours at the temperature of 120 ℃, adding 104 parts of cyclohexanone, fully dispersing uniformly, adding 0.047 part of accelerator hexamethyltetramine, adjusting the forming time of the glue solution, sampling, testing the forming time of the glue solution (210 ℃ hot plate) for 521 seconds by using a knife method, and finishing the preparation of the glue solution.

Examples 1 to 8:

respectively adding 21 parts of bis-o-cresol fluorene epoxy resin (DGEMBF), 2 parts of bisphenol fluorene epoxy resin (DGEBF), 7 parts of alicyclic epoxy resin, 8 parts of bisphenol A novolac epoxy resin, 15 parts of talcum powder and 4 parts of boehmite into a glue preparation tank at room temperature, stirring for 1.25 hours at the temperature of 100 ℃, adding 5 parts of curing agent 4, 4-diaminodiphenyl sulfone and 11 parts of diamine fluorene, stirring for 2.5 hours at the temperature of 145 ℃, adding 30 parts of toluene and 27 parts of alcohol, fully dispersing uniformly, adding 0.023 part of accelerator 2-ethyl-4-methylimidazole to adjust the forming time of the glue solution, sampling, testing the forming time of the glue solution by using a knife method (210 ℃ hot plate) for 520 seconds, and finishing the preparation of the glue solution.

Examples 1 to 9:

respectively adding 16 parts of bis-o-cresol fluorene epoxy resin (DGEDMFF for short), 17 parts of bisphenol fluorene epoxy resin (DGEBF for short), 9 parts of glycidylamine epoxy resin, 9 parts of resorcinol epoxy resin, 17 parts of aluminum hydroxide and 17 parts of montmorillonite into a glue preparation tank at room temperature, stirring for 1.5 hours at the temperature of 90 ℃, adding 3 parts of curing agent 4, 4-diaminodiphenylmethane and 10 parts of diamine fluorene, stirring for 1.5 hours at the temperature of 125 ℃, adding 82 parts of xylene and 53 parts of acetone, fully and uniformly dispersing, adding 0.047 part of accelerant 2-methylimidazole to adjust the molding time of the glue solution, sampling, testing the molding time of the glue solution by a knife method (210 ℃ hot plate) for 524 seconds, and finishing the preparation of the glue solution.

Examples 1 to 10:

respectively adding 19 parts of bis-o-cresol fluorene epoxy resin (DGEDMFF for short), 19 parts of bis-o-cresol fluorene epoxy resin (DGEMBF for short), 15 parts of bisphenol F epoxy resin, 6 parts of alicyclic epoxy resin, 12 parts of kaolin and 30 parts of silicon dioxide micropowder into a glue preparation tank at room temperature, stirring for 1.5 hours at the temperature of 65 ℃, adding 7 parts of curing agent 4, 4-diaminodiphenylmethane and 9 parts of diamine fluorene, stirring for 4 hours at the temperature of 105 ℃, adding 47 parts of ethylene glycol ethyl ether acetate and 38 parts of xylene, fully and uniformly dispersing, adding 0.09 part of accelerator 2-ethyl-4-methylimidazole, adjusting the molding time of the glue solution, sampling, testing the molding time of the glue solution by using a knife method (210 ℃) for 496 seconds, and preparing the glue solution by a hot plate.

Examples 1 to 11:

at room temperature, 20 parts of bis-o-cresol fluorene epoxy resin (DGEDMFF for short), 12 parts of bisphenol fluorene epoxy resin (DGEBF for short), 2 parts of glycidylamine epoxy resin, 6 parts of o-cresol novolac epoxy resin, 12 parts of alumina and 15 parts of silica powder are respectively added into a glue preparation tank, after stirring for 1.75 hours at the temperature of 70 ℃, 12 parts of curing agent 4, 4-diamino diphenyl sulfone and 12 parts of diamine fluorene are added, stirring is carried out for 3.5 hours at the temperature of 115 ℃, 11 parts of toluene and 16 parts of propylene glycol methyl ether are added, after the materials are fully dispersed uniformly, 0.038 part of accelerant 2-methylimidazole is added to adjust the forming time of the glue solution, sampling is carried out, the forming time (210 ℃) of the glue solution is tested by using a knife method for 522 seconds, and the glue solution is prepared by a hot plate.

Examples 1 to 12:

at room temperature, 5 parts of bis-o-cresol fluorene epoxy resin (DGEMBF for short), 19 parts of bisphenol fluorene epoxy resin (DGEBF for short), 12 parts of glycidyl amine epoxy resin, 7 parts of resorcinol epoxy resin, 5 parts of magnesium hydroxide and 18 parts of boehmite are respectively added into a glue preparation tank, after stirring for 1 hour at the temperature of 90 ℃, 2 parts of curing agent 4, 4-diaminodiphenyl sulfone and 11 parts of diamine fluorene are added, stirring is carried out for 2.25 hours at the temperature of 110 ℃, 18 parts of methyl ethyl ketone and 35 parts of alcohol are added, after the materials are fully dispersed uniformly, 0.032 part of accelerant aluminum acetylacetonate is added to adjust the forming time of the glue solution, sampling is carried out, the forming time (210 ℃ hot plate) of the glue solution is tested by using a knife method for 518 seconds, and the preparation is finished.

Examples 1 to 13:

respectively adding 18 parts of bis-o-cresol fluorene epoxy resin (DGEDMFF for short), 12 parts of bis-o-cresol fluorene epoxy resin (DGEMBF for short), 6 parts of alicyclic epoxy resin, 15 parts of resorcinol epoxy resin, 14 parts of graphene and 22 parts of montmorillonite into a glue preparation tank at room temperature, stirring at 85 ℃ for 1.5 hours, adding 5 parts of curing agent 4, 4-diaminodiphenylmethane and 10 parts of diamine fluorene, stirring at 120 ℃ for 3 hours, adding 52 parts of N, N-dimethylformamide and 40 parts of alcohol, fully dispersing uniformly, adding 0.049 part of accelerant 2-methylimidazole to adjust the forming time of the glue solution, sampling, testing the forming time of the glue solution by using a knife method (210 ℃) for 506 seconds, and finishing the preparation of the glue solution.

Examples 1 to 14:

at room temperature, 22 parts of bis-o-cresol fluorene epoxy resin (DGEDMFF for short), 12 parts of bisphenol fluorene epoxy resin (DGEBF for short), 5 parts of glycidyl amine epoxy resin, 3 parts of bisphenol A epoxy resin, 4 parts of o-cresol novolac epoxy resin, 5 parts of kaolin, 12 parts of magnesium hydroxide and 12 parts of talcum powder are respectively added into a glue preparation tank, stirred for 1.75 hours at the temperature of 85 ℃, added with 12 parts of curing agent 4, 4-diaminodiphenyl sulfone and 7 parts of diamine fluorene, stirred for 3.25 hours at the temperature of 115 ℃, added with 11 parts of ethylene glycol dimethyl ether and 8 parts of butanone to be fully and uniformly dispersed, added with 0.028 part of accelerant 2-ethyl-4-methylimidazole to adjust the molding time of the glue solution, sampled, and the molding time (210 ℃ hot plate) of the glue solution is tested by a knife method for 503 seconds, namely the glue solution is prepared.

Examples 1 to 15:

respectively adding 16 parts of bisphenol fluorene epoxy resin (DGEBF for short), 20 parts of bis-o-cresol fluorene epoxy resin (DGEDMFF for short), 2 parts of glycidylamine epoxy resin, 6 parts of isocyanate modified epoxy resin, 4 parts of biphenyl epoxy resin, 4 parts of alumina, 8 parts of hydrotalcite and 21 parts of silica micropowder into a glue preparation tank at room temperature, stirring at 90 ℃ for 2 hours, adding 4 parts of curing agent, 4-diaminodiphenylmethane and 13 parts of bisamine fluorene, stirring at 125 ℃ for 2.5 hours, adding 52 parts of propylene glycol methyl ether and 21 parts of methyl acetate, fully and uniformly dispersing, adding 0.033 part of boron trifluoride serving as an accelerator to adjust the forming time of a knife glue solution, sampling, testing the forming time of the glue solution by using a method (210 ℃ hot plate) for seconds, and completing the preparation of the glue solution.

Examples 1 to 16:

at room temperature, 17 parts of bis-o-cresol fluorene epoxy resin (DGEDMBF for short), 21 parts of bis-o-cresol fluorene epoxy resin (DGEMBF for short), 15 parts of glycidyl amine type epoxy resin, 4 parts of bisphenol A type epoxy resin, 4 parts of alicyclic epoxy resin, 8 parts of kaolin, 19 parts of aluminum hydroxide and 21 parts of fumed silica are respectively added into a glue preparation tank, stirred for 1.5 hours at the temperature of 75 ℃, added with 12 parts of curing agent 4, 4-diaminodiphenyl sulfone and 8 parts of diamine fluorene, stirred for 3.5 hours at the temperature of 105 ℃, added with 65 parts of ethylene glycol dimethyl ether and 27 parts of acetone to be fully and uniformly dispersed, added with 0.09 part of accelerator aluminum acetylacetonate to adjust the molding time of the glue solution, sampled, and tested by a method for molding time (210 ℃ hot plate) seconds, 463 to finish the glue solution preparation.

Examples 1 to 17:

at room temperature, 22 parts of bis-o-cresol fluorene epoxy resin (DGEDMFF for short), 15 parts of bis-o-cresol fluorene epoxy resin (DGEMBF for short), 5 parts of bisphenol fluorene epoxy resin (DGEBF for short), 12 parts of alicyclic epoxy resin, 5 parts of bisphenol A epoxy resin, 18 parts of epoxy resin of dicyclopentadiene or dicyclic diene and phenolic aldehyde polycondensation resin, 21 parts of boehmite, 7 parts of hydrotalcite and 29 parts of silicon dioxide micro powder are respectively added into a glue preparation tank, after stirring for 1.25 hours at the temperature of 105 ℃, 12 parts of curing agent 4, 4-diaminodiphenylmethane, 14 parts of diamine fluorene and 6 parts of 4, 4-diaminodiphenylsulfone are added, stirring is carried out for 2.25 hours at the temperature of 125 ℃, 153 parts of ethylene glycol ethyl ether acetate and 48 parts of N, N-dimethylformamide are added, after full dispersion and uniform dispersion, 0.015 part of accelerant 2-ethyl-4-methylimidazole is added to adjust the forming time of the glue solution, sampling, and testing the molding time (210 ℃ hot plate) 483 seconds of the glue solution by using a knife method to finish the preparation of the glue solution.

Examples 1 to 18:

respectively adding 21 parts of bis-o-cresol fluorene epoxy resin (DGEDMFF for short), 12 parts of bis-o-cresol fluorene epoxy resin (DGEMBF for short), 11 parts of bisphenol fluorene epoxy resin (DGEBF for short), 6 parts of glycidylamine epoxy resin, 10 parts of bisphenol F epoxy resin, 12 parts of isocyanate modified epoxy resin, 11 parts of kaolin, 19 parts of magnesium hydroxide and 24 parts of talcum powder into a glue preparation tank at room temperature, stirring for 1.45 hours at the temperature of 75 ℃, adding 3 parts of curing agent 4, 4-diaminodiphenylmethane, 17 parts of diamine fluorene and 12 parts of 4, 4-diaminodiphenyl sulfone, stirring at 105 deg.C for 2.5 hr, adding 81 parts of cyclohexanone and 102 parts of toluene, dispersing, adding 0.18 part of triethylamine as an accelerator to adjust the forming time of the glue solution, sampling, and testing the forming time (210 ℃ hot plate) of the glue solution for 440 seconds by using a knife method to finish the preparation of the glue solution.

Examples 1 to 19:

respectively adding 12 parts of bis-o-cresol fluorene epoxy resin (DGEDMFF for short), 16 parts of bis-o-cresol fluorene epoxy resin (DGEMBF for short), 2 parts of bisphenol fluorene epoxy resin (DGEBF for short), 15 parts of epoxy resin of dicyclopentadiene or dicyclic diene and phenolic aldehyde polycondensation resin, 12 parts of hydantoin epoxy resin, 12 parts of alicyclic epoxy resin, 6 parts of glycidyl amine type epoxy resin, 34 parts of fumed silica, 4 parts of boehmite and 23 parts of montmorillonite into a glue preparation tank at room temperature, stirring at 90 ℃ for 2 hours, adding 5 parts of curing agent 4, 4-diaminodiphenylmethane, 21 parts of diamine fluorene and 5 parts of 4, 4-diaminodiphenylsulfone, stirring at 125 ℃ for 3.25 hours, adding 15 parts of methyl ethyl ketone and 57 parts of butanone to fully disperse the materials uniformly, adding 0.15 part of accelerant aluminum acetylacetonate to adjust the forming time of the glue solution, sampling, testing the forming time by a hot plate method (210 ℃) for 472 seconds, and finishing the preparation of the glue solution.

Examples 1 to 20:

respectively adding 18 parts of bis-o-cresol fluorene epoxy resin (DGEDMFF for short), 10 parts of bis-o-cresol fluorene epoxy resin (DGEMBF for short), 11 parts of bisphenol fluorene epoxy resin (DGEBF for short), 11 parts of epoxy resin of dicyclopentadiene or dicyclic diene and phenolic aldehyde polycondensation resin, 9 parts of biphenyl epoxy resin, 5 parts of o-cresol novolac epoxy resin, 2 parts of glycidyl amine epoxy resin, 15 parts of graphene, 21 parts of montmorillonite and 14 parts of boehmite into a glue preparation tank at room temperature, stirring at 85 ℃ for 1.75 hours, adding 11 parts of curing agent 4, 4-diaminodiphenylmethane, 15 parts of bisaminofluorene and 2 parts of 4, 4-diaminodiphenylsulfone, stirring at 135 ℃ for 2.75 hours, adding 46 parts of xylene, 35 parts of ethylene glycol dimethyl ether and 31 parts of acetone, fully dispersing uniformly, adding 0.11 part of accelerator 2-ethyl-4-methylimidazole to adjust the molding time of the glue solution, sampling, and testing the molding time (210 ℃ hot plate) of the glue solution for 475 seconds by using a knife method to finish the preparation of the glue solution.

Examples 1 to 21:

respectively adding 15 parts of bis-o-cresol fluorene epoxy resin (DGEDMFF for short), 15 parts of bis-o-cresol fluorene epoxy resin (DGEMBF for short), 13 parts of bisphenol fluorene epoxy resin (DGEBF for short), 8 parts of bisphenol A novolac epoxy resin, 13 parts of isocyanate modified epoxy resin, 8 parts of alicyclic epoxy resin, 3 parts of glycidyl amine epoxy resin, 9 parts of magnesium hydroxide, 16 parts of aluminum oxide and 22 parts of silicon micropowder into a glue preparation tank at room temperature, stirring at 105 ℃ for 2 hours, adding 12 parts of curing agent 4, 4-diaminodiphenylmethane, 13 parts of bisamine fluorene and 9 parts of 4, 4-diaminodiphenylsulfone, stirring at 125 ℃ for 2.75 hours, adding 86 parts of acetone, 65 parts of N, N-dimethylformamide and 46 parts of alcohol, fully dispersing uniformly, adding 0.18 part of accelerant 2-methylimidazole to adjust the forming time of glue solution, sampling, and testing the molding time (210 ℃ hot plate) of the glue solution by using a knife method for 452 seconds to finish the preparation of the glue solution.

Preparation of second part high temperature resistant epoxy alkali-free glass fiber-fabric prepreg

1. Basic processes of examples 2-1 to 2-21:

a. selecting a high-temperature-resistant epoxy adhesive:

the first part of the high temperature resistant epoxy adhesive prepared in the embodiments 1-1 to 1-21 is selected correspondingly in the embodiments 2-1 to 2-21;

b. preparation of high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg

Dipping glass fiber-fabric (alkali-free glass fiber cloth, 7628 electronic grade alkali-free glass fiber cloth, high-strength alkali-free glass fiber cloth, alkali-free glass fiber checkered cloth and glass fiber smoldering treatment cloth) in a horizontal or vertical gluing machine to obtain the high-temperature-resistant epoxy adhesive in the step a, baking the high-temperature-resistant epoxy adhesive through a baking channel of the gluing machine, wherein the baking channel of the gluing machine is 24m long and is divided into 4 sections and 6m each section, the baking temperature range is 70-175 ℃, and the speed of the gluing machine is 8-21 m/min, so that the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg is prepared; the indexes of the fiber-fabric prepreg are as follows: the fluidity is 19 mm-28 mm, the content of soluble resin is more than or equal to 95 percent, and the volatile matter is less than or equal to 2 percent.

2. The specific process parameters and test results of examples 2-1 to 2-21 are shown in Table 1 below:

table 1: the preparation process parameters of the high temperature resistant epoxy alkali-free glass fiber-fabric prepreg are as follows:

preparation of third part high temperature resistant epoxy glass fiber insulating layer and mould pressing part

1. Basic Process for examples 3-1 to 3-21

a. High-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg

The second part of the high temperature resistant epoxy alkali-free glass fiber-fabric prepreg prepared in the examples 2-1 to 2-21 is selected correspondingly in the examples 3-1 to 3-21 respectively;

b. and (3) pressing the high-temperature-resistant epoxy glass fiber insulating layer and a molded part:

taking a high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg cut into a required shape and size according to the process requirements of a high-temperature-resistant epoxy glass fiber insulating layer and a molded part, and placing the prepreg paving layer on a smooth stainless steel mold coated with a release agent on two sides, wherein the mold shape comprises: and (3) feeding the flat plate, the U-shaped or the similar shape and other special shapes into a common hot press or a vacuum hot press with a hot plate, carrying out hot press molding under the conditions that the temperature is controlled to be 130-250 ℃ and the pressure is controlled to be 5-30 MPa, and determining the hot press molding time to be 0.5-30 h according to the thickness of a molded structural part to obtain the high-temperature-resistant epoxy glass fiber insulating layer and the molded part.

2. Specific process parameters of examples 2-1 to 2-21 and technical performance test results of the high temperature resistant epoxy glass fiber insulation layer and the molded part product are respectively shown in the following tables 2 and 3:

table 2: the pressing technological parameters of the high temperature resistant epoxy glass fiber insulating layer and the molded part are as follows:

table 3: the technical performance test results of the high temperature resistant epoxy glass fiber insulating layer and the molded part are as follows:

note: (1) in the above table, the test values are the test results at room temperature and 50% ± 5% humidity, except that the test temperature and humidity of the bending strength are indicated.

(2) The technical performance test method comprises the following steps:

1) bending strength, shear strength: the measurement was carried out according to the method specified in GB/T9341-2008.

2) Water absorption: the measurement was carried out according to the method defined in GB/T1034-2008.

Example 4:

a high temperature resistant epoxy glass fiber insulating layer, mould pressing finished piece, this insulating layer, mould pressing structural part are 2 layers of high temperature resistant epoxy alkali-free glass fiber-fabric prepreg that overlap and make composite material after the hot briquetting;

the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg is an alkali-free glass fiber-fabric impregnating material which is formed by impregnating alkali-free glass fiber-fabric with a high-temperature-resistant epoxy adhesive and then baking (removing part of solvent in the alkali-free glass fiber-fabric), wherein a semi-cured material is arranged on the alkali-free glass fiber-fabric, and the impregnating material comprises the following components in percentage by weight: the weight percentage of the semi-cured product is 32 percent, and the weight percentage of the alkali-free glass fiber-fabric is 68 percent;

the high-temperature-resistant epoxy adhesive comprises the following components in parts by weight: 12 parts of bis-o-cresol fluorene epoxy resin (DGEMBF for short), 7 parts of epoxy resin of dicyclopentadiene or dicycladiene and phenolic aldehyde polycondensation resin, 2 parts of bisphenol A type epoxy resin, 1 part of fumed silica, 4 parts of 4, 4-diaminodiphenyl sulfone, 2 parts of diamine fluorene, 15 parts of methyl acetate and 0.01 part of aluminum acetylacetonate.

Example 5:

a high temperature resistant epoxy glass fiber insulating layer, mould pressing finished piece, the insulating layer, mould pressing structural part are the composite material made after 50 layers of high temperature resistant epoxy alkali-free glass fiber-fabric prepreg that overlap is hot-pressed;

the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg is an alkali-free glass fiber-fabric impregnating material which is formed by impregnating alkali-free glass fiber-fabric with a high-temperature-resistant epoxy adhesive and then baking (removing part of solvent in the alkali-free glass fiber-fabric), wherein a semi-cured material is arranged on the alkali-free glass fiber-fabric, and the impregnating material comprises the following components in percentage by weight: the weight percentage of the semi-cured product is 15 percent, and the weight percentage of the alkali-free glass fiber-fabric is 85 percent;

the high-temperature-resistant epoxy adhesive comprises the following components in parts by weight: 27 parts of bis-o-cresol fluorene epoxy resin (DGEDMFF for short), 21 parts of isocyanate modified epoxy resin, 6 parts of bisphenol A type epoxy resin, 29 parts of silica micropowder, 12 parts of 4, 4-diaminodiphenyl sulfone, 10 parts of diamine fluorene, 61 parts of toluene and 0.075 part of N, N-dimethylbenzylamine.

Example 6:

a high temperature resistant epoxy glass fiber insulating layer, mould pressing finished piece, the insulating layer, mould pressing structural part are the composite material made after 300 layers of high temperature resistant epoxy alkali-free glass fiber-fabric prepreg that overlap is hot-pressed;

the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg is an alkali-free glass fiber-fabric impregnating material which is formed by impregnating alkali-free glass fiber-fabric with a high-temperature-resistant epoxy adhesive and then baking (removing part of solvent in the alkali-free glass fiber-fabric), wherein a semi-cured material is arranged on the alkali-free glass fiber-fabric, and the impregnating material comprises the following components in percentage by weight: the weight percentage of the semi-cured product is 55 percent, and the weight percentage of the alkali-free glass fiber-fabric is 45 percent;

the high-temperature-resistant epoxy adhesive comprises the following components in parts by weight: 19 parts of bis-di-o-cresol fluorene epoxy resin (DGEDMFF for short), 3 parts of biphenyl epoxy resin, 2 parts of bisphenol A epoxy resin, 12 parts of graphene, 2 parts of 4, 4-diaminodiphenylmethane, 4 parts of bisamine fluorene, 9.5 parts of acetone and 0.012 part of boron trifluoride ethylamine.

Example 7:

a high temperature resistant epoxy glass fiber insulating layer, mould pressing finished piece, the insulating layer, mould pressing structural part are the composite material made after 200 layers of high temperature resistant epoxy alkali-free glass fiber-fabric prepreg that overlap is hot-pressed;

the high-temperature-resistant epoxy adhesive comprises the following components in parts by weight: 14 parts of bis-o-cresol fluorene epoxy resin (DGEMBF for short), 14 parts of bisphenol fluorene epoxy resin (DGEBF for short), 10 parts of phenol novolac epoxy resin, 12 parts of bisphenol A epoxy resin, 38 parts of silica powder, 12 parts of 4, 4-diaminodiphenyl sulfone, 4 parts of diamine fluorene, 104 parts of cyclohexanone and 0.047 part of hexamethyltetramine.

Examples 8 to 14:

a high temperature resistant epoxy glass fiber insulating layer, mould pressing finished piece, the insulating layer, mould pressing structural part are one or more layers of high temperature resistant epoxy alkali-free glass fiber-fabric prepreg that overlap and make the composite material after the hot-pressing shaping;

the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg is an alkali-free glass fiber-fabric impregnating material which is formed by impregnating alkali-free glass fiber-fabric with a high-temperature-resistant epoxy adhesive and then baking the impregnated material, wherein the impregnating material comprises the following components in percentage by weight: the weight percentage of the semi-cured material is 15-55 percent, and the weight percentage of the alkali-free glass fiber-fabric is 45-85 percent;

the high-temperature-resistant epoxy adhesive comprises the following components in parts by weight: 12-45 parts of epoxy resin, 5-35 parts of modified epoxy resin, 1-61 parts of filler, 6-34 parts of curing agent, 9.5-201 parts of solvent and 0.01-0.18 part of accelerator.

The specific weight parts of the raw materials of each component in each example are shown in the following table 4:

table 4: the specific weight parts of the raw materials of each component in examples 8-14 are as follows:

in the above embodiments 4 to 14: the alkali-free glass fiber-fabric is one or a mixture of more than two of alkali-free glass fiber cloth, 7628 electronic grade alkali-free glass fiber cloth, high-strength alkali-free glass fiber cloth, alkali-free glass fiber checkered cloth and glass fiber smoldering treatment cloth;

in the above embodiments 8 to 14: the epoxy resin is one or a mixture of more than two of bisphenol fluorene epoxy resin (DGEBF for short), bis-o-cresol fluorene epoxy resin (DGEMBF for short) and bis-di-o-cresol fluorene epoxy resin (DGEDMFF for short);

in the above embodiments 8 to 14: the modified epoxy resin is one or a mixture of more than two of alicyclic glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, biphenyl type epoxy resin, phenol type novolac epoxy resin, o-cresol type novolac epoxy resin, bisphenol A novolac epoxy resin, resorcinol type epoxy resin, epoxy resin of dicyclopentadiene or dicyclic diene and novolac polycondensation resin, isocyanate modified epoxy resin and hydantoin epoxy resin;

in the above embodiments 8 to 14: the curing agent is a mixture of two or more than two of 4, 4-diaminodiphenylmethane, 4-diaminodiphenyl sulfone and diamine fluorene;

in the above embodiments 8 to 14: the filler is one or a mixture of more than two of aluminum hydroxide, alumina, boehmite, silica micropowder, hydrotalcite and talcum powder;

in the above embodiments 8 to 14: the accelerant is one or a mixture of more than two of 2-methylimidazole, 2-ethyl-4-methylimidazole, N-dimethylbenzylamine, boron trifluoride ethylamine, triethylamine, hexamethyltetramine and aluminum acetylacetonate;

in the above embodiments 8 to 14: the solvent is one or a mixture of more than two of toluene, xylene, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, propylene glycol methyl ether, methyl ethyl ketone, cyclohexanone, methyl acetate, butanone, acetone, DMF and ethanol.

Example 15:

a preparation method of a high temperature resistant epoxy glass fiber insulating layer and a molded part comprises the following steps:

a. preparing a high-temperature-resistant epoxy adhesive:

(a) preparing materials: taking raw materials of the components according to the weight ratio of 12-45 parts of epoxy resin, 5-35 parts of modified epoxy resin, 1-61 parts of filler, 6-34 parts of curing agent, 9.5-201 parts of solvent and 0.01-0.18 part of accelerator; the specific raw materials and the weight parts are the same as those in any one of the embodiments 4 to 14;

(b) adding the epoxy resin, the modified epoxy resin and the filler in the formula amount in the step (a) into a glue preparation tank at room temperature, stirring for 2 hours at the temperature of 90 ℃, adding a curing agent, stirring for 2.5 hours at the temperature of 125 ℃, fully and uniformly dispersing, adding an accelerant to adjust the forming time of the glue solution, sampling, testing the forming time of the glue solution by using a knife method, and preparing the high-temperature-resistant epoxy adhesive when the forming time is 440-530 seconds under the condition of a hot plate at 210 ℃, thus obtaining the high-temperature-resistant epoxy adhesive;

b, dipping the alkali-free glass fiber-fabric into the high-temperature-resistant epoxy adhesive in the step a through a horizontal or vertical gluing machine, and baking the high-temperature-resistant epoxy adhesive through a baking channel of the gluing machine, wherein the baking channel of the gluing machine is 24m long and is divided into 4 sections with each section being 6m, the baking temperature is 85-165 ℃, the speed of the gluing machine is 16m/min, and the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg is prepared after baking;

the alkali-free glass fiber-fabric is one or a mixture of more than two of alkali-free glass fiber cloth, 7628 electronic grade alkali-free glass fiber cloth, high-strength alkali-free glass fiber cloth, alkali-free glass fiber checkered cloth and glass fiber smoldering treatment cloth;

cutting the prepared high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg into a required shape and size according to the requirements of a high-temperature-resistant epoxy glass fiber insulating layer and a drawing (process) of a molded part, placing the 2 layers of the cut high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg on a (smooth) stainless steel mold coated with a release agent on two sides, sending the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg into a common hot press or a vacuum hot press with a hot plate, controlling the temperature to be 130-250 ℃ and the pressure to be 5-30 MPa for hot press molding, and controlling the hot press molding time to be 0.5h to obtain the high-temperature-resistant epoxy glass fiber insulating layer and the molded part.

Example 16:

a. preparing a high-temperature-resistant epoxy adhesive:

(b) adding the epoxy resin, the modified epoxy resin and the filler in the formula amount in the step (a) into a glue preparation tank at room temperature, stirring for 1.5 hours at the temperature of 75 ℃, adding a curing agent, stirring for 3.5 hours at the temperature of 105 ℃, adding an accelerant to adjust the forming time of the glue solution after the glue solution is fully dispersed uniformly, sampling, testing the forming time of the glue solution by using a knife method, and completing preparation of the high-temperature-resistant epoxy adhesive when the forming time is 440-530 seconds under the condition of a hot plate at the temperature of 210 ℃ to obtain the high-temperature-resistant epoxy adhesive;

b, dipping the alkali-free glass fiber-fabric into the high-temperature-resistant epoxy adhesive in the step a through a horizontal or vertical gluing machine, and baking the high-temperature-resistant epoxy adhesive through a baking channel of the gluing machine, wherein the baking channel of the gluing machine is 24m long and is divided into 4 sections with each section being 6m, the baking temperature is 75-165 ℃, the speed of the gluing machine is 18m/min, and the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg is prepared after baking;

the alkali-free glass fiber fabric was the same as in example 15;

cutting the prepared high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg into a required shape and size according to the drawing (process) requirements of a high-temperature-resistant epoxy glass fiber insulating layer and a molded part, placing 300 layers of the cut high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg on a (smooth) stainless steel mold coated with a release agent on two sides, sending the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg into a common hot press or a vacuum hot press with a hot plate, controlling the temperature to be 130-250 ℃ and the pressure to be 5-30 MPa, and carrying out hot press molding for 30 hours to obtain the high-temperature-resistant epoxy glass fiber insulating layer and the molded part.

Example 17:

a. preparing a modified epoxy adhesive:

(a) preparing materials: taking raw materials of the components according to the weight ratio of 12-45 parts of epoxy resin, 5-35 parts of modified epoxy resin, 1-61 parts of filler, 6-34 parts of curing agent, 9.5-201 parts of solvent and 0.01-0.18 part of accelerator; (ii) a The specific raw materials and the weight parts are the same as those in any one of the embodiments 4 to 14;

(b) adding the epoxy resin, the modified epoxy resin and the filler in the formula amount in the step (a) into a glue preparation tank at room temperature, stirring for 1.25 hours at 105 ℃, adding a curing agent, stirring for 2.25 hours at 125 ℃, adding an accelerant to adjust the forming time of the glue solution after the glue solution is fully dispersed uniformly, sampling, testing the forming time of the glue solution by using a knife method, and completing preparation of the high-temperature-resistant epoxy adhesive when the forming time is 440-530 seconds under the condition of a hot plate at 210 ℃ to obtain the high-temperature-resistant epoxy adhesive;

b, dipping the alkali-free glass fiber-fabric into the high-temperature-resistant epoxy adhesive in the step a through a horizontal or vertical gluing machine, and baking the high-temperature-resistant epoxy adhesive through a baking channel of the gluing machine, wherein the baking channel of the gluing machine is 24m long and is divided into 4 sections and 6m in each section, the baking temperature is 80-165 ℃, the speed of the gluing machine is 16m/min, and the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg is prepared after baking;

the alkali-free glass fiber fabric was the same as in example 15;

cutting the prepared high temperature resistant epoxy alkali-free glass fiber-fabric prepreg into required shape and size according to the drawing (process) requirements of the insulation layer and the mould pressing structural member for the extra-high voltage direct current power transmission and transformation, placing 150 layers of the cut high temperature resistant epoxy alkali-free glass fiber-fabric prepreg on a (smooth) stainless steel mould coated with a release agent on two sides, sending the high temperature resistant epoxy alkali-free glass fiber-fabric prepreg into a common hot press or a vacuum hot press with a hot plate, controlling the temperature to be 130-250 ℃ and the pressure to be 5-30 MPa for hot press molding, and obtaining the high temperature resistant epoxy glass fiber insulation layer and the mould pressing part within the hot press molding time of 16 h.

Example 18:

a high temperature resistant epoxy glass fiber insulating layer, mould pressing finished piece, the insulating layer, mould pressing finished piece are one deck or more than one deck high temperature resistant epoxy alkali-free glass fiber-fabric prepreg that overlap and make composite material after the hot briquetting;

the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg is formed by impregnating alkali-free glass fiber-fabric with a high-temperature-resistant epoxy adhesive and then baking (removing part of solvent in the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg) the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg with a semi-cured material on the alkali-free glass fiber-fabric; in the high temperature resistant epoxy alkali-free glass fiber-fabric prepreg: the weight percentage of the semi-cured product is 35 percent, and the weight percentage of the alkali-free glass fiber-fabric is 65 percent;

the high-temperature-resistant epoxy adhesive comprises the following components in parts by weight: 28 parts of epoxy resin, 20 parts of modified epoxy resin, 20 parts of curing agent, 31 parts of filler, 105 parts of solvent and 0.09 part of accelerator.

Example 19:

the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg is formed by impregnating alkali-free glass fiber-fabric with a high-temperature-resistant epoxy adhesive and then baking (removing part of solvent in the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg) the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg with a semi-cured material on the alkali-free glass fiber-fabric; in the high temperature resistant epoxy alkali-free glass fiber-fabric prepreg: the weight percentage of the semi-cured product is 15 percent, and the weight percentage of the alkali-free glass fiber-fabric is 85 percent;

the high-temperature-resistant epoxy adhesive comprises the following components in parts by weight: 12 parts of epoxy resin, 5 parts of modified epoxy resin, 6 parts of curing agent, 1 part of filler, 9.5 parts of solvent and 0.01 part of accelerator.

Example 20:

the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg is formed by impregnating alkali-free glass fiber-fabric with a high-temperature-resistant epoxy adhesive and then baking (removing part of solvent in the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg) the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg with a semi-cured material on the alkali-free glass fiber-fabric; in the high temperature resistant epoxy alkali-free glass fiber-fabric prepreg: the weight percentage of the semi-cured product is 55 percent, and the weight percentage of the alkali-free glass fiber-fabric is 45 percent;

the high-temperature-resistant epoxy adhesive comprises the following components in parts by weight: 45 parts of epoxy resin, 35 parts of modified epoxy resin, 34 parts of curing agent, 61 parts of filler, 201 parts of solvent and 0.18 part of accelerator.

Example 21:

a. preparing a high-temperature-resistant epoxy adhesive:

(a) preparing materials: taking raw materials of the components according to the composition and the weight ratio of 29 parts of epoxy resin, 21 parts of modified epoxy resin, 20 parts of curing agent, 32 parts of filler, 110 parts of solvent and 0.1 part of accelerator;

(b) adding the epoxy resin, the modified epoxy resin and the filler in the formula amount in the step (a) into a glue preparation tank at room temperature, stirring for 1.2 hours at the temperature of 85 ℃, adding a curing agent, stirring for 2.5 hours at the temperature of 122 ℃, adding a solvent, fully and uniformly dispersing, adding an accelerant to adjust the forming time of the glue solution, sampling, testing the forming time of the glue solution by using a knife method, and completing preparation of the high-temperature-resistant epoxy adhesive when the forming time is 440-530 seconds under the condition of a hot plate at 210 ℃ to obtain the high-temperature-resistant epoxy adhesive;

b, dipping the alkali-free glass fiber-fabric into the high-temperature-resistant epoxy adhesive in the step a by a gluing machine (which can be a horizontal or vertical gluing machine), and baking by a baking channel of the gluing machine, wherein the baking channel of the gluing machine is 24m long and is divided into 4 sections and 6m in each section, the baking temperature range is 70-175 ℃, the speed of the gluing machine is 15m/min, and the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg is prepared after baking;

and (c) cutting the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg prepared in the step (b) into a required shape and size according to the requirements of a high-temperature-resistant epoxy glass fiber insulating layer and a drawing (process) of a molded part, placing the cut layer of high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg on a smooth stainless steel mold (coated with a release agent on two sides), sending the cut layer of high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg into a hot press (which can be a common hot press or a vacuum hot press) with a hot plate, controlling the temperature at 190 ℃ and the pressure at 17MPa for hot press molding, and carrying out hot press molding for 0.5h to obtain the high-temperature-resistant epoxy glass fiber insulating layer and the molded part.

Example 22:

a. preparing a high-temperature-resistant epoxy adhesive:

(a) preparing materials: taking raw materials of the components according to the composition and the weight ratio of 12 parts of epoxy resin, 6 parts of modified epoxy resin, 6 parts of curing agent, 1 part of filler, 9.5 parts of solvent and 0.01 part of accelerator;

(b) adding the epoxy resin, the modified epoxy resin and the filler in the formula amount in the step (a) into a glue preparation tank at room temperature, stirring for 2 hours at 55 ℃, adding a curing agent, stirring for 4 hours at 100 ℃, adding a solvent, fully and uniformly dispersing, adding an accelerant to adjust the forming time of the glue solution, sampling, testing the forming time of the glue solution by using a knife method, and preparing the high-temperature-resistant epoxy adhesive when the forming time is 440-530 seconds under the condition of a hot plate at 210 ℃ to obtain the high-temperature-resistant epoxy adhesive;

b, dipping the alkali-free glass fiber-fabric into the high-temperature-resistant epoxy adhesive in the step a by a gluing machine (which can be a horizontal or vertical gluing machine), and baking by a baking channel of the gluing machine, wherein the baking channel of the gluing machine is 24m long and is divided into 4 sections and 6m in each section, the baking temperature range is 70-175 ℃, the speed of the gluing machine is 8m/min, and the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg is prepared after baking;

and (b) cutting the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg prepared in the step (b) into a required shape and size according to the drawing (process) requirements of the high-temperature-resistant epoxy glass fiber insulating layer and a molded part, placing the cut high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg overlapped by more than 8 layers on a smooth stainless steel mold (coated with a release agent on two surfaces), sending the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg into a hot press (a common hot press or a vacuum hot press), controlling the temperature to be 130 ℃ and the pressure to be 5MPa, and carrying out hot press molding for 3 hours to obtain the high-temperature-resistant epoxy glass fiber insulating layer and the molded part.

Example 23:

a. preparing a high-temperature-resistant epoxy adhesive:

(a) preparing materials: taking raw materials of the components according to the composition and the weight ratio of 45 parts of epoxy resin, 35 parts of modified epoxy resin, 33 parts of curing agent, 60 parts of filler, 201 parts of solvent and 0.18 part of accelerator;

(b) adding the epoxy resin, the modified epoxy resin and the filler in the formula amount in the step (a) into a glue preparation tank at room temperature, stirring for 0.5 hour at the temperature of 115 ℃, adding a curing agent, stirring for 1 hour at the temperature of 145 ℃, adding a solvent, fully and uniformly dispersing, adding an accelerant to adjust the molding time of the glue solution, sampling, testing the molding time of the glue solution by using a knife method, and completing preparation of the high-temperature-resistant epoxy adhesive when the molding time is 440-530 seconds under the condition of a hot plate at 210 ℃ to obtain the high-temperature-resistant epoxy adhesive;

b, dipping the alkali-free glass fiber-fabric into the high-temperature-resistant epoxy adhesive in the step a by a gluing machine (which can be a horizontal or vertical gluing machine), and baking by a baking channel of the gluing machine, wherein the baking channel of the gluing machine is 24m long and is divided into 4 sections and 6m in each section, the baking temperature range is 70-175 ℃, the speed of the gluing machine is 21m/min, and the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg is prepared after baking;

cutting the high temperature resistant epoxy alkali-free glass fiber-fabric prepreg prepared in the step b into a required shape and size according to the drawing (process) requirements of the high temperature resistant epoxy glass fiber insulating layer and a molded part, placing the cut 30 layers of overlapped high temperature resistant epoxy alkali-free glass fiber-fabric prepreg on a smooth stainless steel mold (coated with a release agent on two surfaces), sending the stainless steel mold into a hot press (which can be a common hot press or a vacuum hot press) provided with a hot plate, controlling the temperature to be 250 ℃ and the pressure to be 30MPa, and carrying out hot press molding for 30 hours to obtain the high temperature resistant epoxy glass fiber insulating layer and the molded part.

In the above embodiments 18 to 23:

the epoxy resin is one or a mixture of two of bisphenol fluorene epoxy resin (DGEBF for short), bis-o-cresol fluorene epoxy resin (DGEMBF for short) and bis-di-o-cresol fluorene epoxy resin (DGEDMFF for short);

the curing agent is a mixture of two or more than two of 4, 4-diaminodiphenylmethane, 4-diaminodiphenyl sulfone and diamine fluorene;

the alkali-free glass fiber-fabric is one or a mixture of more than two of alkali-free glass fiber cloth, 7628 electronic grade alkali-free glass fiber cloth, high-strength alkali-free glass fiber cloth, alkali-free glass fiber checkered cloth and glass fiber braising treatment cloth.

In the above embodiments 21 to 23: the high temperature resistant epoxy alkali-free glass fiber-fabric prepreg prepared in the step b is a high temperature resistant epoxy alkali-free glass fiber-fabric prepreg with a semi-cured product on the alkali-free glass fiber-fabric, wherein the high temperature resistant epoxy alkali-free glass fiber-fabric prepreg comprises the following components in percentage by weight: the weight percentage of the semi-cured material is 15-55 percent, and the weight percentage of the alkali-free glass fiber-fabric is 45-85 percent;

in the above embodiments 15 to 17, 21 to 23: the shape of the stainless steel die in the step c is a flat plate shape, a U-shaped shape or the like, and other special shapes.

In the above embodiments 21 to 23: the performance indexes of the high-temperature-resistant epoxy glass fiber insulating layer and the molded part prepared in the step c are as follows: the mechanical strength is more than 225MPa at the temperature of 230 ℃, the bending strength is more than 225MPa at the temperature of 121 ℃ and the humidity of 100% for 96h, the shear strength is more than or equal to 15MPa, and the water absorption is less than or equal to 2%.

In the above embodiment: the percentages used, not specifically noted, are weight (mass) percentages or percentages known to those skilled in the art; the proportions used, not specifically noted, are weight (mass) proportions; the parts by weight may each be grams or kilograms.

In the above embodiment: the process parameters (temperature, pressure, time, concentration, vehicle speed, etc.) and the amounts of the components in each step are within the range, and any point can be applicable.

The present invention and the technical contents not specifically described in the above examples are the same as those of the prior art, and the raw materials are all commercially available products.

The present invention is not limited to the above-described embodiments, and the present invention can be implemented with the above-described advantageous effects.

Claims

1. A high temperature resistant epoxy glass fiber insulating layer, mould pressing finished piece, its characteristic is: the insulating layer and the molded part are made of composite materials by hot-press molding one or more layers of overlapped high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg;

the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg is formed by impregnating alkali-free glass fiber-fabric with a high-temperature-resistant epoxy adhesive and then baking the high-temperature-resistant epoxy alkali-free glass fiber-fabric prepreg with a semi-cured product on the alkali-free glass fiber-fabric;

the alkali-free glass fiber-fabric is a mixture of two or more than two of alkali-free glass fiber cloth, 7628 electronic grade alkali-free glass fiber cloth, high-strength alkali-free glass fiber cloth, alkali-free glass fiber checkered cloth and glass fiber smoldering treatment cloth;

the epoxy resin is one or a mixture of more than two of bisphenol fluorene epoxy resin, bis-o-cresol fluorene epoxy resin and bis-di-o-cresol fluorene epoxy resin;

the modified epoxy resin is one or a mixture of more than two of bisphenol A epoxy resin, bisphenol F epoxy resin, alicyclic epoxy resin, glycidyl amine epoxy resin, biphenyl epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, resorcinol epoxy resin, epoxy resin of dicyclopentadiene or dicyclopentadiene and phenolic polycondensation resin, isocyanate modified epoxy resin and hydantoin epoxy resin;

2. The high temperature resistant epoxy glass fiber insulation layer and molded part as claimed in claim 1, wherein: in the high temperature resistant epoxy alkali-free glass fiber-fabric prepreg: the weight percentage of the semi-cured material is 15-55 percent, and the weight percentage of the alkali-free glass fiber-fabric is 45-85 percent.

3. The high temperature resistant epoxy glass fiber insulation layer and molded part according to claim 1 or 2, which is characterized in that: the high temperature resistant epoxy glass fiber insulating layer and the molded part have mechanical strength of more than 225MPa at 230 ℃, bending strength of more than 225MPa at 121 ℃ for 96h under the environment of 100% humidity, shearing strength of more than or equal to 15MPa, and water absorption of less than or equal to 2%.

4. A preparation method of a high temperature resistant epoxy glass fiber insulating layer and a molded part is characterized by comprising the following steps:

a. preparing a high-temperature-resistant epoxy adhesive:

(b) adding the epoxy resin, the modified epoxy resin and the filler in the formula amount in the step (a) into a glue preparation tank at room temperature, stirring for 0.5-2 hours at the temperature of 55-115 ℃, adding a curing agent, stirring for 1-4 hours at the temperature of 100-145 ℃, adding a solvent, dispersing uniformly, adding an accelerator to adjust the forming time of the glue solution, sampling, testing the forming time of the glue solution by using a knife method, and preparing the high-temperature-resistant epoxy adhesive after the high-temperature-resistant epoxy adhesive is prepared under the condition of a 210 ℃ hot plate and when the forming time is 440-530 seconds;

coating the high-temperature-resistant epoxy adhesive in the step a on an alkali-free glass fiber-fabric by a gluing machine, and baking the alkali-free glass fiber-fabric by a baking channel of the gluing machine, wherein the baking channel of the gluing machine is 24m long and is divided into 4 sections and 6m in each section, the baking temperature range is 70-175 ℃, the speed of the gluing machine is 8-21 m/min, and the high-temperature-resistant epoxy alkali-free glass fiber-prepreg fabric is prepared after baking;

cutting the high temperature resistant epoxy alkali-free glass fiber-fabric prepreg prepared in the step b into a required shape and size according to the drawing requirements of the high temperature resistant epoxy glass fiber insulating layer and a molded part, placing one or more layers of the cut high temperature resistant epoxy alkali-free glass fiber-fabric prepreg on a stainless steel mold, sending the high temperature resistant epoxy alkali-free glass fiber-fabric prepreg into a hot press with a hot plate, controlling the temperature to be 130-250 ℃ and the pressure to be 5-30 MPa for hot press molding, and determining the hot press molding time to be 0.5-30 h according to the thickness of a molded structural part to be 0.2-150 mm, thus obtaining the high temperature resistant epoxy glass fiber insulating layer and the molded part.

5. The method for preparing the high temperature resistant epoxy glass fiber insulating layer and the molded part according to claim 4 is characterized in that: the high temperature resistant epoxy alkali-free glass fiber-fabric prepreg prepared in the step b is a high temperature resistant epoxy alkali-free glass fiber-fabric prepreg with a semi-cured product on the alkali-free glass fiber-fabric, wherein the high temperature resistant epoxy alkali-free glass fiber-fabric prepreg comprises the following components in percentage by weight: the weight percentage of the semi-cured material is 15-55 percent, and the weight percentage of the alkali-free glass fiber-fabric is 45-85 percent.

6. The method for preparing the high temperature resistant epoxy glass fiber insulating layer and the molded part according to claim 4 is characterized in that: the shape of the stainless steel die in the step c is a flat plate shape, a U-shaped shape or a similar shape.

7. The method for preparing the high temperature resistant epoxy glass fiber insulating layer and the molded part according to the claim 4, 5 or 6 is characterized in that: the high temperature resistant epoxy glass fiber insulation layer and the molded part prepared in the step c have the mechanical strength of more than 225MPa at the temperature of 230 ℃, the bending strength of more than 225MPa at the temperature of 121 ℃ for 96 hours in the environment with the humidity of 100 percent, the shear strength of more than or equal to 15MPa and the water absorption of less than or equal to 2 percent.