CN114410065B - Epoxy resin composition, carbon fiber prepreg and carbon fiber composite material - Google Patents
Epoxy resin composition, carbon fiber prepreg and carbon fiber composite material Download PDFInfo
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- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2463/04—Epoxynovolacs
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- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- 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
Abstract
The application relates to the technical field of epoxy resin for carbon fiber composite materials, and particularly discloses an epoxy resin composition, a carbon fiber prepreg and a carbon fiber composite material. The epoxy resin composition comprises the following raw materials in parts by weight: 50-80 parts of epoxy resin, 5-15 parts of polyimide resin, 10-30 parts of toughening agent, 1-10 parts of nano particles, 10-30 parts of epoxy resin curing agent, 0.5-3 parts of triglycidyl isocyanurate, 0.2-5 parts of imidazole accelerator and 0.01-2 parts of antioxidant; the viscosity of the epoxy resin composition at 90 ℃ is 5000-70000mPa.s, and the epoxy equivalent of the epoxy resin is 100-500 g/eq. The carbon fiber composite material prepared from the epoxy resin composition has the advantages of high compression strength, high tensile strength and high tensile modulus after impact.
Description
Technical Field
The application relates to the technical field of epoxy resin for carbon fiber composite materials, in particular to an epoxy resin composition, a carbon fiber prepreg and a carbon fiber composite material.
Background
The carbon fiber is a high-strength high-modulus fiber with carbon content of more than 90%. High temperature resistance is the first of all chemical fibers. The carbon fiber is prepared by taking acrylic fiber and viscose fiber as raw materials and carrying out high-temperature oxidation and carbonization. The method is widely applied in the field of aerospace. It has the advantages of high temperature resistance, friction resistance, electric conduction, heat conduction, corrosion resistance and the like. The carbon fiber is fibrous in shape, and has high strength and modulus along the fiber axis direction due to the preferred orientation of the graphite microcrystalline structure along the fiber axis. The carbon fibers have a low density and thus a high specific strength and a high specific modulus. The carbon fiber is mainly used as a reinforcing material to be compounded with resin, metal, ceramic, carbon and the like to manufacture an advanced composite material.
The resin-based carbon fiber composite material has the advantages of high specific strength, high specific rigidity, strong designability, good fatigue resistance and the like, and is widely applied to the fields of aerospace, ocean engineering, weaponry, civil construction, transportation, daily life and the like. Among them, the specific strength and specific modulus of the carbon fiber reinforced epoxy resin composite material are the highest among the existing engineering materials. However, carbon fiber reinforced epoxy resin composites are often damaged by low energy impacts from various foreign objects during manufacturing, use and maintenance, and the depth of surface pits formed by such impacts is even less than 0.5mm, which is difficult to detect visually. After the airplane encounters bird collision, the flight safety is seriously influenced; after the carbon fiber reinforced epoxy resin composite material is impacted, the inside of the carbon fiber reinforced epoxy resin composite material is subjected to intralaminar damage and interlaminar layered damage such as fiber compression, fiber fracture, matrix compression, matrix cracking and the like, so that the mechanical property of the resin-based composite material is remarkably reduced, the structural bearing capacity is obviously reduced, and the flight safety is seriously influenced. In addition, since the epoxy resin has a significant influence on the strength of the carbon fiber reinforced epoxy resin composite material, the development of an epoxy resin composition capable of reinforcing the carbon fiber reinforced epoxy resin composite material has been desired, so that the carbon fiber reinforced epoxy resin composite material has high tensile strength, tensile modulus, and compressive strength.
Disclosure of Invention
In order to improve carbon fiber reinforced epoxy resin composite's tensile strength, compressive strength, improve its tensile modulus simultaneously, this application provides an epoxy resin composition and carbon fiber prepreg, carbon fiber composite.
In a first aspect, the present application provides an epoxy resin composition, which adopts the following technical scheme:
an epoxy resin composition comprises the following raw materials in parts by weight: 50-80 parts of epoxy resin, 5-15 parts of polyimide resin, 10-30 parts of toughening agent, 1-10 parts of nano particles, 10-30 parts of epoxy resin curing agent, 0.5-3 parts of triglycidyl isocyanurate, 0.2-5 parts of imidazole accelerator and 0.01-2 parts of antioxidant; the viscosity of the epoxy resin at 90 ℃ is 5000-70000mPa.s, and the epoxy equivalent of the epoxy resin is 100-500 g/eq.
By adopting the technical scheme, the carbon fiber composite material prepared from the epoxy resin composition and the T800-grade carbon fiber has high toughness and high rigidity, and the tensile strength range of the carbon fiber composite material is 2949-2967 MPa; the tensile modulus ranges from 164-172 GPa; the compressive strength ranges from 1493-1514 MPa; the compression strength after impact is in the range of 295-307 MPa. Through the mutual cooperation of the raw materials in the epoxy resin composition, the strength between the carbon fiber layers and the compression strength of the carbon fiber composite material after impact are improved, so that the epoxy resin composition is more widely applied in the aerospace field and meets the market demand.
In the application, the toughness and the heat resistance of the epoxy resin are improved by adding the polyimide resin; by adding the nano particles, the toughness of the resin matrix is improved, and the tensile strength, rigidity, impact strength and wear resistance of the resin matrix are improved; by adding triglycidyl isocyanurate, the compatibility, rigidity and toughness of raw materials in the epoxy resin composition can be improved, and the curing of epoxy resin can be promoted, wherein the triglycidyl isocyanurate contains a six-membered ring, three epoxypropyl groups are distributed and connected on the six-membered ring at intervals, an epoxy group can generate hydrogen bond interaction force with hydroxyl groups in epoxy resin and polyimide resin and hydrogen atoms in amino groups, and a methylene group contained in the triglycidyl isocyanurate is a flexible group and can play a toughening role; in addition, triglycidyl isocyanurate has a symmetrical structure and a large molecular structure, and the distance between epoxy groups is long, so that the distance between polymer molecules can be increased, and the polymer molecules are not easy to intertwine, so that the rigidity of the epoxy resin composition is further increased, and the prepared carbon fiber composite material has high toughness and high rigidity.
In addition, the applicant has found that if the viscosity of the epoxy resin is less than 10mpa.s, the overall performance of the epoxy resin composition is not optimal, and the use of too much low viscosity epoxy resin results in too much rigidity and too low strength, which makes the prepreg processing and the lay-up process in the post-production of composite products difficult to operate; if the viscosity of the epoxy resin is higher than 30000mPa.s, the viscosity of the final resin composition becomes too high after the addition of the rest of the raw materials to the epoxy resin composition, resulting in polymerization of the resin composition during hot-melt coating at a higher temperature and difficulty in the post-lamination process for fabricating the composite article.
When the epoxy equivalent is less than 100g/eq, the activity is too large, so that the heat release is too large and the stress is too concentrated during curing, and the cured epoxy resin composition has high rigidity, poor toughness, poor fatigue resistance and low compressive strength after impact; when the epoxy equivalent is more than 500g/eq, the molecular weight is too large, the viscosity is high, the prepreg is not easy to coat and process, and no viscosity exists when the prepreg is laid, so that the carbon fiber composite material has excellent toughness, but insufficient rigidity, too low modulus and poor heat resistance.
When the content of each raw material, the viscosity of the epoxy resin composition, and the epoxy equivalent of the epoxy resin are within the above ranges, the influence on the performance test results is within a predictable range.
Optionally, the polyimide resin comprises the following raw materials in parts by weight: 15-18 parts of 3,3',4,4' -benzophenone tetracarboxylic dianhydride, 8-10 parts of diphenyl sulfide dianhydride, 20-24 parts of 2,2' -difluoro-4, 4' - (9-fluorenylidene) diphenylamine, 10-13 parts of 1,1' -bis (4-aminophenyl) cyclohexane, 55-65 parts of phenol and 75-80 parts of water.
By adopting the technical scheme, the flexibility of the polyimide resin can be improved and the solubility of the polyimide resin can be improved by carbonyl in 3,3',4,4' -benzophenone tetracarboxylic dianhydride and disulfide bonds in diphenyl sulfide dianhydride; meanwhile, 2 '-difluoro-4, 4' - (9-fluorenylidene) diphenylamine is added, and a large amount of benzene rings are introduced, so that the polyimide resin contains a large conjugated system, the thermal stability and the mechanical property of the polyimide resin are not reduced, and the prepared polyimide resin is applied to an epoxy resin composition, so that the mechanical property of the polyimide resin can be improved, and the tensile modulus and the impact compression strength of the carbon fiber composite material are improved. And when the content of each raw material in the polyimide resin is within the above range, the influence on the performance test result is within a predictable range.
Optionally, the epoxy resin is a mixture of glycidyl ether epoxy resin and glycidyl amine epoxy resin.
Optionally, the toughening agent is in the form of powder with a particle size of 0.1-100 μm.
By adopting the technical scheme, the toughening agent can be uniformly, quickly and effectively dispersed in the epoxy resin at high temperature.
Optionally, the nano particles are a mixture of inorganic nano particles and nano rubber particles in a mass ratio of 1 (2-4).
By adopting the technical scheme, the inorganic nano particles are one or more of nano aluminum oxide and nano silicon dioxide, and are rigid nano particles, and the rigid nano particles are filled into the defects of the high molecular polymer, so that the stress concentration of the resin matrix is changed, the resin matrix around the nano particles is induced to yield and deform, and a certain deformation work is absorbed to realize toughening; the nanometer rubber particle is mainly formed into a block through the interaction of active end groups such as carboxyl, hydroxyl and amino with active groups such as epoxy group and hydroxyl in the epoxy resin, so as to realize the strengthening and toughening of the epoxy resin; by the synergy of the two, the toughness of the epoxy resin composition can be further improved, and the toughness of the carbon fiber composite material can be further improved.
Optionally, the nanoparticles are subjected to surface treatment and dispersion before use, and the specific operations are as follows: adding the nano particles into the mixture according to the mass ratio of 20: and (3) uniformly mixing the silane coupling agent and the silane coupling agent, then carrying out ultrasonic treatment for 40-60min, and stirring for 20-30min at the speed of 600-800 r/min.
By adopting the technical scheme, the agglomeration of the nano particles is inhibited, and the solubility of the nano particles in an organic medium is enhanced by the nano particles treated by the silane coupling agent, so that the nano particles can be well dispersed in an organic matrix; the epoxy silane coupling agent can generate an interaction force with the nanoparticles, and can generate an interaction force with epoxy resin and polyimide resin to form a nanoparticle surface graft polymer, modify active groups on the surfaces of the nanoparticles, and enhance the dispersibility of the nanoparticles in a resin matrix; the agglomeration of the nano particles can be further reduced by ultrasonic treatment and high-speed stirring, and the dispersibility of the nano particles in the resin matrix is improved. And when the operating conditions and the added amount of the silane coupling agent are within the above ranges, respectively, the influence on the performance test results is within a predictable range.
Optionally, the silane coupling is an epoxy silane coupling agent.
By adopting the technical scheme, epoxy groups can be introduced to the surfaces of the nanoparticles through the epoxy silane coupling agent, so that the compatibility of the nanoparticles in epoxy resin and polyimide resin is improved.
In a second aspect, the present application provides a carbon fiber prepreg, which adopts the following technical scheme:
the carbon fiber prepreg is prepared by impregnating the epoxy resin composition into carbon fibers.
In a third aspect, the present application provides a carbon fiber composite material, which adopts the following technical scheme:
a carbon fiber composite material, characterized in that it is obtained by curing the carbon fiber prepreg according to claim 9.
By adopting the technical scheme, the prepared carbon fiber composite material has high tensile strength, tensile modulus, compressive strength and post-impact compressive strength, and is more suitable for various aerospace products.
In summary, the present application has at least the following beneficial effects:
firstly, triglycidyl isocyanurate is added into raw materials of the epoxy resin composition, and the prepared epoxy resin composition is applied to a carbon fiber composite material through the mutual synergistic effect of the triglycidyl isocyanurate and the raw materials in the epoxy resin composition, so that the carbon fiber composite material has high toughness and rigidity, the tensile strength of the carbon fiber composite material is 2952MPa, the tensile modulus is 166GPa, the compressive strength is 1496MPa, and the compressive strength after impact is 298 MPa;
secondly, a polyimide resin prepared from 3,3',4,4' -benzophenone tetracarboxylic dianhydride, diphenyl sulfide dianhydride, 2' -difluoro-4, 4' - (9-fluorenylidene) diphenylamine and 1,1' -bis (4-aminophenyl) cyclohexane is applied to an epoxy resin composition, so that the tensile strength of the carbon fiber composite material is increased to 2957MPa, the tensile modulus is increased to 168GPa, the compressive strength is increased to 1501MPa, and the compressive strength after impact is increased to 300 MPa;
thirdly, the mixture of the nano-alumina and the nano-rubber particles is used as the nano-particles, and the nano-particles are subjected to surface treatment and dispersion, so that the tensile strength of the carbon fiber composite material is increased to 2967MPa, the tensile modulus is increased to 172GPa, the compressive strength is increased to 1514MPa, and the compressive strength after impact is increased to 307 MPa.
Detailed Description
The present invention will be described in further detail with reference to examples.
Raw materials
The silane coupling agent (gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane) is selected from new materials, Inc. of Jie, Guangzhou; the silane coupling agent (vinyltris (. beta. -methoxyethoxy) silane) is selected from Nanjing Roen silicon materials, Inc.; the polyimide resin is sold in the market, and the trade name is SF-1; the polyetherimide is selected from Rich middle plastic raw material Co., Ltd of Dongguan; the nano alumina is selected from alloy materials of Zhongzhou, Qinghe county, Co.Ltd; the nano-silica is selected from Pander (Shanghai) International trade company; the nano rubber particles are VP501 and selected from the chemical research institute of Beijing, China petrochemical; the polyethersulfone is selected from high standing plastics Co., Ltd, Dongguan; the polysulfone is selected from Guangdong Yuzhou plastic new material science and technology Co., Ltd; the linear o-cresol formaldehyde polyglycidyl ether is selected from the group consisting of novolac polyglycidyl ether, allyl glycidyl ether, bisphenol A glycidyl ether, and is selected from Shenzhen Jia Dida New Material science and technology Co., Ltd; diaminodiphenylmethane tetraglycidyl amine, triglycidyl-p-aminophenol, diglycidyl aniline, selected from the group consisting of the materials science and technology company, Jiannshend, Hunan.
Preparation example
Preparation example 1
A polyimide resin is prepared by adopting the following method:
under the protection of nitrogen, 23kg of 2,2 '-difluoro-4, 4' - (9-fluorenylidene) diphenylamine and 10kg of 1,1 '-bis (4-aminophenyl) cyclohexane are added into 62kg of phenol, stirred until the 2,2' -difluoro-4, 4'- (9-fluorenylidene) diphenylamine and the 1,1' -bis (4-aminophenyl) cyclohexane are completely dissolved, then under the stirring condition, 17kg of 3,3',4,4' -benzophenone tetracarboxylic dianhydride and 8kg of diphenyl sulfide dianhydride are added to react for 24h, then 80kg of deionized water is added to stir for 8min, the mixture is stood for 5min, filtered, filter residue is taken out, and the filter residue is dried in a vacuum oven at the temperature of 82 ℃ to obtain the polyimide resin.
Preparation example 2
A polyimide resin which is different from preparation example 1 in that 2,2' -difluoro-4, 4' - (9-fluorenylidene) diphenylamine is replaced with an equal amount of 1,1' -bis (4-aminophenyl) cyclohexane and the remainder is the same as in preparation example 1.
Preparation example 3
A polyimide resin which is different from preparation example 1 in that diphenyl sulfide dianhydride is replaced with an equal amount of 3,3',4,4' -benzophenone tetracarboxylic dianhydride and the rest is the same as preparation example 1.
Examples
Example 1
An epoxy resin composition, which is prepared by the following method:
dissolving 10kg of commercially available polyimide resin in 40kg of dioxane, adding 60kg of epoxy resin under stirring, stirring for 30min, removing a solvent (dioxane), adding 3kg of triglycidyl isocyanurate under stirring, stirring for 10min, adding 6kg of nanoparticles, 22kg of epoxy resin curing agent, 2kg of imidazole accelerator and 1kg of antioxidant, and stirring until the mixture is uniformly mixed to obtain an epoxy resin composition;
the epoxy resin is a mixture of linear o-cresol formaldehyde polyglycidyl ether, linear phenol aldehyde polyglycidyl ether, allyl glycidyl ether and diaminodiphenylmethane tetraglycidyl amine in a mass ratio of 2:2:1: 5;
the epoxy resin curing agent is 3,3' -diamino diphenyl sulfone;
imidazole promoted is dimethylimidazole;
the toughening agent is polyetherimide, and is ground and sieved to ensure that the grain size of the toughening agent is 0.1-100 mu m continuous gradation;
the nano particles are nano aluminum oxide.
The viscosity of the epoxy resin composition at 90 ℃ was 45000mPa.s, and the epoxy equivalent of the epoxy resin was 160 g/eq.
Example 2
An epoxy resin composition which is different from that of example 1 in that the epoxy resin is a mixture of linear o-cresol formaldehyde polyglycidyl ether, phenol novolac polyglycidyl ether, polypropylene glycol diglycidyl ether, bisphenol a glycidyl ether, triglycidyl-p-aminophenol in a mass ratio of 2:2:0.5:0.5: 5; the epoxy resin curing agent is 3,3' -diamino diphenyl sulfone; imidazole promoting is 2-methyl-5-nitroimidazole; the toughening agent is polyether sulfone;
this epoxy resin composition was different from example 1 in that the viscosity at 90 ℃ was 36500mPa.s, the epoxy equivalent of the epoxy resin was 140g/eq, and the rest was the same as in example 1.
Example 3
An epoxy resin composition which is different from that of example 1 in that the epoxy resin is a mixture of linear o-cresol formaldehyde polyglycidyl ether, linear phenol aldehyde polyglycidyl ether, diaminodiphenylmethane tetraglycidyl amine, triglycidyl-p-aminophenol in a mass ratio of 2:2:3: 3; the epoxy resin curing agent is 3,3 '-diamino diphenyl sulfone and 4,4' -diamino diphenyl sulfone in the weight ratio of 1: 1; imidazole promoting is 2-heptadecyl-imidazole; the nano particles are nano aluminum oxide and nano silicon oxide in a weight ratio of 1: 1;
it is also different from example 1 in that the epoxy resin composition has a viscosity of 42700mPa.s at 90 ℃ and an epoxy equivalent of 120g/eq, and the rest is the same as example 1.
Example 4
An epoxy resin composition which is different from that of example 1 in that the epoxy resin is a mixture of o-cresol novolac polyglycidyl ether, phenol novolac polyglycidyl ether, bisphenol a glycidyl ether, diglycidyl aniline, triglycidyl-p-aminophenol in a mass ratio of 2:3:2:1: 2; the epoxy resin curing agent is 4,4' -diamino diphenyl sulfone; imidazole promotion is 1-benzyl-2-phenylimidazole; the toughening agent is polyether sulfone and polysulfone in a weight ratio of 1: 1;
it is also different from example 1 in that the viscosity of the epoxy resin composition at 90 ℃ is 28500mPa.s, the epoxy equivalent of the epoxy resin is 170g/eq, and the rest is the same as example 1.
Example 5
An epoxy resin composition, which is different from example 1 in that a polyimide resin was prepared as in preparation example 1, and the rest was the same as in example 1.
Example 6
An epoxy resin composition, which is different from example 5 in that a polyimide resin was prepared as in preparation example 2, and the rest was the same as example 5.
Example 7
An epoxy resin composition, which is different from example 5 in that a polyimide resin was prepared as in preparation example 3, and the rest was the same as example 5.
Example 8
An epoxy resin composition, which is different from example 5 in that the nano particles are nano rubber particles, namely nano fully vulcanized powder carboxylated nitrile rubber, and the rest is the same as example 5.
Example 9
An epoxy resin composition which is different from example 8 in that nanoparticles are a mixture of nano alumina and nano rubber particles in a mass ratio of 1:3, and the rest is the same as example 8.
Example 10
An epoxy resin composition, which is different from the epoxy resin composition of example 9 in that the nanoparticles are subjected to surface treatment and dispersion before use, specifically comprising: adding 1.2kg of silane coupling agent into the nanoparticles, stirring until the mixture is uniformly mixed, then carrying out ultrasonic treatment for 60min, then stirring for 30min at the speed of 800r/min to obtain surface-treated and dispersed nanoparticles, and then using the nanoparticles in the preparation of the epoxy resin composition, wherein the silane coupling agent is gamma- (2, 3-glycidoxy) propyl trimethoxy silane, and the rest is the same as that in the example 9.
Example 11
An epoxy resin composition which is different from example 10 in that the silane coupling agent is vinyltris (. beta. -methoxyethoxy) silane in an amount equivalent to that in example 10 and the remainder is the same as in example 10.
Comparative example
Comparative example 1
An epoxy resin composition which is different from example 1 in that triglycidyl isocyanurate is not added to the raw materials of the epoxy resin composition, and the rest is the same as example 1.
Application example
Application example 1
A carbon fiber composite material is prepared by adopting the following method:
adhesive film preparation the epoxy resin composition prepared in example 1 was applied to a coating machine at a coating weight of 33g/m 2 Coating at 90 deg.C to obtain a glue film;
and (2) preparing prepreg, namely compounding the prepared adhesive films on a prepreg machine, respectively placing the two adhesive films on the upper surface and the lower surface of the T800 carbon fiber, performing hot-pressing compounding under a hot-pressing roller at the temperature of 110 ℃, infiltrating the carbon fiber to obtain the prepreg, wherein the width of the prepreg is 1m, and the surface density is 200g/m 2 。
Preparing a fiber composite material: cutting, paving and assembling the prepreg, putting the prepreg into a vacuum bag, and curing by adopting an autoclave process, wherein the curing process is 185 ℃, and the curing time is 120min, so as to prepare the carbon fiber composite material.
Application examples 2 to 11
The carbon fiber composite materials of application examples 2 to 11 were different from application example 1 in that epoxy resin compositions were prepared in the order of examples 2 to 11, respectively, and the rest were the same as application example 1.
Comparative application
Comparative application example 1
A carbon fiber composite material which differs from application example 1 in that epoxy resin compositions were respectively prepared in the following order from comparative example 1, and the rest were the same as application example 1.
Performance test
The following performance tests were performed on 12 carbon fiber composite materials prepared in application examples 1 to 11 and application comparative example 1:
according to ASTM D3039, the tensile strength and tensile modulus of the 11 carbon fiber composite materials are detected;
according to ASTM D6641, testing the compression strength of the 11 carbon fiber composite materials;
the compression strength after impact of the 11 carbon fiber composites was measured according to ASTM D7136, Standard test method for measuring the loss of drop weight impact resistance of fiber-reinforced Polymer matrix composites and ASTM D7137, Standard test method for residual compressive Strength of damaged laminates of Polymer matrix composites, and the results are shown in Table 1.
TABLE 1 test results
As can be seen from Table 1, the carbon fiber composite material prepared from the epoxy resin composition has the advantages of high rigidity, good toughness, high tensile strength, high tensile modulus, high compressive strength and high post-impact compressive strength, wherein the range of the tensile strength is 2949-2967 MPa; the tensile modulus ranges from 164-172 GPa; the compressive strength ranges from 1493-1514 MPa; the compression strength after impact is in the range of 295-307 MPa. In the application, the rigidity and toughness of the carbon fiber composite material are obviously improved through the mutual synergistic effect of the raw materials in the epoxy resin composition, so that the carbon fiber composite material is more suitable for various aerospace products and meets the market demand.
Comparing application comparative example 1 with application example 1, wherein the tensile strength of the carbon fiber composite material prepared in application example 1 is 2952MPa, the tensile modulus is 166GPa, the compressive strength is 1496MPa, and the compressive strength after impact is 298 MPa; the carbon fiber composite material prepared in application comparative example 1 has tensile strength of 2924MPa, tensile modulus of 145GPa, compressive strength of 1467MPa and compressive strength after impact of 274 MPa. The epoxy resin composition of application example 1 was prepared from example 1, and the epoxy resin composition of application comparative example 1 was prepared from comparative example 1. Compared with example 1, triglycidyl isocyanurate is not added into the raw materials of the epoxy resin composition in the comparative example 1, so that when the prepared epoxy resin composition is applied to a carbon fiber composite material, the toughness and rigidity of the carbon fiber composite material are reduced. The triglycidyl isocyanurate contains three epoxy groups, wherein oxygen atoms can generate hydrogen bond interaction with hydrogen atoms in polar groups such as amino groups and hydroxyl groups in epoxy resin and polyimide resin, and the epoxy groups in the triglycidyl isocyanurate are all connected with methylene, so that intermolecular acting force can be improved, certain flexibility is kept, toughness and processability of the epoxy resin composition are facilitated, and compression strength of the carbon fiber composition after impact is improved. And the triglycidyl isocyanurate has a symmetrical structure and contains six-membered rings, so that the rigidity of the triglycidyl isocyanurate cannot be reduced when the triglycidyl isocyanurate is introduced into the epoxy resin composition. Thereby enabling to improve the tensile strength, tensile modulus, compressive strength, post-impact compressive strength of the carbon fiber composite material.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (7)
1. The epoxy resin composition is characterized by comprising the following raw materials in parts by weight: 50-80 parts of epoxy resin, 5-15 parts of polyimide resin, 10-30 parts of toughening agent, 1-10 parts of nano particles, 10-30 parts of epoxy resin curing agent, 0.5-3 parts of triglycidyl isocyanurate, 0.2-5 parts of imidazole accelerator and 0.01-2 parts of antioxidant; the viscosity of the epoxy resin composition at 90 ℃ is 5000-70000mPa.s, and the epoxy equivalent of the epoxy resin is 100-500 g/eq;
the polyimide resin is prepared from the following raw materials in parts by weight: 15-18 parts of 3,3',4,4' -benzophenone tetracarboxylic dianhydride, 8-10 parts of diphenyl sulfide dianhydride, 20-24 parts of 2,2' -difluoro-4, 4' - (9-fluorenylidene) diphenylamine, 10-13 parts of 1,1' -bis (4-aminophenyl) cyclohexane, 55-65 parts of phenol and 75-80 parts of water;
the nano particles are a mixture of inorganic nano particles and nano rubber particles with the mass ratio of 1 (2-4); the inorganic nano particles are one or more of nano aluminum oxide and nano silicon dioxide.
2. The epoxy resin composition as claimed in claim 1, wherein the epoxy resin is a mixture of a glycidyl ether epoxy resin and a glycidyl amine epoxy resin.
3. The epoxy resin composition as claimed in claim 1, wherein the toughening agent is in the form of a powder having a particle size of 0.1 to 100 μm.
4. The epoxy resin composition as claimed in claim 1, wherein the nanoparticles are surface treated and dispersed before use by: adding a silane coupling agent into nanoparticles, wherein the mass ratio of the nanoparticles to the silane coupling agent is 20: (3-4), uniformly mixing, then carrying out ultrasonic treatment for 40-60min, and stirring for 20-30min at the speed of 600-800 r/min.
5. The epoxy resin composition as claimed in claim 4, wherein the silane coupling agent is an epoxy silane coupling agent.
6. A carbon fiber prepreg prepared by impregnating carbon fibers with the epoxy resin composition according to any one of claims 1 to 5.
7. A carbon fiber composite material, characterized in that it is obtained by curing the carbon fiber prepreg according to claim 6.
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| CN1625577A (en) * | 2002-05-13 | 2005-06-08 | 日立化成工业株式会社 | Novel sulfurized phenolic resin, process for producing the same, phenol derivative having thioether structure or disulfide structure, process for producing the same, and epoxy resin composition and ad |
| CN109181622A (en) * | 2018-09-03 | 2019-01-11 | 浙江福斯特新材料研究院有限公司 | A kind of highly heat-resistant polyimide insulating materials of low-temperature setting |
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| JPH08311162A (en) * | 1995-03-16 | 1996-11-26 | Nissan Chem Ind Ltd | Epoxy resin composition for heat-resistant laminated sheet |
| JP3796953B2 (en) * | 1997-04-21 | 2006-07-12 | 東レ株式会社 | Resin composition for fiber reinforced composite material, prepreg and fiber reinforced composite material |
| KR100930937B1 (en) * | 2002-01-31 | 2009-12-10 | 디아이씨 가부시끼가이샤 | Thermosetting polyimide resin composition and manufacturing method of polyimide resin |
| TWI435887B (en) * | 2008-02-26 | 2014-05-01 | Toray Industries | Epoxy resin composition, prepreg and fiber-reinforced composite material |
| EP2623533B1 (en) * | 2010-09-28 | 2020-04-29 | Toray Industries, Inc. | Epoxy resin composition, prepreg and fiber-reinforced compound material |
| WO2014112180A1 (en) * | 2013-01-15 | 2014-07-24 | 東レ株式会社 | Epoxy resin composition, prepreg, and carbon-fiber-reinforced composite material |
| CN107698761A (en) * | 2017-11-03 | 2018-02-16 | 杭州超通科技有限公司 | A kind of preparation method of polyimides |
| KR20200080225A (en) * | 2017-11-14 | 2020-07-06 | 도레이 카부시키가이샤 | Prepreg and fiber reinforced composite material |
| JPWO2020100785A1 (en) * | 2018-11-12 | 2021-09-27 | 三菱ケミカル株式会社 | Method for manufacturing thermosetting epoxy resin composition, thermosetting molding material, thermosetting molding material, fiber-reinforced composite material |
| JP2020176249A (en) * | 2019-04-23 | 2020-10-29 | 帝人株式会社 | Epoxy resin composition, prepreg, method for manufacturing prepreg, and method for producing fiber-reinforced composite material |
| CN112226042A (en) * | 2020-10-13 | 2021-01-15 | 中航复合材料有限责任公司 | Self-adhesive flame-retardant epoxy resin and preparation method thereof |
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| CN1625577A (en) * | 2002-05-13 | 2005-06-08 | 日立化成工业株式会社 | Novel sulfurized phenolic resin, process for producing the same, phenol derivative having thioether structure or disulfide structure, process for producing the same, and epoxy resin composition and ad |
| CN109181622A (en) * | 2018-09-03 | 2019-01-11 | 浙江福斯特新材料研究院有限公司 | A kind of highly heat-resistant polyimide insulating materials of low-temperature setting |
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