CN110791053A - Epoxy resin composition containing microcapsule curing agent, and prepreg and composite material thereof - Google Patents

Epoxy resin composition containing microcapsule curing agent, and prepreg and composite material thereof Download PDF

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Publication number
CN110791053A
CN110791053A CN201911118414.3A CN201911118414A CN110791053A CN 110791053 A CN110791053 A CN 110791053A CN 201911118414 A CN201911118414 A CN 201911118414A CN 110791053 A CN110791053 A CN 110791053A
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China
Prior art keywords
curing agent
epoxy resin
resin composition
microcapsule
microcapsule curing
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CN201911118414.3A
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Chinese (zh)
Inventor
许虹霞
李克
黄宜帆
任华
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Xi'an Long Technology & Development Co Ltd
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Xi'an Long Technology & Development Co Ltd
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Priority to CN201911118414.3A priority Critical patent/CN110791053A/en
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    • 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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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/10—Next to a fibrous or filamentary layer
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
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    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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    • 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
    • C08G59/188—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 using encapsulated compounds
    • 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
    • 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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    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
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Abstract

The invention discloses an epoxy resin composition containing a microcapsule curing agent, and a prepreg and a composite material thereof, wherein the epoxy resin composition comprises the microcapsule curing agent, epoxy resin and a diluent, and the weight parts of the components are as follows: the epoxy resin curing agent comprises 80-100 parts of epoxy resin, 15-30 parts of a microcapsule curing agent and 10-20 parts of a diluent, wherein the microcapsule curing agent consists of a thermoplastic shell and the epoxy resin curing agent, the epoxy resin curing agent is wrapped inside the thermoplastic shell, and the particle size of the microcapsule curing agent is 3-20 microns.

Description

Epoxy resin composition containing microcapsule curing agent, and prepreg and composite material thereof
Technical Field
The invention belongs to the technical field of toughening modification of epoxy resin, and particularly relates to an epoxy resin composition containing a microcapsule curing agent, and a prepreg and a composite material thereof.
Background
The fiber reinforced composite material is widely applied to structural members, aerospace products, automobile outer plates, display shells and the like due to light weight, high strength and attractive appearance, and the prepreg can be used in the manufacturing method. The prepreg is a sheet-shaped intermediate material obtained by infiltrating uncured matrix resin into reinforcing fibers, and a fiber-reinforced composite material is obtained by layering a plurality of prepregs and heating and pressurizing the layers.
Epoxy resin is an epoxy oligomer, can form three-dimensional reticular thermosetting plastic when reacting with a curing agent, has the characteristics of small shrinkage rate in the curing reaction process, and excellent cohesiveness, heat resistance, chemical resistance, mechanical property and electrical property of a cured product, is a variety with larger application amount in thermosetting resin, has the defect of poor toughness, and therefore, the toughness of the cured product needs to be improved by a certain method.
The toughening modification of the epoxy resin is an important research content of basic research and application development in the field of polymer science, and the epoxy resin is toughened by only adopting rubber, an elastomer or rigid particles, which has some defects. For example, the toughening effect can be achieved only by adopting rubber or elastomer to toughen the epoxy resin and usually by adding 20 percent of the epoxy resin; the inorganic rigid particles are adopted for toughening, the rigid particles are strict in size requirement, and are not beneficial to toughening when being too large, and in addition, the rigid particles need to have proper elastic modulus and good interface compatibility with an epoxy resin matrix, so that the rigid particles are required to be modified, the manufacturability is reduced, and the cost is increased.
At present, the service life of a large amount of supplied prepreg is generally 30 days at normal temperature, the prepreg is generally required to be stored in a freezing mode, the freezing storage temperature is-18 ℃, and a prepreg user needs to be equipped with a refrigeration house or freezing equipment, so that the use cost is increased.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides an epoxy resin composition containing a microcapsule curing agent, and a prepreg and a composite material thereof, and overcomes the defects of 1: the toughening epoxy resin is toughened by only adopting rubber or elastomer, and the toughening effect can be achieved only by the addition of 20 percent of the epoxy resin; 2: the inorganic rigid particles are adopted for toughening, the rigid particles have strict requirements on the size, and are not beneficial to toughening when being too large, and in addition, the rigid particles need to have proper elastic modulus and good interface compatibility with an epoxy resin matrix, so that the rigid particles are required to be modified, the manufacturability is reduced, and the cost is increased; 3: the working life of the existing prepreg at normal temperature is generally 30 days, the prepreg is generally required to be frozen and stored at the temperature of-18 ℃, and a prepreg user needs to be equipped with a refrigeration house or refrigeration equipment, so that the use cost is increased, and the like.
In order to solve the technical problem, the technical scheme of the invention is as follows: the epoxy resin composition containing the microcapsule curing agent comprises the microcapsule curing agent, epoxy resin and a diluent, wherein the weight parts of the components are as follows: the epoxy resin curing agent comprises 80-100 parts of epoxy resin, 15-30 parts of a microcapsule curing agent and 10-20 parts of a diluent, wherein the microcapsule curing agent consists of a thermoplastic shell and the epoxy resin curing agent, the epoxy resin curing agent is wrapped inside the thermoplastic shell, and the particle size of the microcapsule curing agent is 3-20 microns.
Preferably, the paint also comprises one or more of a flame retardant, a UV absorbent, an antistatic agent and an electromagnetic shielding agent, wherein the weight parts of each component are as follows: 100 parts of epoxy resin, 15-20 parts of microcapsule curing agent, 10-15 parts of diluent, 0-15 parts of flame retardant, 0-15 parts of UV absorbent, 0-15 parts of antistatic agent and 0-15 parts of electromagnetic shielding agent.
Preferably, the thermoplastic shell is selected from the group consisting of polymethylmethacrylate, polyethylmethacrylate, polymethylmethacrylate, polybutylacrylate, polypropylpropyl acrylate, nylon 6, nylon 12, nylon 6/12 copolymer, nylon 11, polyethersulfone, polyetherethersulfone, polyetherimide, PEEK, PEK, or PEKK.
Preferably, the epoxy resin curing agent is selected from imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-phenylimidazole, 1-cyano-2-ethyl-4-methylimidazole, 1-cyano-2-phenylimidazole, dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, aminobenzoate, methylhexahydrophthalic anhydride, phthalic anhydride, pyromellitic dianhydride, trimellitic anhydride, eleostearic anhydride, nadic anhydride, glutaric anhydride, or terpene-based anhydride.
Preferably, the epoxy resin is selected from liquid bisphenol A epoxy resin, liquid bisphenol F epoxy resin, E-51, E-44, E-42 or YDF-1020.
Preferably, the diluent is a reactive diluent or a non-reactive diluent, wherein the reactive diluent is selected from butyl glycidyl ether, benzyl glycidyl ether, glycidyl oleate, glycidyl benzoate, phenyl glycidyl ether, bis (2, 3-epoxycyclopentyl) ether or dicyclopentadiene dioxide, and wherein the non-reactive diluent is selected from acetone, absolute ethanol, toluene, xylene, styrene, ethyl acetate, butyl acetate, dimethylformamide, a polyol or benzyl alcohol.
Preferably, the flame retardant is selected from melamine polyphosphate, coated red phosphorus, methyl dimethyl phosphate, DOPO, aluminum hydroxide, magnesium hydroxide, triphenyl phosphate, chlorohydrocarbon 50, decabromodiphenyl oxide or antimony trioxide, the UV absorbent is selected from UV531, UV326, UV327, UV234, UV329, UV-P, UV328, UV360, UV622, UV770 and UV284, the antistatic agent is selected from Hostapur 93, Hostastat HS-1, Mersolat H95, Irgastat P18, PELECTRON PVL, ionics LQ01, CHEMISTAT 3033, CHEMISTAT 3500 or PESTAT LE1251, and the electromagnetic shielding agent is selected from silver-nickel-glass bead powder, copper powder, SAS, carbon black, graphene, carbon nanotube or iron-silver composite powder.
Preferably, the prepreg prepared by using the epoxy resin composition containing the microcapsule curing agent as described in any one of the above is prepared by adding the epoxy resin composition containing the microcapsule curing agent into a dip tank of a prepreg device, fully soaking the epoxy resin composition containing the microcapsule curing agent in a fiber material after the device is operated, and rolling to obtain the prepreg, wherein the fiber material is a unidirectional fiber bundle, plain cloth or twill cloth.
Preferably, the composite material prepared by using the epoxy resin composition containing the microcapsule curing agent as described in any one of the above comprises the epoxy resin composition containing the microcapsule curing agent, a sandwich structure and a prepreg, and the preparation process comprises the following steps:
step 1) brushing an epoxy resin composition containing a microcapsule curing agent on two surfaces of a sandwich structure;
step 2) respectively paving and sticking a plurality of layers of prepreg on two surfaces of the sandwich structure coated with the epoxy resin composition containing the microcapsule curing agent;
and 3) vacuumizing, heating and curing for 2 hours in an oven at the temperature of 90-130 ℃, and demolding to obtain the composite material of the epoxy resin composition containing the microcapsule curing agent.
Preferably, in the step 2), 2-10 layers of prepreg are respectively paved on two surfaces of the sandwich structure coated with the epoxy resin composition containing the microcapsule curing agent.
Compared with the prior art, the invention has the advantages that:
(1) the epoxy resin composition containing the microcapsule curing agent comprises the microcapsule curing agent, epoxy resin and a diluent, wherein the microcapsule curing agent consists of a thermoplastic shell and the epoxy resin curing agent, the epoxy resin curing agent is wrapped in the thermoplastic shell, and the particle size of the microcapsule curing agent is 3-20 mu m; because the epoxy resin curing agent is wrapped by the thermoplastic shell, the epoxy resin curing agent and the epoxy resin can be fully isolated, so that the quality guarantee period of the prepreg obtained by soaking the epoxy resin composition of the microcapsule curing agent is longer, can reach 180 days at normal temperature, and the quality guarantee period of the prepreg is greatly prolonged because the common prepreg is only 30 days;
(2) the microcapsule curing agent of the epoxy resin composition containing the microcapsule curing agent consists of a thermoplastic shell and the epoxy resin curing agent, wherein the thermoplastic microcapsule gradually collapses under the action of heating and a diluent, the epoxy resin curing agent flows out of the thermoplastic shell or the epoxy resin permeates into the thermoplastic shell to participate in reaction, and a three-dimensional network structure penetrating through the thermoplastic shell, namely a semi-interpenetrating network structure (semi-IPN) is gradually formed, and the domain size of a composite material system obtained by infiltrating the epoxy resin composition of the microcapsule curing agent after curing of a prepreg is about 2 microns, so that the toughness of the composite material is obviously improved;
(3) the prepreg prepared by the epoxy resin composition containing the microcapsule curing agent does not need to be stored in a freezing way, and only needs to be placed in a normal-temperature drying and sealing environment, so that the cost is greatly reduced, the storage stability is high, and the epoxy resin composition containing the microcapsule curing agent has a simple preparation method and reasonable compatibility of components.
Drawings
FIG. 1 is a particle size diagram of a microcapsule curing agent of the present invention;
FIG. 2 is a schematic diagram showing the coating rate of the microcapsule curing agent of the present invention;
FIG. 3 is a schematic view of a fracture surface of an epoxy resin composition containing a microcapsule curing agent according to the present invention;
FIG. 4 is a schematic diagram showing the glass transition temperature of the epoxy resin composition containing a microcapsule curing agent of the present invention.
Detailed Description
The following describes embodiments of the present invention with reference to examples:
it should be noted that the structures, proportions, sizes, and other elements shown in the specification are included for the purpose of understanding and reading only, and are not intended to limit the scope of the invention, which is defined by the claims, and any modifications of the structures, changes in the proportions and adjustments of the sizes, without affecting the efficacy and attainment of the same.
In addition, the terms "upper", "lower", "left", "right", "middle" and "one" used in the present specification are for clarity of description, and are not intended to limit the scope of the present invention, and the relative relationship between the terms and the terms is not to be construed as a scope of the present invention.
Example 1
The invention discloses an epoxy resin composition containing a microcapsule curing agent, which is characterized in that: the microcapsule curing agent comprises a microcapsule curing agent, epoxy resin and a diluent, wherein the microcapsule curing agent comprises the following components in parts by weight: the epoxy resin curing agent comprises 80-100 parts of epoxy resin, 15-30 parts of a microcapsule curing agent and 10-20 parts of a diluent, wherein the microcapsule curing agent consists of a thermoplastic shell and the epoxy resin curing agent, the epoxy resin curing agent is wrapped inside the thermoplastic shell, and the particle size of the microcapsule curing agent is 3-20 microns.
Example 2
The invention discloses an epoxy resin composition containing a microcapsule curing agent, which is characterized in that: the microcapsule curing agent comprises a microcapsule curing agent, epoxy resin and a diluent, wherein the microcapsule curing agent comprises the following components in parts by weight: the epoxy resin curing agent comprises 80-100 parts of epoxy resin, 15-30 parts of a microcapsule curing agent and 10-20 parts of a diluent, wherein the microcapsule curing agent consists of a thermoplastic shell and the epoxy resin curing agent, the epoxy resin curing agent is wrapped inside the thermoplastic shell, and the particle size of the microcapsule curing agent is 3-20 microns.
Preferably, the paint also comprises one or more of a flame retardant, a UV absorbent, an antistatic agent and an electromagnetic shielding agent, wherein the weight parts of each component are as follows: 100 parts of epoxy resin, 15-20 parts of microcapsule curing agent, 10-15 parts of diluent, 0-15 parts of flame retardant, 0-15 parts of UV absorbent, 0-15 parts of antistatic agent and 0-15 parts of electromagnetic shielding agent.
Example 3
The invention discloses an epoxy resin composition containing a microcapsule curing agent, which is characterized in that: the microcapsule curing agent comprises a microcapsule curing agent, epoxy resin and a diluent, wherein the microcapsule curing agent comprises the following components in parts by weight: the epoxy resin curing agent comprises 80-100 parts of epoxy resin, 15-30 parts of a microcapsule curing agent and 10-20 parts of a diluent, wherein the microcapsule curing agent consists of a thermoplastic shell and the epoxy resin curing agent, the epoxy resin curing agent is wrapped inside the thermoplastic shell, and the particle size of the microcapsule curing agent is 3-20 microns.
Preferably, the paint also comprises one or more of a flame retardant, a UV absorbent, an antistatic agent and an electromagnetic shielding agent, wherein the weight parts of each component are as follows: 100 parts of epoxy resin, 15-20 parts of microcapsule curing agent, 10-15 parts of diluent, 0-15 parts of flame retardant, 0-15 parts of UV absorbent, 0-15 parts of antistatic agent and 0-15 parts of electromagnetic shielding agent.
Preferably, the thermoplastic shell is selected from the group consisting of polymethylmethacrylate, polyethylmethacrylate, polymethylmethacrylate, polybutylacrylate, polypropylpropyl acrylate, nylon 6, nylon 12, nylon 6/12 copolymer, nylon 11, polyethersulfone, polyetherethersulfone, polyetherimide, PEEK, PEK, or PEKK.
Preferably, the epoxy resin curing agent is selected from imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-phenylimidazole, 1-cyano-2-ethyl-4-methylimidazole, 1-cyano-2-phenylimidazole, dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, aminobenzoate, methylhexahydrophthalic anhydride, phthalic anhydride, pyromellitic dianhydride, trimellitic anhydride, eleostearic anhydride, nadic anhydride, glutaric anhydride, or terpene-based anhydride.
Preferably, the epoxy resin is selected from liquid bisphenol A epoxy resin, liquid bisphenol F epoxy resin, E-51, E-44, E-42 or YDF-1020.
Preferably, the diluent is a reactive diluent or a non-reactive diluent, wherein the reactive diluent is selected from butyl glycidyl ether, benzyl glycidyl ether, glycidyl oleate, glycidyl benzoate, phenyl glycidyl ether, bis (2, 3-epoxycyclopentyl) ether or dicyclopentadiene dioxide, and wherein the non-reactive diluent is selected from acetone, absolute ethanol, toluene, xylene, styrene, ethyl acetate, butyl acetate, dimethylformamide, a polyol or benzyl alcohol.
Preferably, the flame retardant is selected from melamine polyphosphate, coated red phosphorus, methyl dimethyl phosphate, DOPO, aluminum hydroxide, magnesium hydroxide, triphenyl phosphate, chlorohydrocarbon 50, decabromodiphenyl oxide or antimony trioxide, the UV absorbent is selected from UV531, UV326, UV327, UV234, UV329, UV-P, UV328, UV360, UV622, UV770 and UV284, the antistatic agent is selected from Hostapur 93, Hostastat HS-1, Mersolat H95, Irgastat P18, PELECTRON PVL, ionics LQ01, CHEMISTAT 3033, CHEMISTAT 3500 or PESTAT LE1251, and the electromagnetic shielding agent is selected from silver-nickel-glass bead powder, copper powder, SAS, carbon black, graphene, carbon nanotube or iron-silver composite powder.
Example 4
The invention discloses an epoxy resin composition containing a microcapsule curing agent, which is characterized in that: the microcapsule curing agent comprises a microcapsule curing agent, epoxy resin and a diluent, wherein the microcapsule curing agent comprises the following components in parts by weight: the epoxy resin curing agent comprises 80-100 parts of epoxy resin, 15-30 parts of a microcapsule curing agent and 10-20 parts of a diluent, wherein the microcapsule curing agent consists of a thermoplastic shell and the epoxy resin curing agent, the epoxy resin curing agent is wrapped inside the thermoplastic shell, and the particle size of the microcapsule curing agent is 3-20 microns.
Preferably, the paint also comprises one or more of a flame retardant, a UV absorbent, an antistatic agent and an electromagnetic shielding agent, wherein the weight parts of each component are as follows: 100 parts of epoxy resin, 15-20 parts of microcapsule curing agent, 10-15 parts of diluent, 0-15 parts of flame retardant, 0-15 parts of UV absorbent, 0-15 parts of antistatic agent and 0-15 parts of electromagnetic shielding agent.
Preferably, the thermoplastic shell is selected from the group consisting of polymethylmethacrylate, polyethylmethacrylate, polymethylmethacrylate, polybutylacrylate, polypropylpropyl acrylate, nylon 6, nylon 12, nylon 6/12 copolymer, nylon 11, polyethersulfone, polyetherethersulfone, polyetherimide, PEEK, PEK, or PEKK.
Preferably, the epoxy resin curing agent is selected from imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-phenylimidazole, 1-cyano-2-ethyl-4-methylimidazole, 1-cyano-2-phenylimidazole, dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, aminobenzoate, methylhexahydrophthalic anhydride, phthalic anhydride, pyromellitic dianhydride, trimellitic anhydride, eleostearic anhydride, nadic anhydride, glutaric anhydride, or terpene-based anhydride.
Preferably, the epoxy resin is selected from liquid bisphenol A epoxy resin, liquid bisphenol F epoxy resin, E-51, E-44, E-42 or YDF-1020.
Preferably, the diluent is a reactive diluent or a non-reactive diluent, wherein the reactive diluent is selected from butyl glycidyl ether, benzyl glycidyl ether, glycidyl oleate, glycidyl benzoate, phenyl glycidyl ether, bis (2, 3-epoxycyclopentyl) ether or dicyclopentadiene dioxide, and wherein the non-reactive diluent is selected from acetone, absolute ethanol, toluene, xylene, styrene, ethyl acetate, butyl acetate, dimethylformamide, a polyol or benzyl alcohol.
Preferably, the flame retardant is selected from melamine polyphosphate, coated red phosphorus, methyl dimethyl phosphate, DOPO, aluminum hydroxide, magnesium hydroxide, triphenyl phosphate, chlorohydrocarbon 50, decabromodiphenyl oxide or antimony trioxide, the UV absorbent is selected from UV531, UV326, UV327, UV234, UV329, UV-P, UV328, UV360, UV622, UV770 and UV284, the antistatic agent is selected from Hostapur 93, Hostastat HS-1, Mersolat H95, Irgastat P18, PELECTRON PVL, ionics LQ01, CHEMISTAT 3033, CHEMISTAT 3500 or PESTAT LE1251, and the electromagnetic shielding agent is selected from silver-nickel-glass bead powder, copper powder, SAS, carbon black, graphene, carbon nanotube or iron-silver composite powder.
Preferably, the prepreg prepared by using the epoxy resin composition containing the microcapsule curing agent as described in any one of the above is prepared by adding the epoxy resin composition containing the microcapsule curing agent into a dip tank of a prepreg device, fully soaking the epoxy resin composition containing the microcapsule curing agent in a fiber material after the device is operated, and rolling to obtain the prepreg.
Example 5
The invention discloses an epoxy resin composition containing a microcapsule curing agent, which is characterized in that: the microcapsule curing agent comprises a microcapsule curing agent, epoxy resin and a diluent, wherein the microcapsule curing agent comprises the following components in parts by weight: the epoxy resin curing agent comprises 80-100 parts of epoxy resin, 15-30 parts of a microcapsule curing agent and 10-20 parts of a diluent, wherein the microcapsule curing agent consists of a thermoplastic shell and the epoxy resin curing agent, the epoxy resin curing agent is wrapped inside the thermoplastic shell, and the particle size of the microcapsule curing agent is 3-20 microns.
Preferably, the paint also comprises one or more of a flame retardant, a UV absorbent, an antistatic agent and an electromagnetic shielding agent, wherein the weight parts of each component are as follows: 100 parts of epoxy resin, 15-20 parts of microcapsule curing agent, 10-15 parts of diluent, 0-15 parts of flame retardant, 0-15 parts of UV absorbent, 0-15 parts of antistatic agent and 0-15 parts of electromagnetic shielding agent.
Preferably, the thermoplastic shell is selected from the group consisting of polymethylmethacrylate, polyethylmethacrylate, polymethylmethacrylate, polybutylacrylate, polypropylpropyl acrylate, nylon 6, nylon 12, nylon 6/12 copolymer, nylon 11, polyethersulfone, polyetherethersulfone, polyetherimide, PEEK, PEK, or PEKK.
Preferably, the epoxy resin curing agent is selected from imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-phenylimidazole, 1-cyano-2-ethyl-4-methylimidazole, 1-cyano-2-phenylimidazole, dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, aminobenzoate, methylhexahydrophthalic anhydride, phthalic anhydride, pyromellitic dianhydride, trimellitic anhydride, eleostearic anhydride, nadic anhydride, glutaric anhydride, or terpene-based anhydride.
Preferably, the epoxy resin is selected from liquid bisphenol A epoxy resin, liquid bisphenol F epoxy resin, E-51, E-44, E-42 or YDF-1020.
Preferably, the diluent is a reactive diluent or a non-reactive diluent, wherein the reactive diluent is selected from butyl glycidyl ether, benzyl glycidyl ether, glycidyl oleate, glycidyl benzoate, phenyl glycidyl ether, bis (2, 3-epoxycyclopentyl) ether or dicyclopentadiene dioxide, and wherein the non-reactive diluent is selected from acetone, absolute ethanol, toluene, xylene, styrene, ethyl acetate, butyl acetate, dimethylformamide, a polyol or benzyl alcohol.
Preferably, the flame retardant is selected from melamine polyphosphate, coated red phosphorus, methyl dimethyl phosphate, DOPO, aluminum hydroxide, magnesium hydroxide, triphenyl phosphate, chlorohydrocarbon 50, decabromodiphenyl oxide or antimony trioxide, the UV absorbent is selected from UV531, UV326, UV327, UV234, UV329, UV-P, UV328, UV360, UV622, UV770 and UV284, the antistatic agent is selected from Hostapur 93, Hostastat HS-1, Mersolat H95, Irgastat P18, PELECTRON PVL, ionics LQ01, CHEMISTAT 3033, CHEMISTAT 3500 or PESTAT LE1251, and the electromagnetic shielding agent is selected from silver-nickel-glass bead powder, copper powder, SAS, carbon black, graphene, carbon nanotube or iron-silver composite powder.
Preferably, the prepreg prepared by using the epoxy resin composition containing the microcapsule curing agent as described in any one of the above is prepared by adding the epoxy resin composition containing the microcapsule curing agent into a dip tank of a prepreg device, fully soaking the epoxy resin composition containing the microcapsule curing agent in a fiber material after the device is operated, and rolling to obtain the prepreg, wherein the fiber material is a unidirectional fiber bundle, plain cloth or twill cloth.
Preferably, the composite material prepared by using the epoxy resin composition containing the microcapsule curing agent as described in any one of the above comprises the epoxy resin composition containing the microcapsule curing agent, a sandwich structure and a prepreg, and the preparation process comprises the following steps:
step 1) brushing an epoxy resin composition containing a microcapsule curing agent on two surfaces of a sandwich structure;
step 2) respectively paving and sticking a plurality of layers of prepreg on two surfaces of the sandwich structure coated with the epoxy resin composition containing the microcapsule curing agent;
and 3) vacuumizing, heating and curing for 2 hours in an oven at the temperature of 90-130 ℃, and demolding to obtain the composite material of the epoxy resin composition containing the microcapsule curing agent.
Preferably, in the step 2), 2-10 layers of prepreg are respectively paved on two surfaces of the sandwich structure coated with the epoxy resin composition containing the microcapsule curing agent.
The microcapsule shell used in the prior art is a reaction product of any 2 or more than 2 of isocyanate compound, active hydrogen compound, curing agent for epoxy resin, epoxy resin and low molecular amine compound, the microcapsule shell has the functions of isolating the curing agent and resin and increasing solvent resistance and moisture resistance, and the microcapsule shell is an epoxy resin curing system and is different from the thermoplastic shell.
The epoxy resin is preferably a low-viscosity liquid bisphenol A epoxy resin or liquid bisphenol F epoxy resin, and examples thereof include domestic E-51, E-44 and E-42, 6004, 6005, 6010, 6020 and 6030 available from GIba-Gelgy, EPON826, EPON828 and EPON830 available from Shell, and domestic YDF-1020 available from Shell.
The fiber material plays a bearing role in the composite material, and is selected from glass fiber, carbon fiber, silicon carbide fiber, high silica fiber, boron carbide fiber, quartz fiber and the like. The fibrous material may be unidirectional fiber bundles, plain or twill.
The sandwich structure in the composite material mainly bears the transverse shear stress transmitted by the panels, stabilizes the upper and lower panels and prevents local yielding. The sandwich structure is Nomex honeycomb, PVC foam, PMI foam, polyurethane foam, balsa wood and the like.
The thermoplastic shell is made of a material with good compatibility with epoxy resin, and the molecular weight of the thermoplastic shell is 10000-1000000. The microcapsule curing agent is prepared by any one of a solvent volatilization method, a spray freezing method, a spray drying method or an interfacial polymerization method.
The prepregs of the present invention may be prepared on prepreg equipment in a manner which is conventional to those skilled in the art.
The composite material is prepared in a drying room or an autoclave, wherein the preparation method is vacuum bag pressing method or autoclave forming method. The various materials described herein are commercially available.
Example 6
Fully mixing 100g of epoxy resin E-51, 20g of a microcapsule curing agent (the particle diameter is 3-20 mu m) of polymethyl methacrylate wrapping 2-phenylimidazole and 15g of a diluent benzyl glycidyl ether by using a mixing device to obtain an epoxy resin composition containing the microcapsule curing agent;
adding the prepared epoxy resin composition containing the microcapsule curing agent into a glue dipping tank of prepreg equipment, fully soaking the epoxy resin composition containing the microcapsule curing agent into a fiber material after the equipment runs, and rolling to obtain a prepreg;
brushing the epoxy resin composition containing the microcapsule curing agent on two surfaces of a sandwich structure, paving two layers of prepreg on the two surfaces of the sandwich structure respectively, vacuumizing, heating and curing for 2 hours in an oven at 90-130 ℃, demolding to obtain the composite material of the epoxy resin composition containing the microcapsule curing agent, and cutting the demolded sample into sample strips with the thickness of 75 x 10 x 5 mm.
Example 7
By utilizing a mixing device, fully mixing 80g of epoxy resin E-44, 15g of imidazole-coated polyethylene methacrylate microcapsule curing agent (the particle size is 3-20 mu m) and 10g of diluent butyl glycidyl ether to obtain an epoxy resin composition containing the microcapsule curing agent;
adding the prepared epoxy resin composition containing the microcapsule curing agent into a glue dipping tank of prepreg equipment, fully soaking the epoxy resin composition containing the microcapsule curing agent into a fiber material after the equipment runs, and rolling to obtain a prepreg;
brushing the epoxy resin composition containing the microcapsule curing agent on two surfaces of a sandwich structure, paving two layers of prepreg on the two surfaces of the sandwich structure respectively, vacuumizing, heating and curing for 2 hours in an oven at 90-130 ℃, demolding to obtain the composite material of the epoxy resin composition containing the microcapsule curing agent, and cutting the demolded sample into sample strips with the thickness of 75 x 10 x 5 mm.
Example 8
By utilizing a mixing device, fully mixing 90g of epoxy resin E-42, 18g of microcapsule curing agent (the particle size is 3-20 mu m) of polymethyl acrylate wrapping 2-methylimidazole, 15g of diluent glycidyl oleate, 15g of melamine polyphosphate, 10gUV531, 5g of Hostapur SAS93 and 5g of silver-nickel-glass bead powder to obtain an epoxy resin composition containing the microcapsule curing agent;
adding the prepared epoxy resin composition containing the microcapsule curing agent into a glue dipping tank of prepreg equipment, fully soaking the epoxy resin composition containing the microcapsule curing agent into a fiber material after the equipment runs, and rolling to obtain a prepreg;
brushing the epoxy resin composition containing the microcapsule curing agent on two surfaces of a sandwich structure, paving two layers of prepreg on the two surfaces of the sandwich structure respectively, vacuumizing, heating and curing for 2 hours in an oven at 90-130 ℃, demolding to obtain the composite material of the epoxy resin composition containing the microcapsule curing agent, and cutting the demolded sample into sample strips with the thickness of 75 x 10 x 5 mm.
Example 9
Fully mixing 100g of epoxy resin YDF-1020, 30g of a microcapsule curing agent (the particle diameter is 3-20 mu m) of polybutyl acrylate wrapping 2-ethylimidazole, 20g of diluent glycidyl benzoate, 10g of coated red phosphorus, 15gUV326, 15g of Hostastat HS-1 and 10g of copper powder by using a mixing device to obtain an epoxy resin composition containing the microcapsule curing agent;
adding the prepared epoxy resin composition containing the microcapsule curing agent into a glue dipping tank of prepreg equipment, fully soaking the epoxy resin composition containing the microcapsule curing agent into a fiber material after the equipment runs, and rolling to obtain a prepreg;
brushing the epoxy resin composition containing the microcapsule curing agent on two surfaces of a sandwich structure, paving two layers of prepreg on the two surfaces of the sandwich structure respectively, vacuumizing, heating and curing for 2 hours in an oven at 90-130 ℃, demolding to obtain the composite material of the epoxy resin composition containing the microcapsule curing agent, and cutting the demolded sample into sample strips with the thickness of 75 x 10 x 5 mm.
Example 10
An epoxy resin composition containing a microcapsule curing agent was obtained by thoroughly mixing 100g of a liquid bisphenol A epoxy resin, 20g of a microcapsule curing agent (particle diameter: 3 to 20 μm) of 2-ethyl-4-methylimidazole-coated nylon 12, 15g of a diluent, phenyl glycidyl ether, 5g of dimethyl methyl phosphate, 5gUV234, 10g of Irgastat P18 and 15g of carbon black in a mixing apparatus;
adding the prepared epoxy resin composition containing the microcapsule curing agent into a glue dipping tank of prepreg equipment, fully soaking the epoxy resin composition containing the microcapsule curing agent into a fiber material after the equipment runs, and rolling to obtain a prepreg;
brushing the epoxy resin composition containing the microcapsule curing agent on two surfaces of a sandwich structure, paving two layers of prepreg on the two surfaces of the sandwich structure respectively, vacuumizing, heating and curing for 2 hours in an oven at 90-130 ℃, demolding to obtain the composite material of the epoxy resin composition containing the microcapsule curing agent, and cutting the demolded sample into sample strips with the thickness of 75 x 10 x 5 mm.
Comparative example 1
100g of epoxy resin E-51, 2g of 2-phenylimidazole curing agent and 15g of benzyl glycidyl ether as a diluent were thoroughly mixed by a mixing device to obtain an epoxy resin composition, and a prepreg and a composite material were prepared from the epoxy resin composition.
Comparative example 2
100g of epoxy resin E-51, 2g of 2-phenylimidazole curing agent, 18g of polymethyl methacrylate powder (particle size: about 10 μm), and 15g of benzyl glycidyl ether as a diluent were thoroughly mixed by a mixing device to obtain an epoxy resin composition, and a prepreg and a composite material were prepared from the epoxy resin composition.
Comparative example 3
100g of epoxy resin E-51, 2g of 2-phenylimidazole, 28g of polymethyl methacrylate microcapsule curing agent and 15g of diluent benzyl glycidyl ether are fully mixed by a mixing device to obtain an epoxy resin composition, and the epoxy resin composition is used for preparing prepregs and composite materials.
Measurement of Room temperature storage period of prepreg obtained by impregnating epoxy resin composition containing microcapsule curing agent
The prepreg obtained in the embodiment 6-10 is placed in a normal-temperature dry closed environment, the prepreg state is checked after 40 days, and the prepreg has consistent touch feeling compared with a fresh prepreg and is not hardened; the prepreg state was checked after 180 days and was consistent with a fresh prepreg to the touch and not stiff.
And (3) placing the prepreg obtained in the comparative examples 1-3 in a normal-temperature dry closed environment, and checking the state of the prepreg after 40 days to make the prepreg hard.
Impact power and impact toughness detection of composite material prepared from prepreg soaked by epoxy resin composition containing microcapsule curing agent
Brushing the epoxy resin composition on two surfaces of a sandwich structure, respectively laying two layers of epoxy prepregs containing the microcapsule curing agent on the two surfaces of the sandwich structure, vacuumizing, heating and curing in an oven at 90-130 ℃ for 2 hours, demolding, cutting a demolded sample into sample strips of 75 x 10 x 5mm, testing impact energy and impact toughness according to the standard ISO 179-1:2000, and testing the results as shown in Table 1:
TABLE 1 impact work and impact toughness of the composites
Figure BDA0002274719990000101
As can be seen from Table 1, the composite material prepared from the prepreg impregnated with the epoxy resin composition containing the microcapsule curing agent has impact energy and impact toughness both significantly higher than those of the comparative examples, and has impact toughness higher than that of the comparative examples, and the toughness is improved by 95.8% at most.
As can be seen from the comparison between example 6 and comparative example 2, the toughening mechanism of the epoxy cured product of the present invention is no longer the conventional blending toughening, but a new structure semi-interpenetrating network structure semi-IPN is formed, and the semi-IPN can effectively prevent crack propagation and improve the toughness of the composite material.
The invention has the following characteristics on the particle size of the microcapsule curing agent: the particle size of the microcapsule curing agent can be characterized by a polarizing microscope, as shown in fig. 1, and the characterization result is as follows: the microcapsule curing agent has a particle size of about 3 to 20 μm.
The invention has the characteristics of the coating rate of the microcapsule curing agent: the invention adopts a thermogravimetric analyzer to represent the coating rate of the microcapsule curing agent, as shown in figure 2:
as can be seen from FIG. 2, the temperature at which the thermoplastic shell (shell) starts to decompose is about 380 ℃ and the temperature at which the epoxy resin curing agent (core) starts to decompose is about 180 ℃. The epoxy resin curing agent is wrapped in the thermoplastic shell to form the microcapsule curing agent (microcapsule), the decomposition temperature starts to move towards the high temperature direction, as can be seen from fig. 2, the decomposition temperature of the microcapsule curing agent is about 250 ℃, a step appears at about 350 ℃, the decomposition temperature curve after the step is consistent with the decomposition temperature trend and the inclination of the thermoplastic shell, which shows that the thermoplastic shell is decomposed after the step, and the epoxy resin curing agent (core) is decomposed at the step. By comparing the left coordinates, the coating rate of the epoxy resin curing agent was about 10%.
The invention is characterized in that the fracture surface of the epoxy resin composition containing the microcapsule curing agent is as follows: the fracture surface of the epoxy resin composition containing the microcapsule curing agent can be characterized by a scanning electron microscope, as shown in fig. 3, the microcapsule curing agent already participates in the reaction, the fracture surface after the reaction is not a smooth section, but is a stacked spherical particle, the particle size is about 2 μm and is less than 3-20 μm of the microcapsule size, the microcapsule curing agent is a multi-core structure, each core is a reaction center, and each reaction center forms a micron-sized semi-interpenetrating network structure semi-IPN with the epoxy resin.
The invention is characterized by the glass transition temperature of the epoxy resin composition containing the microcapsule curing agent: the glass transition temperature of the epoxy resin composition containing the microcapsule curing agent can be characterized by DMA, as shown in fig. 4:
FIG. 4 is a DMA curve of curing agent and epoxy resin (EP/curing agent), curing agent and epoxy system with the addition of pure shell microspheres (EP/curing agent + thermoplastic shell), and epoxy resin with the addition of microcapsule curing agent (EP/microcapsule curing agent). The temperature corresponding to the peak value of the curve is the glass transition temperature of the system, and compared with the three curves, the EP/microcapsule curing agent system has the lowest glass transition temperature, the EP/curing agent + thermoplastic shell is the second order, and the highest EP/curing agent system. Therefore, the thermoplastic shell material has a toughening effect on an epoxy resin system, the glass transition temperature can be reduced to a certain extent by simply mixing, and the toughness of the system is improved, but the effects of reducing the glass transition temperature and improving the toughness of the microcapsule curing agent are better.
The reaction principle of the invention is as follows:
the microcapsule curing agent of the invention is composed of a thermoplastic shell and an epoxy resin curing agent, after the microcapsule curing agent is added into epoxy resin, under the action of heating and a diluent, the thermoplastic shell gradually collapses, the epoxy resin curing agent flows out of the thermoplastic shell or the epoxy resin permeates into the thermoplastic shell to participate in reaction, and a three-dimensional network structure penetrating through the thermoplastic microcapsule shell is gradually formed, namely a semi-interpenetrating network structure (semi-IPN), because the microsphere phase size of a cured material system is smaller than the microcapsule size, as can be seen from the comparison of figure 1 and figure 3, the microcapsule is a multi-core structure. Each microcapsule curing agent forms a plurality of micron-sized semi-IPN structures (as shown in figure 3), and when cracks expand to the surface of a micro semi-IPN spherical structure, the crack expansion can be effectively blocked, namely the toughness of a cured product is effectively improved. The thermoplastic shell material has good compatibility with the epoxy matrix, and the thermoplastic shell material has softer segments than the epoxy matrix, and can act as a plasticizer for the epoxy matrix, as evidenced by the decrease in glass transition temperature (as shown in fig. 4).
The epoxy resin composition containing the microcapsule curing agent comprises the microcapsule curing agent, epoxy resin and a diluent, wherein the microcapsule curing agent consists of a thermoplastic shell and the epoxy resin curing agent, the epoxy resin curing agent is wrapped in the thermoplastic shell, and the particle size of the microcapsule curing agent is 3-20 mu m; because the epoxy resin curing agent is wrapped by the thermoplastic shell, the epoxy resin curing agent and the epoxy resin can be fully isolated, so that the shelf life of the prepreg obtained by soaking the epoxy resin composition of the microcapsule curing agent is longer, can reach 180 days at normal temperature, and the shelf life of the prepreg is greatly prolonged because the common prepreg is only 30 days.
The microcapsule curing agent of the epoxy resin composition containing the microcapsule curing agent comprises a thermoplastic shell and the epoxy resin curing agent, wherein the thermoplastic microcapsule gradually collapses under the action of heating and a diluent, the epoxy resin curing agent flows out of the thermoplastic shell or the epoxy resin permeates into the thermoplastic shell to participate in reaction, and a three-dimensional network structure penetrating through the thermoplastic shell, namely a semi-interpenetrating network structure (semi-IPN) is gradually formed, and the domain size of a composite material system obtained by impregnating the epoxy resin composition of the microcapsule curing agent after curing of a prepreg is about 2 microns, so that the toughness of the composite material is obviously improved.
The prepreg prepared by the epoxy resin composition containing the microcapsule curing agent does not need to be stored in a freezing way, and only needs to be placed in a normal-temperature drying and sealing environment, so that the cost is greatly reduced, the storage stability is high, and the epoxy resin composition containing the microcapsule curing agent has a simple preparation method and reasonable compatibility of components.
While the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Many other changes and modifications can be made without departing from the spirit and scope of the invention. It is to be understood that the invention is not to be limited to the specific embodiments, but only by the scope of the appended claims.

Claims (10)

1. An epoxy resin composition containing a microcapsule curing agent, characterized in that: the microcapsule curing agent comprises a microcapsule curing agent, epoxy resin and a diluent, wherein the microcapsule curing agent comprises the following components in parts by weight: the epoxy resin curing agent comprises 80-100 parts of epoxy resin, 15-30 parts of a microcapsule curing agent and 10-20 parts of a diluent, wherein the microcapsule curing agent consists of a thermoplastic shell and the epoxy resin curing agent, the epoxy resin curing agent is wrapped inside the thermoplastic shell, and the particle size of the microcapsule curing agent is 3-20 microns.
2. The microcapsule curing agent-containing epoxy resin composition according to claim 1, characterized in that: the paint also comprises one or more of a flame retardant, a UV absorbent, an antistatic agent and an electromagnetic shielding agent, wherein the weight parts of the components are as follows: 100 parts of epoxy resin, 15-20 parts of microcapsule curing agent, 10-15 parts of diluent, 0-15 parts of flame retardant, 0-15 parts of UV absorbent, 0-15 parts of antistatic agent and 0-15 parts of electromagnetic shielding agent.
3. The microcapsule curing agent-containing epoxy resin composition according to claim 2, characterized in that: the thermoplastic shell is selected from the group consisting of polymethyl methacrylate, polyethyl methacrylate, polymethyl acrylate, polybutyl acrylate, polypropylene acrylate, nylon 6, nylon 12, nylon 6/12 copolymer, nylon 11, polyethersulfone, polyether ether sulfone, polyetherimide, PEEK, PEK, or PEKK.
4. The microcapsule curing agent-containing epoxy resin composition according to claim 2, characterized in that: the epoxy resin curing agent is selected from imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-phenylimidazole, 1-cyano-2-ethyl-4-methylimidazole, 1-cyano-2-phenylimidazole, dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, aminobenzoate, methylhexahydrophthalic anhydride, phthalic anhydride, pyromellitic dianhydride, trimellitic anhydride, elaeostearic anhydride, nadic anhydride, glutaric anhydride or terpene-based anhydride.
5. The microcapsule curing agent-containing epoxy resin composition according to claim 2, characterized in that: the epoxy resin is selected from liquid bisphenol A epoxy resin, liquid bisphenol F epoxy resin, E-51, E-44, E-42 or YDF-1020.
6. The microcapsule curing agent-containing epoxy resin composition according to claim 2, characterized in that: the diluent is a reactive diluent or a non-reactive diluent, wherein the reactive diluent is selected from butyl glycidyl ether, benzyl glycidyl ether, glycidyl oleate, glycidyl benzoate, phenyl glycidyl ether, bis (2, 3-epoxycyclopentyl) ether or dicyclopentadiene dioxide, and the non-reactive diluent is selected from acetone, absolute ethyl alcohol, toluene, xylene, styrene, ethyl acetate, butyl acetate, dimethylformamide, polyhydric alcohol or benzyl alcohol.
7. The microcapsule curing agent-containing epoxy resin composition according to claim 2, characterized in that: the flame retardant is selected from melamine polyphosphate, coated red phosphorus, methyl dimethyl phosphate, DOPO, aluminum hydroxide, magnesium hydroxide, triphenyl phosphate, chlorocarbon 50, decabromodiphenyl oxide or antimony trioxide, the UV absorbent is selected from UV531, UV326, UV327, UV234, UV329, UV-P, UV328, UV360, UV622, UV770 and UV284, the antistatic agent is selected from Hostapu SAS93, Hostastat HS-1, Mersolat H95, Irgastat P18, PELECTRON PVL, Basionics LQ01, CHEMISTAT 3033, CHEMISTAT 3500 or PELESTAT 1251, and the electromagnetic shielding agent is selected from silver-nickel-glass powder, copper powder, iron powder, carbon black, graphene, carbon nano tube or iron-silver composite powder.
8. A prepreg produced using the microcapsule curing agent-containing epoxy resin composition according to any one of claims 1 to 7, characterized in that: adding the epoxy resin composition containing the microcapsule curing agent into a glue dipping tank of prepreg equipment, fully soaking the epoxy resin composition containing the microcapsule curing agent into a fiber material after the equipment runs, and rolling to obtain the prepreg, wherein the fiber material is a unidirectional fiber bundle, plain cloth or twill cloth.
9. A composite material prepared by using the epoxy resin composition containing the microcapsule curing agent as described in any one of claims 1 to 8, which comprises the epoxy resin composition containing the microcapsule curing agent, a sandwich structure and a prepreg, and the preparation process comprises the following steps:
step 1) brushing an epoxy resin composition containing a microcapsule curing agent on two surfaces of a sandwich structure;
step 2) respectively paving and sticking a plurality of layers of prepreg on two surfaces of the sandwich structure coated with the epoxy resin composition containing the microcapsule curing agent;
and 3) vacuumizing, heating and curing for 2 hours in an oven at the temperature of 90-130 ℃, and demolding to obtain the composite material of the epoxy resin composition containing the microcapsule curing agent.
10. The composite material prepared from the epoxy resin composition containing the microcapsule curing agent according to claim 9, wherein 2-10 layers of prepreg are respectively laid on two surfaces of the sandwich structure coated with the epoxy resin composition containing the microcapsule curing agent in the step 2).
CN201911118414.3A 2019-11-15 2019-11-15 Epoxy resin composition containing microcapsule curing agent, and prepreg and composite material thereof Withdrawn CN110791053A (en)

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CN113817426A (en) * 2021-08-25 2021-12-21 苏州锐朗新材料有限公司 Conductive adhesive applied to bonding of large-size chips and preparation method thereof
CN113908782A (en) * 2021-08-13 2022-01-11 深圳市深赛尔股份有限公司 Environment-friendly epoxy resin self-repairing microcapsule and preparation process thereof

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CN113908782A (en) * 2021-08-13 2022-01-11 深圳市深赛尔股份有限公司 Environment-friendly epoxy resin self-repairing microcapsule and preparation process thereof
CN113817426A (en) * 2021-08-25 2021-12-21 苏州锐朗新材料有限公司 Conductive adhesive applied to bonding of large-size chips and preparation method thereof
CN113817426B (en) * 2021-08-25 2023-06-30 上海锐朗光电材料有限公司 Conductive adhesive applied to large-size chip bonding and preparation method thereof

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