CN112390936B - Toughened epoxy resin composition for winding forming and preparation method thereof - Google Patents
Toughened epoxy resin composition for winding forming and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4284—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with other curing agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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Abstract
The invention relates to a toughening epoxy resin composition for winding forming and a preparation method thereof, and mainly solves the technical problem that the heat resistance is reduced while the toughness of a winding resin matrix is improved in the prior art. The invention adopts a toughening epoxy resin composition for winding forming, which comprises the following components in parts by mass: 1) 100 parts of an epoxy resin mixture; 2) 55-150 parts of a curing agent; 3) 0.1-10 parts of an accelerator; wherein the epoxy resin mixture contains 70-100 parts of liquid epoxy resin and 0-30 parts of diluent; the curing agent is characterized by being a bisphenol compound modified anhydride curing agent, better solving the problem and being applicable to fiber winding forming industrial application of various composite material pressure vessels.
Description
Technical Field
The invention belongs to the field of composite material manufacturing, and particularly relates to a toughening epoxy resin composition for winding forming and a preparation method thereof.
Background
The composite material pressure vessel has the advantages of light weight, high specific strength, good fatigue resistance, good corrosion resistance and the like, is gradually replacing heavy steel pressure vessels, and is applied to the fields of automobiles, fire fighting, medical treatment, hydrogen storage, oil and gas transportation and the like. The winding forming is a main production process of the composite material pressure container, and has the advantages of high fiber content, realization of equal-strength structural design, stable quality, easiness in automatic production and the like. The fiber winding forming method is divided into wet winding, dry winding and semi-dry winding according to the process, wherein the wet winding is the forming method with the widest application range at present.
Matrix resins commonly used for winding are unsaturated polyesters and epoxy resins. The unsaturated polyester has the outstanding advantages of low viscosity, low price, high gelling speed and low comprehensive performance of a cured product, and is mainly applied to the field of civil low-pressure structural materials with low requirements; the epoxy resin has good mechanical property, adhesion, chemical corrosion resistance, low shrinkage and the like, and is a matrix resin which is preferably considered for high-performance resin matrix composite materials. However, the non-toughened epoxy resin is brittle, and easily generates internal defects when subjected to external impact, and cannot well exert the strength required by the high-performance fiber. The development of a resin matrix for winding molding having high modulus and high toughness without excessively lowering the heat resistance of the resin has been a focus of research.
From literature and published patent analysis, CN201310031083.6 provides a method for improving the toughness of prepregs by using polyurethane modified epoxy resin as toughening agent, and the epoxy resin system utilizes the high bonding strength and impact resistance of polyurethane modified epoxy resin, endows the prepregs with high interlaminar shear strength, and improves the toughness of composite materials. However, the addition of the urethane-modified epoxy significantly lowers the heat resistance of the epoxy resin system, resulting in T of the cured product thereof g And is significantly reduced.
Patent CN201310032354.X discloses a preparation method of dimer acid modified epoxy resin toughened carbon fiber prepreg, which improves the wettability of a resin matrix on carbon fibers and improves the toughness of a composite material. The tensile strength of the resin matrix casting body is close to 70MPa, and the interlaminar shear strength of the composite material exceeds 70MPa. But the patent does not disclose data on impact strength.
Disclosure of Invention
One of the technical problems to be solved by the invention is that the existing epoxy resin matrix for fiber winding molding is poor in toughness and short in fatigue life, the heat resistance is reduced while the toughness is improved, and the toughened epoxy resin composition for winding molding is provided.
The second technical problem to be solved by the present invention is to provide a method for preparing a toughening resin matrix for winding corresponding to the first technical problem.
The third technical problem to be solved by the invention is to provide an application method of the toughening resin matrix for winding corresponding to one of the technical problems.
In order to solve one of the technical problems, the invention adopts the following technical scheme: the toughened epoxy resin composition for winding forming comprises the following components in parts by mass:
1) 100 parts of an epoxy resin mixture;
2) 55-150 parts of a curing agent;
3) 0.1 to 10 portions of accelerant;
wherein the epoxy resin mixture contains 70-100 parts of liquid epoxy resin and 0-30 parts of diluent; the curing agent is bisphenol compound modified anhydride curing agent.
The curing agent is characterized in that the molar ratio (0.05-0.5) of the bisphenol compound to the anhydride curing agent in the curing agent is 1.
In the above embodiment, the acid anhydride curing agent is preferably at least one selected from nadic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylene glycol bistrimellitic anhydride, and polysebacic anhydride.
In the above technical solution, the bisphenol compound is preferably at least one selected from the group consisting of diphenol, diphenol propane (bisphenol a), diphenol methane, diphenol sulfone, diphenol ether, diphenol, naphthalenediol, and derivatives thereof containing an alkyl group or a halogen atom in the ring.
In the above technical solution, the liquid epoxy resin mixture is preferably at least one of bisphenol a epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, and glycidyl amine epoxy resin.
In the above technical solution, the diluent is preferably at least one of n-butyl glycidyl ether, polypropylene glycol diglycidyl ether, and diglycidyl aniline.
In the above technical solution, the accelerator is preferably at least one of a quaternary phosphonium salt having a structure represented by formula (I) or a phosphine compound having a structure represented by formula (II),
in the formula, R 1 ～R 7 Each represents at least one hydrocarbon group having 1 to 22 carbon atoms, and X-represents at least one fluoride anion, chloride anion, bromide anion, iodide anion, hydroxide anion, acetate anion, oxalate anion, benzenesulfonate anion, tetrafluoroborate anion, or tetraphenylborate anion.
In the above technical scheme, the modifying method of the curing agent is preferably obtained by mixing the bisphenol compound with an anhydride curing agent for not less than 20min at the temperature of 60-120 ℃ and the humidity of less than 60%.
In order to solve the second technical problem, the invention adopts the technical scheme that: a method for preparing a toughened epoxy resin matrix for winding according to any one of the above technical solutions, comprising the steps of:
(1) Mixing bisphenol compounds and anhydride curing agents according to a molar ratio (0.05-0.5) of 1 at 60-120 ℃ and humidity lower than 60% for not less than 20min to obtain modified curing agents;
(2) And stirring and defoaming the epoxy resin mixture, the modified curing agent and the accelerator completely and uniformly mixing to obtain the toughened epoxy resin composition for winding forming.
In order to solve the third technical problem, the invention adopts the technical scheme that: an application method of the toughening epoxy resin matrix for winding in any technical scheme for solving the technical problems.
In the above technical solutions, the application is not limited in particular, and those skilled in the art can use the technology according to the prior art, for example, but not limited to, the technology and products for winding and forming carbon fiber.
The toughened epoxy resin composition for winding forming and the preparation method thereof have the advantages that:
(1) The impact property of the resin system is improved by adopting the bisphenol compound modified anhydride curing agent, and the heat resistance of the resin system is kept;
(2) The active diluent is adopted to reduce the viscosity of the resin matrix, prolong the service life of the resin matrix, improve the winding process performance of the resin matrix, have simple preparation process and no harsh requirements on production environment, and are convenient for industrial production.
By adopting the technical scheme of the invention, the obtained toughened epoxy resin composition for winding forming has good matrix toughness and strong impact resistance, the elongation at break can reach more than 7.5 percent, and the impact strength can reach 58KJ/m 2 Above, T g The viscosity is less than 1 Pa.s at the temperature of higher than 120 ℃, the working life is longer than 8 hours, and better technical effects are achieved.
The invention is further illustrated by the following examples.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
The examples and comparative examples relate to the following main raw materials:
bisphenol a type liquid epoxy resin: CYD-128, barnyard petrifaction;
bisphenol a type liquid epoxy resin: 332, DOW chemistry;
bisphenol F type liquid epoxy resin: 354,DOW chemistry;
polypropylene glycol diglycidyl ether: DY3601, huntsman corporation;
butanediol diglycidyl ether: new remote company of Anhui province
Bisphenol a (BPA): shandong polycosan chemical Co., ltd;
bisphenol F (BPF): a group of national drugs;
tetrabromobisphenol a (tbrppa): shandong Aner chemical Co., ltd;
methyltetrahydrophthalic anhydride: anhuo Puyang Pucheng electronics corporation;
methylhexahydrophthalic anhydride: anhuo Puyang Pucheng electronics corporation;
methyl nadic anhydride: anhuohuoyang Pucheng electronics corporation;
triphenylphosphine: the group of national medicine.
[ example 1 ] A method for producing a polycarbonate
The resin matrix comprises the following components in percentage by mass:
liquid bisphenol a epoxy resin 332:90 parts of a mixture;
diluent polypropylene glycol diglycidyl ether DY3601:10 parts of a binder;
curing agent: 106 parts of methyl nadic anhydride, wherein the weight part of the methyl nadic anhydride is 96 parts, and the weight part of bisphenol A is 10 parts;
promoter triphenylphosphine: 0.5 part.
The process comprises the following steps:
1) Adding 96 parts of methyl nadic anhydride and 10 parts of bisphenol compounds into a reaction vessel, stirring at 70 ℃ to completely dissolve bisphenol A in the methyl nadic anhydride, preserving the temperature for 30 minutes, and cooling to below 30 ℃ to obtain a curing agent system.
(2) An epoxy resin mixture of 90 parts of liquid bisphenol a epoxy resin 332 and 10 parts of polypropylene glycol diglycidyl ether DY3601 and 0.5 part of triphenylphosphine accelerator were added to the above system, stirred, defoamed completely, and mixed uniformly to obtain an epoxy resin composition.
The performance test method and the execution standard of the epoxy resin composition and the condensate thereof are as follows:
1) Viscosity of resin matrix: the method is carried out on a rotary viscometer of LVDV-III type of Brookfield company in the United states according to GB/T22314-2008 standard;
2) Pot life of the resin matrix: the method is carried out on an LVDV-III type rotary viscometer of the Brookfield company in the United states according to the standard requirement of GB/T7123.1-7123.2-2002, and the time for the viscosity of the system to reach twice of the initial viscosity at the test temperature is taken as the pot life of the system at the temperature;
5) Tensile Properties of cured products: the method is carried out on a universal testing machine of Instron corporation in the United states according to the requirements of ASTM D638 standard, and the tensile rate is 5mm/min;
6) Bending property of cured product: the method is carried out on a universal testing machine of Kinston company in the United states according to the ASTM D790 standard, and the testing speed is 2mm/min;
7) The non-gap impact strength of the cured simply supported beam is as follows: the method is carried out on a Resil pendulum impact tester of Ceast Italy according to the GB/T2567-2008 standard, the pendulum impact energy is 5J, and the impact speed is 2.9m/s;
8) T of cured product g : the method is carried out on a Q800 type dynamic mechanical property analyzer of the American TA company, and a single cantilever mode is adopted during testing, the temperature rise speed is 3 ℃/min, the temperature measuring range is RT-250 ℃, and the method is selected
The peak temperature of (a) is defined as T of a cured product g 。
The test results are shown in Table 1.
[ example 2 ]
The resin matrix comprises the following components in percentage by mass:
liquid bisphenol F epoxy resin 354:95 parts of (1);
diluent polypropylene glycol diglycidyl ether DY3601:5 parts of a mixture;
curing agent: 114 parts of methylhexahydrophthalic anhydride and 20 parts of bisphenol A, wherein the methylhexahydrophthalic anhydride is 94 parts;
promoter ethyl triphenyl phosphonium bromide: 1.0 part.
Referring to example 1, the epoxy resin composition and the cured product thereof were tested for properties in the same manner as in example 1, and the test results are shown in Table 1.
[ example 3 ]
The resin matrix comprises the following components in percentage by mass:
liquid bisphenol a epoxy resin 332:80 parts of a binder;
diluent butanediol diglycidyl ether: 20 parts of (1);
curing agent: 115 parts of methyl nadic anhydride and 15 parts of tetrabromobisphenol A, wherein the parts by weight of the methyl nadic anhydride are 100 parts;
promoter triphenylphosphine: 0.7 part.
Referring to example 1, the epoxy resin composition and the cured product thereof were tested for properties in the same manner as in example 1, and the test results are shown in Table 1.
[ example 4 ] A method for producing a polycarbonate
The resin matrix comprises the following components in percentage by mass:
liquid bisphenol F epoxy resin 354:100 parts of (A);
curing agent: 113 parts, wherein the methyl nadic anhydride is 103 parts, and the tetrabromobisphenol A is 10 parts;
promoter ethyl triphenyl phosphonium bromide: 1.0 part.
Referring to example 1, the epoxy resin composition and the cured product thereof were tested for properties in the same manner as in example 1, and the test results are shown in Table 1.
[ example 5 ]
The resin matrix comprises the following components in percentage by mass:
liquid bisphenol a epoxy resin 332:95 parts of (C);
diluent polypropylene glycol diglycidyl ether DY3601:5 parts of a mixture;
curing agent: 110 parts of methyl nadic anhydride and 10 parts of bisphenol A, wherein the weight parts of the methyl nadic anhydride are 100 parts;
promoter triphenylphosphine: 0.7 part.
Referring to example 1, the epoxy resin composition and the cured product thereof were tested for properties in the same manner as in example 1, and the test results are shown in Table 1.
[ example 6 ] A method for producing a polycarbonate
The resin matrix comprises the following components in percentage by mass:
liquid bisphenol a epoxy resin CYD-128:95 parts of (C);
diluent butanediol diglycidyl ether: 5 parts of a mixture;
curing agent: 102 parts of methylhexahydrophthalic anhydride and 10 parts of bisphenol A, wherein the total weight of the components is 92 parts;
promoter triphenylphosphine: 1.5 parts.
Referring to example 1, the epoxy resin composition and the cured product thereof were tested for properties in the same manner as in example 1, and the test results are shown in Table 1
[ example 7 ]
The resin matrix comprises the following components in percentage by mass:
liquid bisphenol a epoxy resin CYD-128:90 parts of a mixture;
diluent butanediol diglycidyl ether: 10 parts of a binder;
curing agent: 115 parts, wherein the content of methylhexahydrophthalic anhydride is 95 parts, and the content of bisphenol A is 20 parts;
promoter triphenylphosphine: 1.2 parts.
Referring to example 1, the method for testing the properties of the epoxy resin composition and the cured product thereof was the same as in example 1, and the test results are shown in Table 1
[ example 8 ]
The resin matrix comprises the following components in percentage by mass:
liquid bisphenol a epoxy resin CYD-128:80 parts of a mixture;
diluent butanediol diglycidyl ether: 20 parts of (1);
curing agent: 129 parts, wherein the methyl hexahydrophthalic anhydride accounts for 99 parts, and the bisphenol A accounts for 30 parts;
promoter triphenylphosphine: 1.2 parts.
Referring to example 1, the method for testing the properties of the epoxy resin composition and the cured product thereof was the same as in example 1, and the test results are shown in Table 1
[ example 9 ]
The resin matrix comprises the following components in percentage by mass:
liquid bisphenol a epoxy resin CYD-128:90 parts of a mixture;
diluent butanediol diglycidyl ether: 10 parts of (A);
curing agent: 115 parts, wherein the content of methylhexahydrophthalic anhydride is 95 parts, and the content of bisphenol F is 20 parts;
promoter triphenylphosphine: 1.2 parts.
Referring to example 1, the method for testing the properties of the epoxy resin composition and the cured product thereof was the same as in example 1, and the test results are shown in Table 1
[ example 10 ] A method for producing a polycarbonate
The resin matrix comprises the following components in percentage by mass:
liquid bisphenol a epoxy resin CYD-128:80 parts of a mixture;
diluent butanediol diglycidyl ether: 20 parts of (1);
curing agent: 129 parts, wherein the methyl hexahydrophthalic anhydride accounts for 99 parts, and the bisphenol F accounts for 30 parts;
promoter triphenylphosphine: 1.2 parts.
The procedure was the same as in example 1, the method for testing the properties of the epoxy resin composition and the cured product thereof was the same as in example 1, and the test results are shown in Table 1
[ COMPARATIVE EXAMPLE 1 ]
The resin matrix comprises the following components in percentage by mass:
liquid bisphenol a epoxy resin 332:95 parts of (1);
diluent polypropylene glycol diglycidyl ether DY3601:5 parts of a mixture;
98 portions of curing agent methyl nadic anhydride;
promoter triphenylphosphine: 0.7 part.
The process comprises the following steps:
1) And adding the anhydride curing agent, the epoxy resin mixture and the accelerator into a reaction vessel, stirring and defoaming completely, and mixing uniformly to obtain the epoxy resin composition.
The epoxy resin composition and the cured product thereof were tested for the same properties as in example 1, and the test results are shown in Table 1.
[ COMPARATIVE EXAMPLE 2 ]
The resin matrix comprises the following components in percentage by mass:
liquid bisphenol a epoxy resin CYD-128:80 parts of a mixture;
diluent butanediol diglycidyl ether: 20 parts of (1);
97 parts of curing agent methylhexahydrophthalic anhydride;
promoter triphenylphosphine: 1.2 parts.
The epoxy resin composition and the cured product thereof were tested for the same properties as in example 1, and the test results are shown in Table 1.
TABLE 1
Claims (6)
1. The toughened epoxy resin composition for winding forming comprises the following components in parts by mass:
1) 100 parts of an epoxy resin mixture;
2) 55 to 150 parts of a curing agent;
3) 0.1 to 10 parts of an accelerator;
wherein the epoxy resin mixture contains 70 to 100 parts of liquid epoxy resin and 0 to 30 parts of diluent; the curing agent is bisphenol compound modified anhydride curing agent; the modification method of the curing agent is to mix the bisphenol compound with an anhydride curing agent for not less than 20min under the conditions of 60 to 120 ℃ and humidity lower than 60%;
the acid anhydride curing agent is at least one selected from nadic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylene glycol bistrimellitic anhydride and polysebacic anhydride;
the bisphenol compound is at least one of diphenol, diphenol propane, diphenol methane, diphenol sulfone, diphenol ether, diphenol, naphthalenediol and derivatives thereof containing alkyl or halogen atoms on the ring;
the accelerant is at least one of quaternary phosphonium salt with a structure shown in a formula (I) or phosphine compound with a structure shown in a formula (II),
in the formula, R 1 ~R 7 Each represents at least one hydrocarbon group having 1 to 22 carbon atoms, X-represents a fluoride anion, a chloride anion, a bromide anion, an iodide anion,At least one of hydroxide anion, acetic acid anion, oxalic acid anion, benzenesulfonic acid anion, tetrafluoroboric acid anion and tetraphenylboronic acid anion.
2. The toughened epoxy resin composition for winding molding according to claim 1, wherein the molar ratio of the bisphenol compound to the acid anhydride curing agent in the curing agent (0.05 to 0.5) is 1.
3. The toughened epoxy resin composition for winding molding according to claim 1, wherein said liquid epoxy resin is at least one of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a novolac epoxy resin, and a glycidylamine epoxy resin.
4. The toughened epoxy resin composition for winding molding as claimed in claim 1, wherein said diluent is at least one of n-butyl glycidyl ether, polypropylene glycol diglycidyl ether and diglycidyl aniline.
5. A method for preparing the toughened epoxy resin composition for winding forming of any one of claims 1 to 4, comprising the steps of:
(1) Mixing an anhydride curing agent and a bisphenol compound with the anhydride curing agent for not less than 20min according to the molar ratio of an anhydride group to a phenolic hydroxyl group (0.05-0.5) of 1 under the conditions of 60-120 ℃ and humidity lower than 60 percent to obtain the curing agent;
(2) And stirring and defoaming the epoxy resin mixture, the curing agent and the accelerator completely and uniformly mixing to obtain the toughened epoxy resin composition for winding forming.
6. The use of the toughened epoxy resin composition as claimed in any one of claims 1 to 4 in a carbon fiber winding process and a product.
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| CN113897032B (en) * | 2021-09-22 | 2024-01-19 | 山西宇德新材料科技有限公司 | Epoxy resin composite material for fiber winding and preparation method thereof |
| CN114395219A (en) * | 2022-01-17 | 2022-04-26 | 南通中集能源装备有限公司 | Hydrogen storage bottle, liquid epoxy resin system wound by wet method and preparation method thereof |
| CN116003967A (en) * | 2022-12-23 | 2023-04-25 | 国网智能电网研究院有限公司 | High-heat-conductivity epoxy composition, cured product, and preparation method and application thereof |
| CN115926110A (en) * | 2022-12-29 | 2023-04-07 | 江苏扬农锦湖化工有限公司 | Modified epoxy resin and preparation method and application thereof |
| CN117247660A (en) * | 2023-10-08 | 2023-12-19 | 北京科泰克科技有限责任公司 | Epoxy resin composition for winding and preparation method and application thereof |
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