CN115490993A - Epoxy resin composition, preparation method and epoxy glass cloth laminated board - Google Patents
Epoxy resin composition, preparation method and epoxy glass cloth laminated board Download PDFInfo
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- CN115490993A CN115490993A CN202211336213.2A CN202211336213A CN115490993A CN 115490993 A CN115490993 A CN 115490993A CN 202211336213 A CN202211336213 A CN 202211336213A CN 115490993 A CN115490993 A CN 115490993A
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- epoxy resin
- resin composition
- epoxy
- laminated board
- cloth
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 185
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 185
- 239000004744 fabric Substances 0.000 title claims abstract description 148
- 239000000203 mixture Substances 0.000 title claims abstract description 129
- 239000011521 glass Substances 0.000 title claims abstract description 117
- 239000004593 Epoxy Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 17
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 51
- 239000005011 phenolic resin Substances 0.000 claims abstract description 44
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 27
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 25
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 25
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 238000000465 moulding Methods 0.000 claims abstract description 17
- 239000011256 inorganic filler Substances 0.000 claims abstract description 14
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 58
- 239000011259 mixed solution Substances 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 21
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 19
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical compound OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 12
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 12
- 239000000347 magnesium hydroxide Substances 0.000 claims description 12
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 7
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 6
- 239000002383 tung oil Substances 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical group NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 2
- 239000005977 Ethylene Substances 0.000 claims 2
- 238000005452 bending Methods 0.000 abstract description 20
- 238000012360 testing method Methods 0.000 abstract description 6
- 238000003825 pressing Methods 0.000 abstract description 5
- 239000011810 insulating material Substances 0.000 abstract description 4
- 239000003365 glass fiber Substances 0.000 description 16
- 239000004743 Polypropylene Substances 0.000 description 10
- 239000003292 glue Substances 0.000 description 10
- -1 polypropylene Polymers 0.000 description 10
- 229920001155 polypropylene Polymers 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- 238000009833 condensation Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004513 sizing Methods 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- AMOYMEBHYUTMKJ-UHFFFAOYSA-N 2-(2-phenylethoxy)ethylbenzene Chemical compound C=1C=CC=CC=1CCOCCC1=CC=CC=C1 AMOYMEBHYUTMKJ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NJSUFZNXBBXAAC-UHFFFAOYSA-N ethanol;toluene Chemical compound CCO.CC1=CC=CC=C1 NJSUFZNXBBXAAC-UHFFFAOYSA-N 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000003137 locomotive effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
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- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
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- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/546—Flexural strength; Flexion stiffness
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- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- Manufacturing & Machinery (AREA)
- Laminated Bodies (AREA)
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Abstract
The invention relates to the technical field of insulating material preparation, in particular to an epoxy resin composition, a preparation method and an epoxy glass cloth laminated board, wherein the epoxy resin composition comprises the following raw material components in parts by weight: 1 part of polyfunctional epoxy resin, 0.1 to 0.67 part of linear thermoplastic phenolic resin, 0.1 to 0.67 part of thermosetting phenolic resin, 0.25 to 0.4 part of curing agent, 0.13 to 0.72 part of inorganic filler and 0.6 to 1.1 parts of organic solvent. According to the test, the molding time of the epoxy resin composition at 160 ℃ is 1 '51' to 4 '56', the bending strength of the laminated board prepared by the epoxy resin composition is 409 to 424Mpa, the bending strength at 155 ℃ is 125 to 288Mpa, the phenomenon of gummosis hardly occurs during pressing, and the production speed of the grey cloth can reach 10m/min. Solves the problems that the heat-resistant temperature of the laminated board is low, the bending strength at 155 ℃, the forming time of the epoxy resin composition at 160 ℃ is long, the gummed glass grey cloth is easy to flow, the production efficiency of prepregs is low, and the thickness of the laminated board is difficult to control in the prior art.
Description
Technical Field
The invention relates to the technical field of insulating material preparation, in particular to an epoxy resin composition, a preparation method and an epoxy glass cloth laminated board.
Background
Since the 1980 s, several types of insulating laminated board materials have been developed in the insulating material industry in order to meet the needs of the motor and electric appliance industries. In recent years, with the rapid development of the dry-type transformer industry and the development of the motor industry including high-speed locomotive traction motors, large motors, special motors and the like to miniaturization, light weight and high efficiency, the demand for high-temperature-resistant insulating materials is increasing.
Conventional processes have produced epoxy glass cloth laminates used to make slot wedges for various electrical machines, insulators for transformers, and structural parts for various electrical machines and electrical equipment. The method comprises the steps of enabling reinforcing material glass fiber cloth to pass through a resin tank of an epoxy resin composition, impregnating the reinforcing material glass fiber cloth with the epoxy resin composition, baking the impregnated glass fiber cloth through an oven to remove all solvents and part of organic volatile matters, shearing the resin into prepregs with a certain size through a shearing machine after the resin is partially cured or pre-cured, and pressing the prepregs with single layer or multiple layers of superposition into an epoxy glass cloth laminated board under the condition of heating and pressurizing.
At present, the resin system used as the insulating laminated material is mainly an epoxy resin system and other resin systems, wherein the epoxy resin has excellent mechanical and electrical properties, adhesive property, small shrinkage rate, good heat resistance and good chemical stability, and is widely applied.
The components typically used in epoxy resin compositions are bisphenol diglycidyl ether, a curing agent is dicyandiamide, an organic solvent is dimethylformamide and an accelerator imidazole. The laminated board produced by the composition has low heat-resistant temperature and low bending strength at 155 ℃, the epoxy resin composition has long forming time at 160 ℃, the curing degree of the epoxy composition sized glass grey cloth is low, and the epoxy composition sized glass grey cloth is easy to flow, so that the problems of low production efficiency and difficult control of the thickness of the laminated board during the production of the epoxy composition sized glass grey cloth are caused.
Disclosure of Invention
Aiming at the problems that the heat-resistant temperature of the laminated board is low, the bending strength at 155 ℃ is low, the forming time of the epoxy composition at 160 ℃ is long, the curing degree of the epoxy composition sizing glass grey cloth is low, the easy flowing glue is generated, the production efficiency is low when the epoxy composition sizing glass grey cloth is produced, and the thickness of the laminated board is difficult to control in the prior art.
The invention provides an epoxy resin composition, a preparation method and an epoxy glass cloth laminated board.
The invention is realized by the following technical scheme:
the invention provides an epoxy resin composition which comprises the following raw material components in parts by weight: 1 part of polyfunctional epoxy resin, 0.1 to 0.67 part of linear thermoplastic phenolic resin, 0.1 to 0.67 part of thermosetting phenolic resin, 0.25 to 0.4 part of curing agent, 0.13 to 0.72 part of inorganic filler and 0.6 to 1.1 part of organic solvent;
the multifunctional epoxy resin is one or more of bisphenol diglycidyl ether epoxy resin, triphenol triglycidyl ether epoxy resin, tetraphenol tetraglycidyl ether epoxy resin and diphenol phenylethane glycidyl ether epoxy resin.
Preferably, the linear thermoplastic phenolic resin is a thermoplastic phenol-formaldehyde resin;
the thermosetting phenolic resin is o-cresol formaldehyde resin and/or thermosetting phenol formaldehyde resin;
the inorganic filler is one or more of silicon micropowder, aluminum oxide, aluminum hydroxide, calcium carbonate and magnesium hydroxide;
the curing agent is dicyandiamide, phthalic anhydride, tung oil anhydride or 4' diaminodiphenyl sulfone;
the organic solvent is one or more of toluene, methanol, xylene, acetone, dimethylformamide and ethanol.
Preferably, the multifunctional epoxy resin comprises bisphenol diglycidyl ether epoxy resin, triphenol triglycidyl ether epoxy resin, tetraphenol tetraglycidyl ether epoxy resin and diphenol phenylethane glycidyl ether epoxy resin, and the mass ratio of the bisphenol diglycidyl ether epoxy resin to the triphenol triglycidyl ether epoxy resin to the tetraphenol tetraglycidyl ether epoxy resin to the diphenol phenylethane glycidyl ether epoxy resin is 4.
Preferably, the multifunctional epoxy resin has an epoxy equivalent of 220 to 250g/eq.
A preparation method of the epoxy resin composition comprises the following steps:
step 1): dissolving polyfunctional epoxy resin and a curing agent in an organic solvent to obtain an epoxy resin mixture;
step 2): the epoxy resin mixture, the linear thermoplastic phenolic resin, the thermosetting phenolic resin and the inorganic filler are uniformly mixed to prepare the epoxy resin composition.
Further, the specific operation of step 1) is as follows:
step 1.1): dissolving polyfunctional epoxy resin and a curing agent in an organic solvent under the condition of stirring to form a mixed solution;
step 1.2): heating the mixed solution, keeping the temperature until the mixed solution is clear and transparent, reacting for 50-70 min, and cooling to below 50 ℃;
step 1.3): and adding an organic solvent into the cooled mixed solution, and uniformly mixing to form an epoxy resin mixture.
Preferably, the temperature for raising and maintaining the temperature in the step 1.2) is 100-110 ℃.
An epoxy glass cloth laminated board comprises the epoxy resin composition.
Preferably, the epoxy glass cloth laminate has a bending strength of 409 to 424Mpa and a bending strength of 125 to 288Mpa at 155 ℃.
Preferably, the molding time of the epoxy resin composition at 160 ℃ is 1 '51' to 4 '56'.
Compared with the prior art, the invention has the following beneficial effects:
the invention relates to an epoxy resin composition, which takes polyfunctional epoxy resin, linear thermoplastic phenolic resin, thermosetting phenolic resin, curing agent, organic solvent and inorganic filler as raw materials; the addition of the polyfunctional epoxy resin can improve the resin crosslinking density of the whole composition, the rigidity and stability of the resin composition are improved by the curing agent and the inorganic filler, and the rigidity and stability of the resin are improved as the resin crosslinking density is increased, the molecular weight is increased, so that the heat-resistant temperature of the resin is increased; the addition of the linear thermoplastic phenolic resin and the thermosetting phenolic resin promotes the crosslinking of the whole epoxy resin composition, so that the resin molding time is stable, the molding speed is high, the curing time is short, and the heat-resistant temperature of the epoxy resin composition is not influenced, so that the laminated board produced by using the epoxy resin composition has very good heat resistance and bending resistance, and meanwhile, the epoxy resin composition has short curing time, the produced epoxy glass grey cloth has high curing degree, and the epoxy glass grey cloth is not easy to flow. Thereby improving the production efficiency of the prepreg and well controlling the thickness of the laminated board. According to the test, the laminated board prepared by the epoxy resin composition has the bending strength of 409-424 Mpa and the bending strength of 125-288 Mpa at 155 ℃, the molding time of the epoxy resin composition at 160 ℃ is 1 '51' -4 '56', the phenomenon of gummosis is hardly generated when the laminated board is pressed, and the production speed of the gray cloth can reach 10m/min.
The invention provides a preparation method of the epoxy resin composition, which comprises the steps of dissolving polyfunctional epoxy resin and a curing agent in an organic solvent to obtain an epoxy resin mixture; and then uniformly mixing the epoxy resin mixture, the linear thermoplastic phenolic resin, the thermosetting phenolic resin and the inorganic filler to successfully prepare the epoxy resin composition. The preparation method is simple, the reaction is mild, the yield is high, the method is suitable for industrial production, and the prepared epoxy resin composition has the characteristics of high heat-resistant temperature, stable forming, short forming time, high bending strength and good mechanical property.
The invention also provides an epoxy glass cloth laminated board comprising the epoxy resin composition, the bending strength of the epoxy glass cloth laminated board is 409-424 Mpa, the bending strength of the epoxy glass cloth laminated board is 125-288 Mpa at 155 ℃, the curing time of the epoxy resin composition is 1' -51 ' -4 ' at 160 ℃, glue running phenomenon hardly occurs in the laminated board pressing process, the production speed of the gray cloth can reach 10m/min, the curing degree of the epoxy glass cloth laminated board is high in the preparation process, the curing speed is high, glue running does not occur, the thickness of the laminated board can be effectively controlled according to the design, the production efficiency is high, and very good economic benefits can be generated.
Drawings
FIG. 1 is a flow chart of a method for preparing an epoxy resin composition according to the present invention.
FIG. 2 is a flow chart of a method for preparing an epoxy resin mixture in an embodiment of the present invention.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The invention discloses an epoxy resin composition which comprises the following raw material components in parts by weight: 1 part of polyfunctional epoxy resin, 0.1 to 0.67 part of linear thermoplastic phenolic resin, 0.1 to 0.67 part of thermosetting phenolic resin, 0.25 to 0.4 part of curing agent, 0.13 to 0.72 part of inorganic filler and 0.6 to 1.1 part of organic solvent;
the multifunctional epoxy resin is one or more of bisphenol diglycidyl ether epoxy resin, triphenol triglycidyl ether epoxy resin, tetraphenol tetraglycidyl ether epoxy resin and diphenol phenylethane glycidyl ether epoxy resin; preferably, the multifunctional epoxy resin has an epoxy equivalent weight of 220 to 250g/eq, and comprises a bisphenol diglycidyl ether epoxy resin, a triphenol triglycidyl ether epoxy resin, a tetraphenol tetraglycidyl ether epoxy resin and a diphenol styrene glycidyl ether epoxy resin, wherein the mass ratio of the bisphenol diglycidyl ether epoxy resin to the triphenol triglycidyl ether epoxy resin to the tetraphenol tetraglycidyl ether epoxy resin to the diphenol styrene glycidyl ether epoxy resin is 4.
The linear thermoplastic phenolic resin is thermoplastic phenol formaldehyde resin;
the thermosetting phenolic resin is o-cresol formaldehyde resin and/or thermosetting phenol formaldehyde resin; preferably a thermosetting phenol-formaldehyde resin
The inorganic filler is one or more of silicon micropowder, aluminum oxide, aluminum hydroxide, calcium carbonate and magnesium hydroxide; magnesium hydroxide with a fineness of 2500 mesh is preferred.
The curing agent is dicyandiamide, phthalic anhydride, tung oil anhydride or 4'4 diamino diphenyl sulfone; preferably 4' diaminodiphenylsulfone.
The organic solvent is one or more of toluene, methanol, xylene, acetone, dimethylformamide and ethanol; toluene and/or acetone are preferred, and the mass ratio of toluene to acetone is (4-5): 1.
Referring to fig. 1 and 2, the present invention provides a method for preparing the epoxy resin composition, comprising the steps of:
step 1): dissolving polyfunctional epoxy resin and a curing agent in an organic solvent to obtain an epoxy resin mixture, and specifically operating as follows:
step 1.1): dissolving polyfunctional epoxy resin and a curing agent in an organic solvent under the condition of stirring to form a mixed solution;
step 1.2): heating the mixed solution to 100-110 ℃, keeping the temperature until the mixed solution is clear and transparent, reacting for 50-70 min, and cooling to below 50 ℃;
step 1.3): and adding an organic solvent into the cooled mixed solution, and uniformly mixing to form an epoxy resin mixture.
Step 2): uniformly mixing the epoxy resin mixture, the linear thermoplastic phenolic resin, the thermosetting phenolic resin and the inorganic filler to prepare and form the epoxy resin composition, wherein the preparation method comprises the following specific operations: under the condition of stirring, adding the linear thermoplastic phenolic resin, the thermosetting phenolic resin and the inorganic filler into the epoxy resin mixture, and stirring for 2-4 h to form the epoxy resin composition.
The invention also provides an epoxy glass cloth laminated board which comprises the epoxy resin composition. The bending strength of the epoxy glass cloth laminated plate is 409-424 Mpa, and the bending strength at 155 ℃ is 125-288 Mpa; the epoxy resin composition has a curing time of 1 '51' to 4 '56' at 160 ℃.
The preparation method of the epoxy glass cloth laminated board comprises the following steps:
soaking the epoxy resin composition in glass fiber cloth, and baking to obtain sized glass grey cloth;
superposing the sized glass grey cloth, weighing, and calculating the thickness of the sized glass grey cloth; the calculation method is as follows:
the weight (, kilograms) of the laminated sized glass grey cloth is = length × width × thickness × density;
the density of the rubberized glass grey cloth is 1850 to 2000 kilograms per meter 3 。
Superposing the grey sized glass fabric, placing the superposed grey sized glass fabric between two stainless steel plates with smooth surfaces paved with polypropylene films, and extruding the superposed grey sized glass fabric; controlling the unit pressure at 5-6 Mpa and the temperature at 165-175 ℃, keeping for 300min, and cooling to below 30 ℃ to obtain the epoxy glass cloth laminated board with the designed thickness.
Example 1
Placing 0.667 parts of toluene in a reaction kettle, adding 1 part of a mixture of bisphenol diglycidyl ether epoxy resin, triphenol triglycidyl ether epoxy resin, tetraphenol tetraglycidyl ether epoxy resin and diphenol phenethyl ether glycidyl ether epoxy resin in a mass ratio of 4; heating the mixed solution to 100 ℃ under the conditions of stirring and condensation, keeping the temperature until the mixed solution is clear and transparent, reacting for 50min, and cooling to below 50 ℃; 0.166 parts of acetone is added to the cooled mixed solution and mixed uniformly to form an epoxy resin mixture.
0.25 parts of linear thermoplastic phenolic resin, 0.25 parts of thermosetting phenolic resin and 0.175 parts of magnesium hydroxide are added into the epoxy resin mixture under the condition of stirring, and the mixture is stirred for 2 to 4 hours to form the epoxy resin composition. After stirring for 2h, the molding time was measured and recorded using a knife at 160 ℃. + -. 2 ℃.
The resulting epoxy resin composition was impregnated with (210 g/m) 2 ) The method comprises the following steps of (1) preparing glass fiber cloth, baking the glass fiber cloth to obtain sized glass grey cloth, stacking the sized glass grey cloth, weighing the stacked glass grey cloth, and calculating the thickness of the sized glass grey cloth, wherein the thickness of the sized glass grey cloth is preferably set to be 5mm;
superposing the grey sized glass fabric, placing the superposed grey sized glass fabric between two stainless steel plates with smooth surfaces paved with polypropylene films, and extruding the superposed grey sized glass fabric; controlling the unit pressure at 5-6 Mpa and the temperature at 165-175 ℃, keeping the temperature for 300min, and cooling to below 30 ℃ to obtain the epoxy glass cloth laminated board with the thickness of 5 mm.
Example 2
Placing 0.6928 part of toluene in a reaction kettle, adding 1 part of a mixture of bisphenol diglycidyl ether epoxy resin, triphenol triglycidyl ether epoxy resin, tetraphenol tetraglycidyl ether epoxy resin and diphenol phenylethane glycidyl ether epoxy resin in a mass ratio of 4; heating the mixed solution to 110 ℃ under the conditions of stirring and condensation, keeping the temperature until the mixed solution is clear and transparent, reacting for 60min, and cooling to below 50 ℃; 0.1732 parts of acetone is added to the cooled mixed solution and mixed uniformly to form an epoxy resin mixture.
0.227 part of linear thermoplastic phenolic resin, 0.227 part of thermosetting phenolic resin and 0.21 part of magnesium hydroxide are added into the epoxy resin mixture under the condition of stirring, and the mixture is stirred for 2 to 4 hours to form the epoxy resin composition. After stirring for 2h, the molding time was measured and recorded using a knife at 160 ℃. + -. 2 ℃.
The resulting epoxy resin composition was impregnated with (210 g/m) 2 ) Glass fiber cloth is baked to prepare sized glass grey cloth, the sized glass grey cloth is stacked and weighed, and the thickness of the sized glass grey cloth is calculated, wherein the thickness of the sized glass grey cloth is preferably set to be 5mm;
superposing the grey sized glass fabric, placing the superposed grey sized glass fabric between two stainless steel plates with smooth surfaces paved with polypropylene films, and extruding the superposed grey sized glass fabric; controlling the unit pressure at 5-6 Mpa and the temperature at 165-175 ℃, keeping the temperature for 300min, and then cooling to below 30 ℃ to obtain the epoxy glass cloth laminated board with the thickness of 5 mm.
Example 3
Placing 0.675 parts of xylene in a reaction kettle, adding 1 part of a mixture of bisphenol diglycidyl ether epoxy resin, triphenol triglycidyl ether epoxy resin and tetraphenol tetraglycidyl ether epoxy resin in a mass ratio of 6; heating the mixed solution to 105 ℃ under the conditions of stirring and condensation, keeping the temperature until the mixed solution is clear and transparent, reacting for 65min, and cooling to below 50 ℃; 0.225 parts of dimethylformamide is added to the cooled mixed solution, and the mixture is uniformly mixed to form an epoxy resin mixture.
Under the condition of stirring, 0.203 part of linear thermoplastic phenolic resin, 0.203 part of thermosetting phenolic resin and 0.26 part of mixture of magnesium hydroxide and aluminum oxide are added into the epoxy resin mixture, and the mixture is stirred for 2 to 4 hours to form the epoxy resin composition. After stirring for 2h, the molding time was measured and recorded using a knife at 160 ℃. + -. 2 ℃.
The resulting epoxy resin composition was impregnated with (210 g/m) 2 ) Glass fiber cloth, baking to obtain sized glass grey cloth, stacking the sized glass grey cloth, and weighingCalculating the thickness of the sized glass grey cloth, wherein the thickness of the sized glass grey cloth is preferably set to be 5mm;
superposing the grey cloth of the sized glass, placing the superposed grey cloth between two stainless steel plates with smooth surfaces and a polypropylene film, and extruding the superposed grey cloth; controlling the unit pressure at 5-6 Mpa and the temperature at 165-175 ℃, keeping the temperature for 300min, and cooling to below 30 ℃ to obtain the epoxy glass cloth laminated board with the thickness of 5 mm.
Example 4
Placing 0.7475 parts of toluene in a reaction kettle, adding 1 part of a mixture of bisphenol diglycidyl ether epoxy resin, triphenol triglycidyl ether epoxy resin, tetraphenol tetraglycidyl ether epoxy resin and diphenol phenylethane glycidyl ether epoxy resin in a mass ratio of 4; heating the mixed solution to 110 ℃ under the conditions of stirring and condensation, keeping the temperature until the mixed solution is clear and transparent, reacting for 60min, and cooling to below 50 ℃; 0.1869 parts of acetone is added to the cooled mixed solution, and the mixture is uniformly mixed to form an epoxy resin mixture.
0.173 parts of linear thermoplastic phenolic resin, 0.173 parts of thermosetting phenolic resin and 0.43 parts of magnesium hydroxide are added into the epoxy resin mixture under stirring, and stirred for 2-4 h to form the epoxy resin composition. After stirring for 2h, the molding time was measured and recorded using a knife at 160 ℃. + -. 2 ℃.
The resulting epoxy resin composition was impregnated with (210 g/m) 2 ) The method comprises the following steps of (1) preparing glass fiber cloth, baking the glass fiber cloth to obtain sized glass grey cloth, stacking the sized glass grey cloth, weighing the stacked glass grey cloth, and calculating the thickness of the sized glass grey cloth, wherein the thickness of the sized glass grey cloth is preferably set to be 5mm;
superposing the grey sized glass fabric, placing the superposed grey sized glass fabric between two stainless steel plates with smooth surfaces paved with polypropylene films, and extruding the superposed grey sized glass fabric; controlling the unit pressure at 5-6 Mpa and the temperature at 165-175 ℃, keeping the temperature for 300min, and cooling to below 30 ℃ to obtain the epoxy glass cloth laminated board with the thickness of 5 mm.
Example 5
Placing 0.825 parts of xylene in a reaction kettle, adding 1 part of a mixture of bisphenol diglycidyl ether epoxy resin and triphenol triglycidyl ether epoxy resin to dimethylformamide under stirring, and then adding 0.4 part of a mixture of tung oil anhydride and 4' diamino diphenyl sulfone to form a mixed solution; heating the mixed solution to 110 ℃ under the conditions of stirring and condensation, keeping the temperature until the mixed solution is clear and transparent, reacting for 70min, and cooling to below 50 ℃; 0.275 parts of acetone is added to the cooled mixture and mixed uniformly to form an epoxy resin mixture.
0.14 parts of linear thermoplastic phenolic resin, 0.14 parts of thermosetting phenolic resin and 0.504 parts of magnesium hydroxide are added into the epoxy resin mixture under the condition of stirring, and the mixture is stirred for 2 to 4 hours to form the epoxy resin composition. After stirring for 2h, the molding time was measured and recorded using a knife at 160 ℃. + -. 2 ℃.
The resulting epoxy resin composition was impregnated with (210 g/m) 2 ) Glass fiber cloth is baked to prepare sized glass grey cloth, the sized glass grey cloth is stacked and weighed, and the thickness of the sized glass grey cloth is calculated, wherein the thickness of the sized glass grey cloth is preferably set to be 5mm;
superposing the grey sized glass fabric, placing the superposed grey sized glass fabric between two stainless steel plates with smooth surfaces paved with polypropylene films, and extruding the superposed grey sized glass fabric; controlling the unit pressure at 5-6 Mpa and the temperature at 165-175 ℃, keeping the temperature for 300min, and cooling to below 30 ℃ to obtain the epoxy glass cloth laminated board with the thickness of 5 mm.
Example 6
Placing 0.45 part of xylene in a reaction kettle, adding 1 part of bisphenol diglycidyl ether epoxy resin to dimethylformamide under stirring, and then adding 0.25 part of 4' diaminodiphenyl sulfone to form a mixed solution; heating the mixed solution to 110 ℃ under the conditions of stirring and condensation, keeping the temperature until the mixed solution is clear and transparent, reacting for 60min, and cooling to below 50 ℃; and adding 0.15 part of ethanol into the cooled mixed solution, and uniformly mixing to form an epoxy resin mixture.
0.1 part of linear thermoplastic phenolic resin, 0.1 part of thermosetting phenolic resin and 0.13 part of magnesium hydroxide are added into the epoxy resin mixture under the condition of stirring, and the mixture is stirred for 2 to 4 hours to form the epoxy resin composition. After stirring for 2h, the molding time was measured and recorded using a knife at 160 ℃. + -. 2 ℃.
The resulting epoxy resin composition was impregnated with (210 g/m) 2 ) Glass fiber cloth is baked to prepare sized glass grey cloth, the sized glass grey cloth is stacked and weighed, and the thickness of the sized glass grey cloth is calculated, wherein the thickness of the sized glass grey cloth is preferably set to be 5mm;
superposing the grey cloth of the sized glass, placing the superposed grey cloth between two stainless steel plates with smooth surfaces and a polypropylene film, and extruding the superposed grey cloth; controlling the unit pressure at 5-6 Mpa and the temperature at 165-175 ℃, keeping the temperature for 300min, and cooling to below 30 ℃ to obtain the epoxy glass cloth laminated board with the thickness of 5 mm.
Example 7
Placing 0.8 part of toluene in a reaction kettle, adding 1 part of a mixture of bisphenol diglycidyl ether epoxy resin and triphenol triglycidyl ether epoxy resin into the toluene under the condition of stirring, and then adding 0.3 part of tung oil anhydride to form a mixed solution; heating the mixed solution to 110 ℃ under the conditions of stirring and condensation, keeping the temperature until the mixed solution is clear and transparent, reacting for 60min, and cooling to below 50 ℃; and adding 0.2 part of acetone into the cooled mixed solution, and uniformly mixing to form an epoxy resin mixture.
0.67 parts of linear thermoplastic phenolic resin, 0.67 parts of thermosetting phenolic resin and 0.72 parts of magnesium hydroxide are added into the epoxy resin mixture under the condition of stirring, and the mixture is stirred for 2 to 4 hours to form the epoxy resin composition. After stirring for 2h, the molding time was measured and recorded using a knife at 160 ℃. + -. 2 ℃.
The resulting epoxy resin composition was impregnated with (210 g/m) 2 ) Glass fiber cloth is baked to prepare sized glass grey cloth, the sized glass grey cloth is stacked and weighed, and the thickness of the sized glass grey cloth is calculated, wherein the thickness of the sized glass grey cloth is preferably set to be 5mm;
superposing the grey cloth of the sized glass, placing the superposed grey cloth between two stainless steel plates with smooth surfaces and a polypropylene film, and extruding the superposed grey cloth; controlling the unit pressure at 5-6 Mpa and the temperature at 165-175 ℃, keeping the temperature for 300min, and cooling to below 30 ℃ to obtain the epoxy glass cloth laminated board with the thickness of 5 mm.
Example 8
Placing 0.875 part of toluene in a reaction kettle, adding 1 part of a mixture of bisphenol diglycidyl ether epoxy resin and triphenol triglycidyl ether epoxy resin to dimethylformamide under stirring, and then adding 0.4 part of a mixture of tung oil anhydride and 4' diamino diphenyl sulfone to form a mixed solution; heating the mixed solution to 110 ℃ under the conditions of stirring and condensation, keeping the temperature until the mixed solution is clear and transparent, reacting for 70min, and cooling to below 50 ℃; and adding 0.2 part of acetone into the cooled mixed solution, and uniformly mixing to form an epoxy resin mixture.
0.4 parts of linear thermoplastic phenolic resin, 0.4 parts of thermosetting phenolic resin and 0.65 parts of magnesium hydroxide are added into the epoxy resin mixture under the condition of stirring, and the mixture is stirred for 2 to 4 hours to form the epoxy resin composition. After stirring for 2h, the molding time was measured and recorded using a knife at 160 ℃. + -. 2 ℃.
The resulting epoxy resin composition was impregnated with (210 g/m) 2 ) Glass fiber cloth is baked to prepare sized glass grey cloth, the sized glass grey cloth is stacked and weighed, and the thickness of the sized glass grey cloth is calculated, wherein the thickness of the sized glass grey cloth is preferably set to be 5mm;
superposing the grey sized glass fabric, placing the superposed grey sized glass fabric between two stainless steel plates with smooth surfaces paved with polypropylene films, and extruding the superposed grey sized glass fabric; controlling the unit pressure at 5-6 Mpa and the temperature at 165-175 ℃, keeping the temperature for 300min, and cooling to below 30 ℃ to obtain the epoxy glass cloth laminated board with the thickness of 5 mm.
Comparative example 1
To test the beneficial effects of the epoxy resin compositions prepared in the present invention in the preparation of laminates, epoxy resins prepared in the prior art were used as controls: placing 0.45 part of dimethylformamide into a reaction kettle, adding 1 part of bisphenol diglycidyl ether epoxy resin into the dimethylformamide under the condition of stirring, and then adding 0.025 part of dicyandiamide serving as a curing agent and 0.0018 part of imidazole serving as an accelerator to form epoxy resin for a comparative example; after stirring for 2h, the molding time was measured and recorded using a knife at 160 ℃. + -. 2 ℃.
The resulting comparative example epoxy resin composition was impregnated with (210 g/m) 2 ) The method comprises the following steps of (1) preparing glass fiber cloth, baking the glass fiber cloth to obtain sized glass grey cloth, stacking the sized glass grey cloth, weighing the stacked glass grey cloth, and calculating the thickness of the sized glass grey cloth, wherein the thickness of the sized glass grey cloth is preferably set to be 5mm;
superposing the grey cloth of the sized glass, placing the superposed grey cloth between two stainless steel plates with smooth surfaces and a polypropylene film, and extruding the superposed grey cloth; controlling the unit pressure at 5-6 Mpa and the temperature at 165-175 ℃, keeping the temperature for 300min, and cooling to below 30 ℃ to obtain the epoxy glass cloth laminated board with the thickness of 5 mm.
The epoxy glass cloth laminates prepared in examples 1 to 8 and the epoxy glass cloth laminate prepared in comparative example 1 were tested for normal bending strength and 155 ℃ bending strength according to the test method GB/T5130-1997 for thermosetting resin industrial rigid laminates for electrical use. The molding time of the finally obtained epoxy resin composition, the production speed of the sized glass greige cloth, the degree of curing, i.e. the fluidity, and the running condition of the pressed laminated board were compared.
The fluidity test method comprises the following steps: the sizing glass grey cloth obtained under the condition that the temperature of a sizing oven, the vehicle speed and the glue content are the same is characterized in that 8 samples with the area of 100mm multiplied by 100mm are transversely taken along the sizing glass grey cloth, the weight is accurately 0.01g, the 8 samples are overlapped and then placed into a special press with the temperature controlled to be 160 +/-5 ℃ of fluidity, the pressure is controlled to be 2.5MPa, the samples are kept for 5-10 min, the samples are taken out, the glue edges are removed, and the samples are weighed, wherein the calculation method of the fluidity comprises the following steps:
wherein, W1 is the quality of the sized glass grey cloth before being put into the press, and W2 is the quality of the sized glass grey cloth after being pressed by the press.
The forming time testing method comprises the following steps: 1.2g of the finally obtained epoxy resin composition was placed on copper plates of 100mm X100 mm in area and 10mm in thickness, respectively, the temperature was controlled at 160. + -. 2 ℃ and stirred with a knife at a stirring speed of 60 to 100 times per minute, and the curing time was measured.
The grey cloth production speed testing method comprises the following steps: and the production speed is the same under the condition that the indexes of the fluidity of the grey cloth require the same at the same grey cloth production temperature.
The method for testing the flowing glue condition observes the flowing glue amount under the conditions of the same quality of sized glass grey cloth, the same pressing temperature and the same pressing time.
The comparative results are as follows:
in conclusion, the invention provides an epoxy resin composition, a preparation method and an epoxy glass cloth laminate, wherein the epoxy glass cloth laminate prepared from the epoxy resin composition has the bending strength of 409-424 Mpa, the bending strength of 125-288 Mpa at 155 ℃, the molding time of the epoxy resin composition at 160 ℃ is 1 '-51' -4 '-56', glue running hardly occurs during lamination, the production speed of a gray fabric can reach 10m/min, the epoxy glass cloth laminate has high curing degree and high curing speed during preparation, glue does not flow, further the thickness of the laminate can be effectively controlled according to design, the production efficiency is high, and the epoxy glass cloth laminate has very good economic benefits, and the problems that the heat-resistant temperature of the laminate is low at 155 ℃, the bending strength of the epoxy resin composition is long at 160 ℃, the curing degree of the epoxy gray fabric and the glass is low, the glue running is easy to occur during prepreg production, the production efficiency is low, and the thickness of the laminate is difficult to control in the prior art are solved, and are advanced technologies in the technical field of insulation material preparation.
The above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the technical solution of the present invention, and it should be understood by those skilled in the art that the technical solution can be modified and replaced by a plurality of simple modifications and replacements without departing from the spirit and principle of the present invention, and the modifications and replacements also fall into the protection scope covered by the claims.
Claims (10)
1. The epoxy resin composition is characterized by comprising the following raw material components in parts by weight: 1 part of polyfunctional epoxy resin, 0.1 to 0.67 part of linear thermoplastic phenolic resin, 0.1 to 0.67 part of thermosetting phenolic resin, 0.25 to 0.4 part of curing agent, 0.13 to 0.72 part of inorganic filler and 0.6 to 1.1 part of organic solvent;
the polyfunctional epoxy resin is one or more of bisphenol diglycidyl ether epoxy resin, triphenol triglycidyl ether epoxy resin, tetraphenol tetraglycidyl ether epoxy resin and diphenol phenylethane glycidyl ether epoxy resin.
2. The epoxy resin composition according to claim 1,
the linear thermoplastic phenolic resin is thermoplastic phenol formaldehyde resin;
the thermosetting phenolic resin is o-cresol formaldehyde resin and/or thermosetting phenol formaldehyde resin;
the inorganic filler is one or more of silicon micropowder, aluminum oxide, aluminum hydroxide, calcium carbonate and magnesium hydroxide;
the curing agent is dicyandiamide, phthalic anhydride, tung oil anhydride or 4'4 diamino diphenyl sulfone;
the organic solvent is one or more of toluene, methanol, xylene, acetone, dimethylformamide and ethanol.
3. The epoxy resin composition of claim 1, wherein the multifunctional epoxy resin comprises bisphenol diglycidyl ether epoxy resin, triphenol triglycidyl ether epoxy resin, tetraphenol tetraglycidyl ether epoxy resin, and diphenol ethylene glycidyl ether epoxy resin, and the mass ratio of bisphenol diglycidyl ether epoxy resin to triphenol triglycidyl ether epoxy resin to tetraphenol tetraglycidyl ether epoxy resin to diphenol ethylene glycidyl ether epoxy resin is 4.
4. The epoxy resin composition according to any one of claims 1 to 3, wherein the multifunctional epoxy resin has an epoxy equivalent of 220 to 250g/eq.
5. A process for preparing the epoxy resin composition according to any one of claims 1 to 4, comprising the steps of:
step 1): dissolving polyfunctional epoxy resin and a curing agent in an organic solvent to obtain an epoxy resin mixture;
step 2): the epoxy resin mixture, the linear thermoplastic phenolic resin, the thermosetting phenolic resin and the inorganic filler are uniformly mixed to prepare the epoxy resin composition.
6. The method for preparing an epoxy resin composition according to claim 5, wherein the specific operation of step 1) is:
step 1.1): dissolving polyfunctional epoxy resin and a curing agent in an organic solvent under the condition of stirring to form a mixed solution;
step 1.2): heating the mixed solution, keeping the temperature until the mixed solution is clear and transparent, reacting for 50-70 min, and cooling to below 50 ℃;
step 1.3): and adding an organic solvent into the cooled mixed solution, and uniformly mixing to form an epoxy resin mixture.
7. The process for producing an epoxy resin composition according to claim 6, wherein the temperature for the temperature increase and holding in step 1.2) is 100 to 110 ℃.
8. An epoxy glass cloth laminate comprising the epoxy resin composition according to any one of claims 1 to 4.
9. The epoxy glass cloth laminate of claim 8, wherein the epoxy glass cloth laminate has a flexural strength of 409 to 424Mpa and a flexural strength of 125 to 288Mpa at 155 ℃.
10. The epoxy glass cloth laminate according to claim 8 or 9, wherein the molding time of the epoxy resin composition at 160 ℃ is 1 '51' to 4 '56'.
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