CN115109385A - Epoxy resin composition for prepreg and preparation method thereof - Google Patents
Epoxy resin composition for prepreg and preparation method thereof Download PDFInfo
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- CN115109385A CN115109385A CN202110923601.XA CN202110923601A CN115109385A CN 115109385 A CN115109385 A CN 115109385A CN 202110923601 A CN202110923601 A CN 202110923601A CN 115109385 A CN115109385 A CN 115109385A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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- 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
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
- C08G59/60—Amines together with other curing agents with amides
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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
- C08G59/68—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 catalysts used
- C08G59/686—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 catalysts used containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2463/04—Epoxynovolacs
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention provides an epoxy resin composition for a prepreg and a preparation method thereof, wherein the epoxy resin composition for the prepreg comprises 60-90 parts of epoxy resin, 6-12 parts of a curing agent, 8-15 parts of an accelerator and 5-20 parts of a toughening agent; the epoxy resin consists of solid epoxy resin, semi-solid epoxy resin and liquid epoxy resin, and the curing agent consists of low molecular polyamide and diamino diphenyl sulfone; the prepreg epoxy resin composition has long room temperature storage period, and the prepared prepreg has no gel shortage phenomenon, perfect appearance, good high temperature resistance and strength, and can be applied to the fields of traffic, energy, aerospace, electronics, automobiles and the like.
Description
Technical Field
The invention relates to the field of resin-based composite materials (C08L63/00), in particular to an epoxy resin composition for a prepreg and a preparation method thereof.
Background
Prepreg is a composition of a resin matrix and a reinforcement made by impregnating continuous fibers or fabrics with the resin matrix under strictly controlled conditions, and is an intermediate material for making composite materials. Prepregs are classified into thermosetting prepregs and thermoplastic prepregs according to the type of matrix resin. Among them, epoxy resin has become the most commonly used matrix resin in thermosetting resin-based composite materials due to its good mechanical properties, dielectric properties, corrosion resistance, adhesion, wettability, low curing shrinkage and moderate price.
Chinese patent CN103450636A provides a flame-retardant epoxy resin/lignin/organic silicon composite material and a preparation method thereof, and the flame-retardant epoxy resin/lignin/organic silicon composite material has excellent mechanical properties and excellent flame-retardant performance. Chinese patent (CN201410155244.7) discloses a thermosetting resin composition, which comprises o-cresol novolac epoxy resin, linear phenol-formaldehyde resin, tetrabromobisphenol and an accelerator, and increases the toughness of a plate. However, excessive incorporation of tetrabromobisphenol A leads to deterioration of heat resistance and increase of water absorption of the sheet material.
Disclosure of Invention
In order to solve the problems, the invention provides an epoxy resin composition for a prepreg, which comprises 60-90 parts by weight of epoxy resin, 6-12 parts by weight of curing agent, 8-15 parts by weight of accelerator and 5-20 parts by weight of toughener, wherein the epoxy resin is selected from one or more of solid epoxy resin, semi-solid epoxy resin and liquid epoxy resin.
As a preferable technical solution, the solid epoxy resin is selected from one or more of bisphenol a type epoxy resin, o-cresol type novolac epoxy resin, bisphenol S type epoxy resin, and tetrafunctional group epoxy resin.
Further, the solid epoxy resin is preferably a bisphenol a type epoxy resin.
Further, the weight part of the solid epoxy resin is 30-40 parts.
Further, the epoxy equivalent of the solid epoxy resin is 500-2000.
As a preferred technical solution, the semi-solid epoxy resin is selected from one or more of bisphenol a type epoxy resin and phenol type novolac epoxy resin.
Further, the semi-solid epoxy resin is preferably a phenol novolac epoxy resin.
Further, the weight portion of the semi-solid epoxy resin is 10-20 portions.
As a preferable technical solution, the liquid epoxy resin is selected from one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, novolac type epoxy resin, and formaldehyde-novolac type epoxy resin.
Further, the liquid epoxy resin is preferably a bisphenol a type epoxy resin.
Further, the weight part of the liquid epoxy resin is 20-30 parts.
As a preferred technical scheme, the curing agent is selected from one or more of dicyandiamide, sulfur-containing urea ammonium, organic acid hydrazide, boron trifluoride-amine complex, diamino diphenyl sulfone, aliphatic amine, alicyclic amine and low-molecular polyamide.
Further, the curing agent is preferably diaminodiphenyl sulfone and low molecular polyamide.
Further, the low molecular polyamide is one selected from 200 low molecular polyamide, 203 low molecular polyamide, 650 low molecular polyamide and 651 low molecular polyamide.
Further, the low molecular polyamide is preferably 200 low molecular polyamide.
Further, the weight ratio of the low-molecular polyamide to the diamino diphenyl sulfone is (3-5): 1.
as a preferable technical solution, the accelerator is selected from one or more of organic ureas, polyetheramines, phosphines, imidazoles, and imidazole derivatives.
Further, the accelerator is preferably one of imidazole and an imidazole derivative.
Further, the imidazole and imidazole derivatives are preferably 2-ethyl-4-methylimidazole.
As a preferable technical scheme, the toughening agent is selected from one or more of core-shell particle type, epoxy-terminated nitrile rubber, carboxyl-terminated nitrile rubber, hydroxyl-terminated nitrile rubber, phenoxy resin and acrylate polymer.
Further, the toughening agent is preferably epoxy-terminated nitrile rubber.
In a second aspect, the present invention provides a method for preparing an epoxy resin composition for a prepreg, the method comprising:
(1) heating the semi-solid epoxy resin, the solid epoxy resin and the toughening agent to 90-120 ℃, stirring for dissolving, and then cooling to 40-60 ℃ for heat preservation to obtain a component A;
(2) mixing liquid epoxy resin, a curing agent and an accelerator, stirring for 10-60 min, and then grinding to obtain a component B;
(3) and stirring the component A and the component B at the temperature of 45-65 ℃ for 20-40 min to obtain the epoxy resin composition.
In a third aspect, the present invention provides a prepreg composite material containing the epoxy resin composition.
As a preferable technical scheme, the raw materials for preparing the prepreg composite material comprise the epoxy resin composition for the prepreg and a fiber material.
Further, the fiber is selected from one or more of polyethylene fiber, glass fiber, sisal fiber, carbon fiber, aramid fiber and aromatic polyamide fiber.
Further, the weight ratio of the epoxy composition for prepreg to the fiber material is 1: (1-2).
Has the advantages that:
(1) the curing agent, the accelerator, the toughening agent and the epoxy resin are mixed to prepare the epoxy resin composition for the prepreg, in the process of preparing the prepreg, the fiber material has good wettability in the epoxy resin composition for the prepreg, the bonding force between the fiber material and the epoxy resin composition is strong, and the resin is not easy to be pumped from the surface of the fiber, so that the prepared prepreg has no gel shortage phenomenon, perfect appearance, good high temperature resistance and strength, and can be applied to the fields of traffic, energy, aerospace, electronics, automobiles and the like.
(2) According to the invention, by adding the epoxy resins with different physical states, the compatibility among systems is increased, and the normal-temperature storage life of the epoxy resin composition for the prepreg is prolonged; the epoxy group content of the solid epoxy resin and the semi-solid epoxy resin is high, and the viscosity of the system can be adjusted; particularly, the epoxy equivalent of the solid epoxy resin is in the range of 500 to 2000, and when the epoxy equivalent is in the range, the adhesion with the fiber material is excellent, and the toughness is good. When the epoxy equivalent is less than 500, the prepreg has insufficient plastic deformability, and phase separation and insufficient toughness may occur. When the epoxy equivalent exceeds 2000, the heat resistance of the prepreg is insufficient, the viscosity of the epoxy resin composition is increased, and the fluidity is deteriorated. The liquid epoxy resin not only adjusts the viscosity of the system, but also can be used as a carrier of a curing agent and an accelerator to be ground together with the curing agent and the accelerator, so that the accelerating system is conveniently blended into the epoxy resin composition to generate a curing reaction.
(3) According to the invention, diaminodiphenyl sulfone and low molecular polyamide are added as curing agents, and particularly the weight ratio of the low molecular polyamide to the diaminodiphenyl sulfone is (3-5): 1, the prepreg can be cured at room temperature, and the heat resistance can be suitably improved while the toughness of the prepreg can be increased. Wherein, the long carbon chain in the low molecular polyamide can play a toughening role on the epoxy resin, and the existence of primary amine group, secondary amine group and amide group can be cured with the epoxy group; the sulfur atom in the diamino diphenyl sulfone molecular structure is in the highest oxidation state, and meanwhile, the sulfone group changes the electron cloud density of a benzene ring, so that when a large amount of heat energy and radiation energy are absorbed, the electron cloud density can be dissipated through a high-resonance state of the diphenyl sulfone group without chain fracture and crosslinking, and the heat resistance, the thermal oxidation stability and the room-temperature storage period of the epoxy resin are enhanced.
(4) According to the invention, 2-ethyl-4-methylimidazole is added as an accelerator, active hydrogen of secondary amine on 2-ethyl-4-methylimidazole can be added with epoxy group, and the generated product and another epoxy group generate a complex with both positive and negative ions in molecules. The negative ions in the complex can be used as an active center for catalyzing the ring opening of the epoxy group to carry out homopolymerization, and react with the curing agent and other epoxy groups to form a more complete cross-linking structure, so that the epoxy resin complex has higher heat resistance.
(5) The epoxy resin composition for the prepreg has the advantages of simple and easily obtained raw materials, low cost, simple process operation, short curing time, suitability for rapid large-scale production, capability of effectively solving the problems of low heat resistance, poor toughness, short room-temperature storage period and the like of the conventional cured product.
Detailed Description
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Example 1
Embodiment 1 of the present invention provides an epoxy resin composition for a prepreg, which is prepared from, by weight, 30 parts of a bisphenol a type solid epoxy resin, 20 parts of a phenol novolac epoxy resin, 20 parts of a bisphenol a type liquid epoxy resin, 6 parts of a curing agent, 8 parts of 2-ethyl-4-methylimidazole, and 20 parts of epoxy-terminated nitrile rubber.
The weight ratio of 200 low molecular weight polyamide to diamino diphenyl sulfone in the curing agent is 5: 1;
bisphenol a type solid epoxy resin purchased from caston EPON resin 1004F, usa, having an epoxy equivalent of 800;
the phenol novolac epoxy resin is purchased from DEN431 in Olin orchidaceae chemical industry, and has an epoxy equivalent of 172-179;
the bisphenol A type liquid epoxy resin is purchased from NPEL-128 of south Asia plastic industry GmbH, and the epoxy equivalent is 184-190;
diamino diphenyl sulfone CAS number: 80-08-0;
200 low molecular polyamide CAS No.: 70024-79-2;
2-ethyl-4-methylimidazole CAS no: 931 to 36-2;
the epoxy-terminated nitrile rubber is available from DeVott chemical technology, Inc. of Beijing;
the preparation method comprises the following steps: (1) heating bisphenol A type solid epoxy resin, phenol type novolac epoxy resin and epoxy-terminated butadiene-acrylonitrile rubber to 90 ℃, stirring for dissolving, and then cooling to 60 ℃ for heat preservation to obtain a component A;
(2) mixing bisphenol A type liquid epoxy resin, a curing agent and 2-ethyl-4-methylimidazole, stirring for 10min, and then grinding to obtain a component B;
(3) and stirring the component A and the component B for 40min at 45 ℃ to obtain the epoxy resin composition.
Example 2
Embodiment 2 of the present invention provides an epoxy resin composition for a prepreg, which is prepared from, by weight, 35 parts of a bisphenol a type solid epoxy resin, 15 parts of a phenol novolac epoxy resin, 25 parts of a bisphenol a type liquid epoxy resin, 10 parts of a curing agent, 11 parts of 2-ethyl-4-methylimidazole, and 12 parts of epoxy-terminated nitrile rubber.
The weight ratio of 200 low molecular weight polyamide to diaminodiphenyl sulfone in the curing agent is 4: 1;
bisphenol a type solid epoxy resin purchased from caston EPON resin 1004F, usa, having an epoxy equivalent of 800;
the phenol novolac epoxy resin is purchased from DEN431 in Olin orchidaceae chemical industry, and has an epoxy equivalent of 172-179;
the bisphenol A type liquid epoxy resin is purchased from NPEL-128 of south Asia plastic industry GmbH, and the epoxy equivalent is 184-190;
the preparation method comprises the following steps: (1) heating bisphenol A type solid epoxy resin, phenol type novolac epoxy resin and epoxy-terminated butadiene-acrylonitrile rubber to 100 ℃, stirring for dissolving, and then cooling to 50 ℃ for heat preservation to obtain a component A;
(2) mixing bisphenol A liquid epoxy resin, a curing agent and 2-ethyl-4-methylimidazole, stirring for 45min, and grinding to obtain a component B;
(3) and stirring the component A and the component B for 30min at 55 ℃ to obtain the epoxy resin composition.
Example 3
Embodiment 3 of the present invention provides an epoxy resin composition for a prepreg, which is prepared from, by weight, 40 parts of a bisphenol a type solid epoxy resin, 10 parts of a phenol novolac epoxy resin, 30 parts of a bisphenol a type liquid epoxy resin, 12 parts of a curing agent, 15 parts of 2-ethyl-4-methylimidazole, and 5 parts of epoxy-terminated nitrile rubber.
The weight ratio of 200 low molecular weight polyamide to diaminodiphenyl sulfone in the curing agent is 3: 1;
bisphenol a type solid epoxy resin purchased from caston EPON resin 1004F, usa, having an epoxy equivalent of 800;
the phenol novolac epoxy resin is purchased from DEN431 of Olin orchidaceae chemical industry, and has an epoxy equivalent of 172-179;
the bisphenol A type liquid epoxy resin is purchased from NPEL-128 of south Asia plastic industry GmbH, and the epoxy equivalent is 184-190;
the preparation method comprises the following steps: (1) heating bisphenol A type solid epoxy resin, phenol type novolac epoxy resin and epoxy-terminated butadiene-acrylonitrile rubber to 120 ℃, stirring for dissolving, and then cooling to 40 ℃ for heat preservation to obtain a component A;
(2) mixing bisphenol A type liquid epoxy resin, a curing agent and 2-ethyl-4-methylimidazole, stirring for 60min, and then grinding to obtain a component B;
(3) and stirring the component A and the component B at 65 ℃ for 20min to obtain the epoxy resin composition.
Comparative example 1
The invention provides a comparative example 1 of an epoxy resin composition for a prepreg, which is prepared from the following raw materials, by weight, 35 parts of bisphenol A type solid epoxy resin, 15 parts of phenol novolac epoxy resin, 25 parts of bisphenol A type liquid epoxy resin, 10 parts of diaminodiphenyl sulfone, 11 parts of 2-ethyl-4-methylimidazole and 12 parts of epoxy terminated butadiene-acrylonitrile rubber.
Bisphenol a type solid epoxy resin purchased from caston EPON resin 1004F, usa, having an epoxy equivalent of 800;
the phenol novolac epoxy resin is purchased from DEN431 of Olin orchidaceae chemical industry, and has an epoxy equivalent of 172-179;
the bisphenol A liquid epoxy resin is purchased from NPEL-128 of south Asia plastic industry GmbH, and the epoxy equivalent is 184-190;
the preparation method comprises the following steps: (1) heating bisphenol A type solid epoxy resin, phenol type novolac epoxy resin and epoxy-terminated butadiene-acrylonitrile rubber to 100 ℃, stirring for dissolving, and then cooling to 50 ℃ for heat preservation to obtain a component A;
(2) mixing bisphenol A type liquid epoxy resin, diamino diphenyl sulfone and 2-ethyl-4-methylimidazole, stirring for 45min, and grinding to obtain a component B;
(3) and stirring the component A and the component B for 30min at 55 ℃ to obtain the epoxy resin composition.
Comparative example 2
The invention provides a comparative example 2 of an epoxy resin composition for prepreg, which is prepared from the following raw materials, by weight, 35 parts of bisphenol A type solid epoxy resin, 15 parts of phenol novolac epoxy resin, 25 parts of bisphenol A type liquid epoxy resin, 10 parts of 200 low-molecular polyamide, 11 parts of 2-ethyl-4-methylimidazole and 12 parts of epoxy-terminated butadiene-acrylonitrile rubber.
Bisphenol a type solid epoxy resin purchased from caston EPON resin 1004F, usa, having an epoxy equivalent of 800;
the phenol novolac epoxy resin is purchased from DEN431 of Olin orchidaceae chemical industry, and has an epoxy equivalent of 172-179;
the bisphenol A type liquid epoxy resin is purchased from NPEL-128 of south Asia plastic industry GmbH, and the epoxy equivalent is 184-190;
the preparation method comprises the following steps: (1) heating bisphenol A type solid epoxy resin, phenol type novolac epoxy resin and epoxy-terminated butadiene-acrylonitrile rubber to 100 ℃, stirring for dissolving, and then cooling to 50 ℃ for heat preservation to obtain a component A;
(2) mixing bisphenol A type liquid epoxy resin, 200 low molecular weight polyamide and 2-ethyl-4-methylimidazole, stirring for 45min, and grinding to obtain a component B;
(3) and stirring the component A and the component B at 55 ℃ for 30min to obtain the epoxy resin composition.
Performance testing
The epoxy resin compositions for prepregs prepared in examples 1 to 3 and comparative examples 1 to 2 were subjected to the following performance tests. The test results are shown in Table 1.
1. And (3) viscosity testing: 30g of the epoxy resin composition for prepreg was charged into a glass tube, heated in a water bath to raise the temperature, a rotational viscometer was inserted into the glass tube, and the viscosity on the viscometer was read and recorded. And (4) stopping the viscosity test until the sample is heated at the temperature of about 95 +/-2 ℃ and the viscosity rises sharply to cause a curing reaction.
2. Gel time test: 1g of the epoxy resin composition was placed on a GT-2 type gel time measuring apparatus at a temperature of 110 ℃ by a wire drawing method, and the time was recorded.
3. Normal temperature storage period: the longest pot life is obtained when the tack of the epoxy resin composition for prepregs disappears.
Respectively spreading the epoxy resin compositions for the prepregs prepared in the examples 1-3 and the comparative examples 1-2 on glass fibers after hot melting at 70 ℃, wherein the weight ratio of the epoxy resin composition for the prepregs to the glass fibers is 1: 1; and then, curing and forming at 150 ℃ for 5min by adopting a die pressing process to obtain a cured and formed product, and respectively carrying out product appearance quality test and warp-direction tensile strength test. The test results are shown in Table 1.
1. And (3) testing the appearance quality of the product: the appearance of the resulting cured molded product was recorded.
2. Tensile strength in the warp direction: testing was performed according to astm d 3039.
TABLE 1
Claims (10)
1. The epoxy resin composition for the prepreg is characterized by comprising, by weight, 60-90 parts of epoxy resin, 6-12 parts of a curing agent, 8-15 parts of an accelerator and 5-20 parts of a toughening agent, wherein the epoxy resin is selected from one or more of solid epoxy resin, semi-solid epoxy resin and liquid epoxy resin.
2. The epoxy resin composition for a prepreg according to claim 1, wherein the epoxy equivalent of the solid epoxy resin is 500 to 2000.
3. The epoxy resin composition for prepreg according to claim 1, wherein the curing agent is one or more selected from dicyandiamide, sulfur-containing urea ammonium, organic acid hydrazide, boron trifluoride-amine complex, diaminodiphenyl sulfone, aliphatic amine, alicyclic amine, and low molecular weight polyamide.
4. The epoxy resin composition for a prepreg according to claim 3, wherein the curing agent is diaminodiphenyl sulfone and a low-molecular polyamide.
5. The epoxy resin composition for a prepreg according to claim 4, wherein the weight ratio of the diaminodiphenyl sulfone to the low-molecular polyamide is (3 to 5): 1.
6. the epoxy resin composition for prepreg according to claim 1, wherein the accelerator is one or more selected from the group consisting of organic ureas, polyetheramines, phosphines, imidazoles, and imidazole derivatives.
7. The epoxy resin composition for a prepreg according to claim 6, wherein the accelerator is one selected from imidazole and an imidazole derivative.
8. The epoxy resin composition for prepreg according to claim 1, wherein the toughening agent is one or more selected from the group consisting of core-shell particles, epoxy-terminated nitrile rubbers, carboxyl-terminated nitrile rubbers, hydroxyl-terminated nitrile rubbers, phenoxy resins, and acrylate polymers.
9. A method for producing the epoxy resin composition for prepreg according to any one of claims 1 to 8, characterized by comprising the steps of:
(1) heating the semi-solid epoxy resin, the solid epoxy resin and the toughening agent to 90-120 ℃, stirring for dissolving, then cooling to 40-60 ℃, and preserving heat to obtain a component A;
(2) mixing liquid epoxy resin, a curing agent and an accelerator, stirring for 10-60 min, and then grinding to obtain a component B;
(3) and stirring the component A and the component B at the temperature of 45-65 ℃ for 20-40 min to obtain the epoxy resin composition.
10. A prepreg composite material produced from the epoxy resin composition for prepregs according to any one of claims 1 to 8 and a fibrous material as raw materials.
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