CN108485202B - Epoxy resin composition for carbon fiber prepreg - Google Patents
Epoxy resin composition for carbon fiber prepreg Download PDFInfo
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- CN108485202B CN108485202B CN201810362796.3A CN201810362796A CN108485202B CN 108485202 B CN108485202 B CN 108485202B CN 201810362796 A CN201810362796 A CN 201810362796A CN 108485202 B CN108485202 B CN 108485202B
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- 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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- 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
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/06—Unsaturated polyesters
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Abstract
The invention belongs to the field of materials, and particularly relates to an epoxy resin composition for a carbon fiber prepreg, which comprises the following components: 100 parts by weight of bisphenol A epoxy resin; 10-30 parts by weight of unsaturated polyester; 10-50 parts by weight of a carbon chain polymer; 5-50 parts by weight of a filler; 0.2 to 2 parts by weight of an organic peroxide. The epoxy resin composition has strong binding force on a carbon fiber interface, and a composite material obtained by reinforcing carbon fibers has excellent mechanical property, low curing shrinkage rate, high product size precision and sterilization and antibacterial effects.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to an epoxy resin composition for a carbon fiber prepreg.
Technical Field
Epoxy resins are organic compounds that contain two or more epoxy groups in the molecule. Because the molecular structure contains active epoxy groups, the epoxy groups can generate cross-linking reaction with various curing agents to form insoluble high polymers with a three-dimensional network structure. The cured epoxy resin has good physical and chemical properties, excellent bonding strength to the surfaces of metal and non-metal materials, good dielectric property, small deformation shrinkage, good product dimensional stability, high hardness, good flexibility and stability to alkali and most solvents, so that the cured epoxy resin can be widely applied to various fields of production and life of people and can be used for casting, dipping, laminating materials, adhesives, coatings and the like.
The carbon fiber is an inorganic fiber material containing more than 90% of carbon by mass, and has the advantages of low density, high specific strength, high specific modulus, high temperature corrosion resistance, high chemical stability and the like. The carbon fiber is used as a reinforcing material to reinforce the plastic, so that the mechanical property of the plastic, particularly the tensile strength, can be greatly improved, and the carbon fiber reinforced plastic is widely applied to the fields of aerospace, transportation and the like.
However, since carbon fibers are mainly composed of graphite-based carbon, they have natural chemical inertness, high surface energy, poor bonding with resins (particularly epoxy resins), and weak interfacial bonding force, resulting in low compressive, bending and interlaminar shear strength of the composite material, which affects further improvement of material properties and limits the application range thereof.
Through research, people find that the interface binding force of the epoxy resin and the carbon fiber can be improved through modifying the epoxy resin, so that the mechanical property of the composite material is improved.
Chinese patent CN107057283A discloses a method for improving interfacial bonding force of carbon fiber epoxy resin, which is to add graphene oxide, carbon nanotubes and isocyanate to epoxy resin to improve interfacial bonding force and wetting effect of epoxy resin and carbon fiber, thereby improving bending strength and interlaminar shear strength of the composite material. However, graphene oxide and carbon nanotubes have poor dispersibility in epoxy resin, require ultrasonic treatment, have insufficient stability, and cannot be stored for a long time.
Chinese patent CN106046682A discloses a method for improving the performance of epoxy resin fiber composite material, which is to improve the interface bonding force between epoxy resin and fiber by adding halloysite/carbon nano composite material into epoxy resin, thereby improving the performance. This method has a problem that the halloysite/carbon nanocomposite is not easily dispersed in the epoxy resin, resulting in insufficient storage and practicality of the epoxy resin.
Disclosure of Invention
In order to improve the bonding property of the epoxy resin and the carbon fiber and improve the bending strength and the interlaminar shear strength of the composite material, the invention provides an epoxy resin composition for carbon fiber prepreg, which comprises the following components:
100 parts by weight of bisphenol A epoxy resin;
10-30 parts by weight of unsaturated polyester;
10-50 parts by weight of a carbon chain polymer;
5-50 parts by weight of a filler;
0.2 to 2 parts by weight of an organic peroxide.
The unsaturated polyester is further prepared by polycondensation of unsaturated dibasic acid, saturated dibasic acid, tribasic acid and dihydric alcohol, and the weight ratio of the unsaturated dibasic acid to the saturated dibasic acid to the tribasic acid to the dihydric alcohol is 10 (5-10) to 0.1-1 to 10-20.
Preferably, in the raw materials for preparing the unsaturated polyester, the unsaturated dibasic acid is selected from one or more of mesaconic acid and itaconic acid, the saturated dibasic acid is selected from one or more of oxalic acid or 3-phenyl glutaric acid, the tribasic acid is selected from one or more of citric acid or tricarballylic acid, and the dihydric alcohol is selected from one or more of 1, 6-hexanediol or dipropylene glycol.
Further, the viscosity of the unsaturated polyester at 25 ℃ is 1000 to 3000mPa & s.
Further, the carbon chain polymer is selected from one or more of polystyrene and a copolymer thereof, polyvinyl acetate and a copolymer thereof.
Further, the carbon chain polymer is one or more of polyethylene, polystyrene, a polystyrene-polymaleic anhydride block copolymer or a polystyrene-poly (ethylene-butylene) block copolymer.
Further, the filler comprises one or more of silicon carbide, polyphenylene sulfide powder and polystyrene microspheres, wherein the polystyrene microspheres are surface-carboxylated crosslinked polystyrene microspheres.
Preferably, the particle size of the filler is preferably 10-1000 nm, and the particle size distribution is less than 1.3.
Further, the organic peroxide comprises one or more of cyclohexanone peroxide and diacetyl peroxide.
Furthermore, the epoxy resin composition for the carbon fiber prepreg also contains 2-methoxyphenol serving as a free radical inhibitor.
The present invention also includes a cured product obtained by curing the epoxy resin composition for a carbon fiber prepreg, a carbon fiber-reinforced composite material, a prepreg obtained by impregnating carbon fibers with the epoxy resin composition, and a carbon fiber-reinforced material obtained by curing the prepreg.
Has the advantages that: the epoxy resin composition has strong binding force on a carbon fiber interface, and a composite material obtained by reinforcing carbon fibers has excellent mechanical property, low curing shrinkage rate, high product size precision and sterilization and antibacterial effects.
Detailed Description
The epoxy resin composition, the carbon fiber prepreg, and the carbon fiber-reinforced composite material of the present invention will be described in detail below.
The bisphenol A epoxy resin in the epoxy resin composition is a high molecular compound prepared by condensing bisphenol A and epoxy chloropropane under an alkaline condition, is a main component of the resin, and has good physical and mechanical properties, high temperature resistance, chemical resistance and electrical insulation property.
The unsaturated polyester is a polyester containing unsaturated double bonds, which is obtained by polycondensation of polybasic acid and polyhydric alcohol. Can be produced by polycondensation of any of the known unsaturated polybasic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, 2-methylbutenedioic acid, 2, 4-dimethyl-2-pentenedioic acid, 2, 5-dimethyl-2-hexenedioic acid, 2-heptenedioic acid, 3-heptenedioic acid, itaconic acid or any of the known unsaturated polyhydric alcohols such as trimethylolpropane diallyl ether. The unsaturated polyester has excellent processability and corrosion resistance, and has lower price and wide source compared with the epoxy resin. However, the unsaturated polyester has poorer mechanical property and larger curing shrinkage compared with epoxy resin, so the addition amount of the unsaturated polyester is not too much, and the unsaturated polyester is preferably 15 to 20 parts by weight.
The unsaturated polyester is prepared by polycondensation of unsaturated dibasic acid, saturated dibasic acid, tribasic acid and dihydric alcohol, and the weight ratio of the unsaturated dibasic acid to the saturated dibasic acid to the tribasic acid to the dihydric alcohol is (10), (5-10), (0.1-1) and (10-20).
The unsaturated dibasic acid includes maleic acid, fumaric acid, citraconic acid, mesaconic acid, 2, 4-dimethyl-2-glutaconic acid, 2, 5-dimethyl-2-hexenedioic acid, 2-heptenedioic acid, 3-heptenedioic acid, itaconic acid, and the like. Preferably 2, 4-dimethyl-2-pentenedioic acid, 2, 5-dimethyl-2-hexenedioic acid, 2-heptenedioic acid, 3-heptenedioic acid, citraconic acid, mesaconic acid, itaconic acid; more preferably itaconic acid.
The saturated dibasic acid can control the unsaturation degree of the unsaturated polyester resin and the performance of the epoxy resin. The saturated dibasic acid used in the present invention is a known saturated dibasic acid, and examples thereof include phthalic acid, isophthalic acid, terephthalic acid, chlorendic acid, succinic acid, adipic acid, sebacic acid, tetrachlorophthalic acid, tetrabromophthalic acid, endomethylenetetrahydrophthalic acid, 3-phenylpentanedioic acid, and the like, and may be a mixture of one or more of them. Preferably one or more of oxalic acid, adipic acid, phthalic acid, chlorendic acid, succinic acid, 3-phenyl glutaric acid, and more preferably 3-phenyl glutaric acid. Preferably, the weight ratio of the saturated dibasic acid to the unsaturated dibasic acid is (6-8): 10.
the tribasic acid can be a tribasic acid known in the art, and can react with a plurality of diols, organic peroxide and epoxy resin to improve the crosslinking curing rate and improve the performance of the epoxy resin composition after curing. Specifically, trimellitic acid, trimesic acid, tricarballylic acid, citric acid, nitrilotriacetic acid, etc. are preferable from the viewpoint of excellent properties, and in order to obtain an epoxy resin composition having excellent overall properties, the weight ratio of the tribasic acid to the unsaturated dibasic acid is preferably (0.3 to 0.7): 10.
as the diol, there can be used those known in the art, and there may be mentioned, for example, ethylene glycol, propylene glycol, neopentyl glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, pentanediol, hexanediol and the like, and from the viewpoint of excellent properties, one or more of propylene glycol, hexanediol, neopentyl glycol, pentanediol and dipropylene glycol are preferable. In order to obtain the epoxy resin composition with excellent comprehensive performance, the weight ratio of the dihydric alcohol to the unsaturated dibasic acid is preferably (13-18): 10.
the unsaturated polyester can be synthesized by a known method using the kind and amount of the above-mentioned raw materials. Various conditions in the synthesis are set according to the kind and amount of the raw material. Usually, the esterification is carried out under an inert gas atmosphere such as nitrogen and under the condition of using organic metal salt as a catalyst and under the condition of pressurizing or decompressing at the temperature of 140-230 ℃. Specific examples of the catalyst include one or more of manganese acetate, stannous oxalate, zinc acetate, cobalt acetate, and the like.
Further, in order to ensure better compatibility and processability of the unsaturated polyester, the viscosity of the unsaturated polyester at 25 ℃ is preferably 1000 to 3000 mPa.s, more preferably 1500 to 2500 mPa.s at 25 ℃, and the viscosity can be measured by a rotational rheometer.
The carbon chain polymer is a polymer with a macromolecular main chain completely consisting of carbon atoms, and can be used for improving the processing performance of the epoxy resin composition and reducing the curing volume shrinkage. The carbon chain polymer may be one or more of carbon chain polymers well known in the art, such as homopolymers and copolymers of olefin and its derivative polymers, and alkyne and its derivative polymers. Such as polyethylene, polypropylene, polyvinyl alcohol, polyvinyl acid, polymaleic acid, polystyrene, and the like, and copolymers thereof. From the viewpoint of excellent performance, one or more of a polystyrene-polymaleic anhydride block copolymer and a polystyrene-poly (ethylene-butylene) block copolymer are preferred, and a mixture of the two is more preferred, and the weight ratio of the two is 4:1 to 1:1, and the preferred ratio is 2:1 to 1: 2. In order to ensure excellent processability, low curing volume shrinkage and excellent mechanical properties, the carbon chain polymer content is 20-40 parts by weight.
Among them, as a filler in an epoxy resin composition, it is used to improve heat resistance of the composition and a composite material. The filler is preferably one or more of calcium carbonate, graphite, silicon dioxide, silicon carbide, boron nitride, alumina, polyphenylene sulfide powder, polyaniline powder and polystyrene microspheres, the particle size of the filler is preferably 10-1000 nm, more preferably 100-500 nm, and the particle size distribution is less than 1.3, more preferably less than 1.2. Polyphenylene sulfide powder and polystyrene microspheres are more preferable for better compatibility and heat resistance. In order to improve the excellent comprehensive performance of the epoxy resin composition, the content of the filler is preferably 15-40 parts by weight. The polyphenylene sulfide powder is prepared by crushing polyphenylene sulfide at low temperature. The polystyrene microsphere is prepared by synthesizing styrene monomer by a microemulsion polymerization method, an emulsion polymerization method, a dispersion polymerization method, a suspension polymerization method, a seed polymerization method and the like.
Furthermore, the polystyrene microsphere is a crosslinked polystyrene microsphere with carboxylated surface. The compatibility and the dispersion of the filler and the epoxy resin composition are more uniform. The surface carboxylated crosslinked polystyrene microsphere can be prepared by the following method: styrene and acrylic acid are taken as monomers, divinylbenzene is taken as a cross-linking agent, azodiisobutyronitrile is taken as an initiator, and the styrene and acrylic acid copolymer is synthesized by adopting dispersion polymerization and a cross-linking agent post-dropping method. The particle size is preferably 10-1000 nm, and the particle size distribution is less than 1.2.
In the present invention, the particle size of the filler is the number average particle size thereof, and the particle size distribution is the ratio of the weight average particle size to the number average particle size of the filler, and can be measured by a laser particle sizer.
The organic peroxide in the epoxy resin composition can accelerate the curing rate and effect of the epoxy resin composition, and may be any of known organic peroxides, such as one or more of peroxycarbonate, peroxyester, diacyl peroxide, and dialkyl peroxide. The content of the organic peroxide is less than 0.2 part by weight, and the curing acceleration of the epoxy resin composition is not obvious; when the content of the organic peroxide is more than 2 parts by weight, the curing of the epoxy resin composition cannot be accelerated by increasing the content of the organic peroxide, and the content is preferably 0.5 to 1.5 parts by weight.
The preferred epoxy resin compositions are phenol compounds, benzoquinone, hydroquinone, catechol, stable free radical and/or phenothiazine, the amount of free radical inhibitor that can be added can vary over a relatively wide range and can be selected as the primary indicator of achieving the desired gel time, suitable free radical inhibitors can be selected depending on the type of epoxy resin composition, specifically 2-methoxyphenol, 4-methoxyphenol, 2, 6-di-tert-butyl-4-methylphenol, 2, 6-di-tert-butylphenol, 2,4, 6-trimethylphenol, 2,4, 6-tris (dimethylaminomethyl) phenol, 4 ' -thio-bis (3-methyl-6-tert-butylphenol), 4 ' -isopropylidenylidenylphenol, 2, 4-di-tert-butylphenol, 6,6 ' -di-tert-butyl-2, 2 ' -methylenedi-p-cresol, hydroquinone, 2-methylhydroquinone, 2-tert-butylhydroquinone, 2-butylcatechol, 6-butylcatechol, 2,6 ' -di-tert-butylcatechol, 5-tetramethylcatechol, 5-butyl-4-methoxy-4-methyl-4-methylphenol, 6-tetramethyl-2, 6-butyl-4-methoxy-methyl-4-methyl-2, 6-methoxy-2, 2, 5-methoxy-methyl-2, 5-methoxy-methyl-2, 6-methoxy-2, 5-methoxy-methyl-2, 2, 5-methoxy-2, 2, 6-methoxy-2, 2, 6-methoxy-.
The epoxy resin composition for carbon fiber-reinforced composite material of the present invention can be used in combination with a curing agent. The curing agent described here is a curing agent for the epoxy resin contained in the epoxy resin composition of the present invention, and is a compound having an active group capable of reacting with an epoxy group. Specific examples of the curing agent include dicyandiamide, aromatic polyamine, aminobenzoate, various acid anhydrides, phenol novolac, o-cresol novolac, polyphenol compounds, imidazole derivatives, aliphatic amines, tetramethylguanidine, thiourea-added amines, carboxylic acid anhydrides such as methylhexahydrophthalic anhydride, and lewis acid complexes such as hydrazine carboxylate, amine carboxylate, polythiol, and boron trifluoride ethylamine complex.
The preparation method of the epoxy resin composition is to uniformly mix the raw materials of the epoxy resin composition according to the mixture ratio.
The prepreg of the present invention can be produced by the following method: dissolving the epoxy resin composition of the present invention in an organic solvent, impregnating the organic solvent into reinforcing fibers, taking out the reinforcing fibers, and evaporating the solvent using an oven or the like; alternatively, the epoxy resin composition may be heated to impregnate the reinforcing fibers with the epoxy resin composition, and then taken out and cooled.
The carbon fiber reinforced epoxy resin composite material can be prepared by hot-pressing, curing and molding the carbon fiber prepreg.
The epoxy resin composition, the carbon fiber prepreg and the carbon fiber composite material thereof can be applied to various aspects of industrial production and people life, such as the aerospace field, outdoor sports equipment, transportation accessories, industrial production molds, common appliances for daily life and the like.
The epoxy resin composition, the prepreg using the epoxy resin composition, and the carbon fiber-reinforced composite material of the present invention will be described in more detail below with reference to examples. Methods for producing carbon fibers, resin raw materials, prepregs, and carbon fiber-reinforced composite materials, methods for evaluating pore compression strength, and methods for evaluating tensile strength used in examples are as follows.
The unsaturated polyester is synthesized from the following raw materials:
[ unsaturated dibasic acid ]
A1: mesaconic acid, produced by Shanghai Haohua chemical Co., Ltd.;
a2: itaconic acid, produced by chemical industry ltd, Dewang, Henan;
[ saturated dibasic acids ]
B1: adipic acid, available from Shanghai Yuanji Co., Ltd;
b2: 3-phenyl glutaric acid, a product of chemical Limited, Wande Hubei;
[ tribasic acid ]
C1: citric acid, available from shanghai monogao biotechnology limited;
c2: tricarballylic acid, a product of Shanghai Yiji industries, Ltd.;
[ DIETHYLENE ALCOHOL ]
D1: 1, 6-hexanediol, a product of chemical Limited, Wande Hubei;
d2: dipropylene glycol, produced by Kyoto science and technology, Inc., Hubei;
according to the raw materials and the formula shown in the table 1, the unsaturated polyester is obtained by the following preparation method:
1. introducing nitrogen into the reaction kettle to exhaust air, then adding unsaturated dibasic acid, saturated dibasic acid, tribasic acid and polyalcohol, stirring and mixing uniformly;
2. heating the mixture to 130 deg.C or higher to melt it sufficiently, removing water produced by the reaction under reduced pressure, continuously monitoring the viscosity of the system at 25 deg.C, and reducing the temperature to 105 deg.C when the viscosity reaches the corresponding value shown in Table 1;
3. adding 1 weight part of 2-methoxyphenol into the reaction kettle, continuously stirring for 5min, and cooling to obtain the unsaturated polyester resin.
TABLE 1 unsaturated polyesters
The epoxy resin composition comprises the following raw materials:
[ bisphenol A epoxy resin ]
E: the molecular weight of the product of Hubei Chusheng wafer chemical company is 3100-7000;
[ carbon chain polymers ]
F1: polyethylene, produced by China Shenhua coal-to-liquids chemical industry Co., Ltd, and having a trade mark of 8007, a density of 0.963g/cm3, and a melt index of 8.2g/10min at 190 ℃;
f2: polystyrene, manufactured by the Dow group of America, having a designation of 1200, a density of 1.05g/cm3 and a melt index of 5.0g/10min at 200 ℃;
f3: polystyrene-polymaleic anhydride block copolymer: average molecular weight 1700, styrene 68 wt%, acid value 335, from Aldrich Chemicals
375mg KOH/g。
F4: polystyrene-poly (ethylene-butylene) block copolymer: the dynamic viscosity of a 20% toluene solution having an average molecular weight of 89000, manufactured by Aldrich chemical company, was 550 Cp.
[ Filler ]
G1: silicon carbide powder: NO-C-001-1 produced by Shanghai Naiyao nanotechnology Co., Ltd, and having a particle size of 50 nm;
g2: polyphenylene sulfide powder, A360M, a product of Toray corporation, Japan, and having a particle diameter of 200 nm.
G3: dissolving styrene, acrylic acid, divinyl benzene and azobisisobutyronitrile with the mass ratio of 15:1:1:1 in a mixed solution of water and ethanol, and heating to 70 ℃ in the atmosphere of nitrogen to react for 8 hours to obtain crosslinked polystyrene microspheres with carboxylated surfaces, wherein the particle size is 500 nm;
[ organic peroxides ]
H1: cyclohexanone peroxide, manufactured by Hubei Xin Mingtai chemical Co., Ltd;
h2: diacetyl peroxide, a product of Shanghai Hao chemical Co., Ltd;
[ free radical inhibitors ]
I1: 2-methoxyphenol, available from Shanghai Nuotai chemical Co., Ltd
[ carbon fiber ]
CO6142 manufactured by Tokory K.K., thickness of 0.15mm, and areal density of 119g/m 2.
Examples 1 to 17
The epoxy resin compositions of examples 1 to 17 were prepared by adding the raw materials and the compounding ratios shown in Table 2 to an internal mixer, kneading at 160 ℃ for 20min, and cooling to room temperature.
TABLE 2 epoxy resin compositions
Wherein "-" means that no free radical inhibitor is present.
Comparative example 1
The epoxy resin composition of this comparative example contained only bisphenol a epoxy resin.
Comparative example 2
The epoxy resin composition of this comparative example was obtained by mixing only 100 parts by weight of bisphenol A epoxy resin and 10 parts by weight of unsaturated resin a.
Comparative example 3
The epoxy resin composition of this comparative example was prepared by mixing only 100 parts by weight of bisphenol A epoxy resin, 10 parts by weight of unsaturated resin a, and 10 parts by weight of carbon chain compound F1.
Comparative example 4
The epoxy resin composition of this comparative example was prepared by mixing only 100 parts by weight of bisphenol A epoxy resin with 10 parts by weight of unsaturated resin a, 10 parts by weight of carbon chain compound F1, and 5 parts by weight of filler G1.
Comparative example 5
The epoxy resin composition of this comparative example was prepared by mixing only 100 parts by weight of bisphenol A epoxy resin with 10 parts by weight of unsaturated resin a, 5 parts by weight of filler G1, and 0.2 part by weight of organic peroxide H1.
Comparative example 6
The epoxy resin composition of this comparative example was prepared by mixing only 100 parts by weight of bisphenol A epoxy resin with 5 parts by weight of filler G1, 10 parts by weight of carbon chain compound F1, and 0.2 parts by weight of organic peroxide H1.
The epoxy resin compositions prepared in examples and comparative examples were uniformly mixed with a curing agent ethylenediamine (10% by mass of the epoxy resin composition) to obtain an uncured epoxy resin mixture. The epoxy resin composition was subjected to a molding shrinkage test. The test results are shown in table 3.
The obtained uncured epoxy resin mixed solution was applied to a release paper with a weight per resin unit area of 50g/m2 using a blade coater to prepare a resin film. The resin film was superposed on both sides of a carbon fiber (CO 6142, manufactured by Tokory Co., Ltd., thickness 0.15mm, area density, 119g/m2) gathered unidirectionally, and the carbon fiber was impregnated with the epoxy resin composition by heating and pressurizing to 1MPa at 100 ℃ and 1 atm with a hot roll to obtain a prepreg. The multilayer prepregs were stacked in order and cured under heat pressing at 100 ℃ under 1MPa for 10 hours to obtain carbon fiber reinforced composite samples. The composite was tested for tensile strength, flexural strength and interlaminar shear strength. The test results are shown in table 3.
The invention relates to a property to be measured and a method for measuring the same.
Tensile strength: the prepreg was cut into a predetermined size, 6 sheets were laminated in one direction, vacuum-packed, and cured at 180 ℃ and 6kg/cm2 for 2 hours using an autoclave to obtain a carbon fiber-reinforced composite material. The unidirectional reinforcing material was cut into pieces having a width of 12.7mm and a length of 230mm, and thin pieces made of glass fiber reinforced plastic having a length of 1.2mm and a length of 50mm were bonded to both ends of the pieces to obtain test pieces. The test piece was subjected to a tensile test using an Instron universal tester in accordance with the specification of JIS K7073-1988.
Bending strength, namely, orderly stacking a plurality of prepared prepregs, carrying out hot-pressing curing for 10 hours at the temperature of 100 ℃ and under the pressure of 1MPa to obtain the carbon fiber reinforced composite material, processing a bending strength test sample with the length of ×, the width of × and the thickness of 100mm × 15mm, 15mm and × 4mm, and testing according to GB/T1449-2005.
Interlaminar shear strength: the prepared prepregs are orderly stacked together in multiple layers, are subjected to hot pressing and curing for 10 hours at the temperature of 100 ℃ and under the pressure of 1MPa to obtain the carbon fiber reinforced composite material, are processed into a standard interlaminar shear strength test sample, and are measured by taking GB/T1450.1-2005 as a reference.
Molding shrinkage rate: 10 layers of cut carbon fiber cloth (CO 6142, manufactured by Tokory Co., Ltd., Japan, thickness 0.15mm, areal density 119 g)/m2) The carbon fiber reinforced composite material was obtained by stacking the carbon fiber reinforced composite material in order in a closed mold having a length of ×, a width of × and a thickness of 100mm × 100mm × 4mm, filling the mold with a mixture of the epoxy resin compositions of the examples and comparative examples and a curing agent ethylenediamine (10% by mass of the epoxy resin composition), sealing and heating the mixture to 100 ℃ to cure and mold the mixture, and measuring the volume of the composite material:
the molding shrinkage rate (volume of the carbon fiber reinforced composite material/volume of the mold) is × 100%.
Table 3 results of performance testing
As shown in Table 3, compared with comparative examples 1-6, the epoxy resin compositions of the examples and the carbon fiber prepregs and carbon fiber reinforced composite materials prepared from the epoxy resin compositions are greatly improved in mechanical properties and molding shrinkage.
The above description is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto. Any person skilled in the art should be able to substitute or change the technical solution of the present invention and its inventive concept within the technical scope of the present invention.
Claims (8)
1. An epoxy resin composition for a carbon fiber prepreg, characterized by comprising the following components:
the unsaturated polyester is prepared by the polycondensation of unsaturated dibasic acid, saturated dibasic acid, tribasic acid and dihydric alcohol, and the weight ratio of the unsaturated dibasic acid to the saturated dibasic acid to the tribasic acid to the dihydric alcohol is 10 (5-10) to (0.1-1) to (10-20),
wherein the unsaturated dibasic acid is selected from one or more of mesaconic acid or itaconic acid, the saturated dibasic acid is selected from one or more of oxalic acid or 3-phenyl glutaric acid, the tribasic acid is selected from one or more of citric acid or tricarballylic acid, and the dihydric alcohol is selected from one or more of 1, 6-hexanediol or dipropylene glycol.
2. The epoxy resin composition for a carbon fiber prepreg according to claim 1, wherein the viscosity of the unsaturated polyester at 25 ℃ is 1000 to 3000 mPa-s.
3. The epoxy resin composition for carbon fiber prepreg according to claim 1, wherein the carbon chain polymer is one or more selected from the group consisting of polystyrene and a copolymer thereof, and polyvinyl acetate and a copolymer thereof.
4. The epoxy resin composition for carbon fiber prepreg according to claim 3, wherein the carbon chain polymer is one or more of polystyrene, polystyrene-polymaleic anhydride block copolymer, or polystyrene-poly (ethylene-butylene) block copolymer.
5. The epoxy resin composition for carbon fiber prepreg according to claim 1, wherein the filler comprises one or more of silicon carbide, polyphenylene sulfide powder, polystyrene microspheres, wherein the polystyrene microspheres are surface carboxylated crosslinked polystyrene microspheres.
6. The epoxy resin composition for a carbon fiber prepreg according to claim 5, wherein the filler has a particle diameter of preferably 10 to 1000nm, and the particle diameter distribution is less than 1.3.
7. The epoxy resin composition for carbon fiber prepreg according to claim 1, wherein the organic peroxide comprises one or more of cyclohexanone peroxide and diacetyl peroxide.
8. The epoxy resin composition for a carbon fiber prepreg according to any one of claims 1 to 7, characterized by further comprising a radical inhibitor 2-methoxyphenol.
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| JP2005060644A (en) * | 2003-08-11 | 2005-03-10 | Biruken Kk | Epoxy/unsaturated polyester/methyl trisilane containing silicone dispersion composite resin composition |
| CN104262903A (en) * | 2014-09-09 | 2015-01-07 | 丹阳丹金汽车部件有限公司 | Modified carbon fiber composite material with strong bond force and preparation method thereof |
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| JP2005060644A (en) * | 2003-08-11 | 2005-03-10 | Biruken Kk | Epoxy/unsaturated polyester/methyl trisilane containing silicone dispersion composite resin composition |
| CN104262903A (en) * | 2014-09-09 | 2015-01-07 | 丹阳丹金汽车部件有限公司 | Modified carbon fiber composite material with strong bond force and preparation method thereof |
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