CN113980246A - Curable resin composition, composite material and preparation method thereof - Google Patents
Curable resin composition, composite material and preparation method thereof Download PDFInfo
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- CN113980246A CN113980246A CN202111337321.7A CN202111337321A CN113980246A CN 113980246 A CN113980246 A CN 113980246A CN 202111337321 A CN202111337321 A CN 202111337321A CN 113980246 A CN113980246 A CN 113980246A
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- epoxy resin
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- 239000011342 resin composition Substances 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000004593 Epoxy Substances 0.000 claims abstract description 13
- 125000000524 functional group Chemical group 0.000 claims abstract description 10
- 239000003822 epoxy resin Substances 0.000 claims description 28
- 229920000647 polyepoxide Polymers 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- -1 amine compounds Chemical class 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 239000004845 glycidylamine epoxy resin Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 2
- 150000004714 phosphonium salts Chemical group 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 239000005056 polyisocyanate Substances 0.000 claims description 2
- 229920001228 polyisocyanate Polymers 0.000 claims description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 230000003014 reinforcing effect Effects 0.000 claims description 2
- 150000003384 small molecules Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 230000008719 thickening Effects 0.000 claims description 2
- 239000004843 novolac epoxy resin Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 5
- 239000012205 single-component adhesive Substances 0.000 abstract description 4
- 238000003541 multi-stage reaction Methods 0.000 abstract description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 11
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000000835 fiber Substances 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 229920002748 Basalt fiber Polymers 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- LSEFCHWGJNHZNT-UHFFFAOYSA-M methyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 LSEFCHWGJNHZNT-UHFFFAOYSA-M 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4057—Carbamates
-
- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2463/04—Epoxynovolacs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Emergency Medicine (AREA)
- Manufacturing & Machinery (AREA)
- Reinforced Plastic Materials (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention provides a curable resin composition, a composite material and a method for preparing the same, wherein the curing reaction of the curable resin composition is not only the reaction of a curing agent and an epoxy functional group, but also the composite reaction of a plurality of reactions. Meanwhile, the curable resin composition has latency and can be used for preparing a composite material prepreg and a single-component adhesive.
Description
Technical Field
The invention relates to a curable resin composition, a composite material and a preparation method thereof, belonging to the field of polymer composite materials.
Background
In the curing of epoxy resins, various types of curing agents can be added to crosslink and cure the epoxy resins by reacting the curing agents with epoxy functional groups.
In the application fields of composite prepreg, single-component adhesive and the like, the epoxy resin and the curing agent are expected to react slowly at low temperature and have long storage life after being mixed; and after the reaction is heated to a high temperature, the reaction can be rapidly carried out, namely the latency. The latent curing agent for epoxy resin mainly comprises dicyandiamide and modified products thereof, modified imidazole, modified tertiary amine and the like, and the latent curing agent is mainly used for curing the resin by reacting with epoxy functional groups of the epoxy resin. However, conventional latent curing agents for epoxy resins tend to have a conflict in latency and reactivity, i.e., the better the latency, the lower the reactivity, and the better the reactivity, the worse the latency. Conventional latent curing systems for epoxy resins require low temperature refrigeration storage.
In addition, the composite prepreg is desired to have a low viscosity of the resin when impregnating the fibers and a high viscosity of the resin after completion of impregnation. The conventional method is to adopt a solvent to dissolve high-viscosity epoxy resin, then impregnate the fiber, and then dry the solvent after the impregnation is finished; or heating the high-viscosity epoxy resin to reduce the viscosity of the epoxy resin, then impregnating the fiber, and cooling to increase the viscosity after the impregnation is finished. The traditional method has poor environmental friendliness, high energy consumption and poor economic and social benefits.
The curing reaction of the common epoxy curing agent and the epoxy resin is usually a single reaction, so the requirements of the process conditions and the reaction ratio are severe. A more relaxed process window can be obtained by developing a more relaxed free compounding reaction of the curable resin composition.
Disclosure of Invention
An object of the present invention is to provide a curable resin composition, a composite material and a method for producing the same, in which a curing reaction of the curable resin composition is not only a reaction of a curing agent with an epoxy functional group but also a complex reaction of a plurality of reactions. Meanwhile, the curable resin composition has latency and can be used for preparing a composite material prepreg and a single-component adhesive.
In order to achieve the purpose, the invention adopts the technical scheme that:
the present invention provides a curable resin composition comprising the following components:
a first component: epoxy resin and oligomer containing epoxy functional group and hydroxyl functional group in molecular structure;
a second component: small molecules and/or oligomers having a molecular structure comprising one or more structural units represented by formula 1;
in the formula 1, R1、R2、R3、R4、R5Each is independently any one of hydrogen, carbon, methyl, methylene, methine, ethyl, propyl, butyl and halogen;
the first component contains a molar ratio of hydroxyl functional groups to functional groups represented by formula 1 of 0.3:1 to 3: 1.
Preferably, the oligomer containing both epoxy functional groups and hydroxyl functional groups includes, but is not limited to, oligomers of low molecular weight epoxy resins produced by chain extension of one or more of amine compounds (having a functionality of 2 or more, as active hydrogen, including ethanolamine), polyphenolic compounds, polycarboxylic acids, polyisocyanates, and mixtures thereof.
More preferably, the epoxy resin is one or a mixture of more of (hydrogenated) bisphenol A/F epoxy resin, phenolic epoxy resin, glycidyl amine epoxy resin and glycidyl ester epoxy resin.
Preferably, representative structures of the second component include, but are not limited to:
preferably, the composition may also contain a small amount of accelerator or no accelerator (i.e., 0% by weight), typically 0.5-3% by weight.
More preferably, the accelerator comprises one or more of a tertiary phosphine, a quaternary phosphonium salt, a blocked tertiary amine and a blocked imidazole.
When the curable resin composition is heated and cured, the curing reaction is a composite reaction, and the main reaction comprises the following steps:
a. the second component decomposes to produce segments containing isocyanate functional groups and segments containing phenol functional groups;
b. the fragments containing the phenol functional groups generated by the decomposition of the second component react with the epoxy functional groups of the first component to generate hydroxyl functional groups;
c. the fragments containing the isocyanate functional groups generated by the decomposition of the second component react with the hydroxyl functional groups contained in the first component and the hydroxyl functional groups generated by the reaction to generate a carbamate structure; in addition, it is also possible for the isocyanato function to react with epoxy groups, but this reaction is much slower than the isocyanato function and hydroxyl groups and therefore less predominant.
d. The above 3 reactions cooperate with each other to crosslink and cure the resin composition.
The invention also provides a composite material comprising the curable resin composition.
Preferably, the composite material also comprises a reinforcing component, a filler and an auxiliary agent.
More preferably, the reinforcement component includes carbon fibers, glass fibers, quartz fibers, basalt fibers, aramid fibers and other fibers useful for composite reinforcement.
The invention also provides a preparation method of the composite material, which comprises the following steps: the preparation method comprises the steps of firstly preparing the prepreg, and then thermally curing to prepare a final product, wherein the prepreg can be prepared by firstly preparing the prepolymer and then dipping the prepolymer in glue, and can also be chemically thickened by utilizing the chain extension reaction of the first component during the dipping in glue.
The invention has the beneficial effects that: the curing reaction mode of the epoxy resin is expanded, and the epoxy resin is cured quickly by adopting a composite curing reaction, so that the epoxy resin has excellent latency. In addition, the reaction of the isocyanate group and the hydroxyl group blocks the hydroxyl group, so that the hydrophilicity of the cured resin can be reduced and the insulating property of the cured resin can be improved. Meanwhile, the curable resin composition can be used for preparing the prepreg by chemical thickening, so that the production process difficulty of the prepreg can be reduced, and the production cost can be reduced.
The curable resin composition of the present invention has a slow chemical reaction rate at a temperature of less than 40 ℃; when the temperature is higher than 100 ℃, the chemical reaction speed is very high, namely the latent property is realized, and the method can be used for preparing the prepreg of the composite material and the single-component adhesive.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be described in further detail with reference to examples. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
100 parts of low molecular weight bisphenol A epoxy resin with the epoxy equivalent of 180-190 is put into a reaction kettle, 30 parts of bisphenol A is added, the temperature is heated to 80 ℃, and the bisphenol A is dissolved by stirring. Then 1 part of methyl triphenyl phosphonium bromide is added, after being stirred evenly, the temperature is raised to 120 ℃, and the bisphenol A starts to react with the epoxy resin in an exothermic way. After the heat release is finished, the temperature is increased to 160 ℃, and the reaction is carried out for 3 hours under the heat preservation condition, so as to obtain the first component.
Taking a micromolecular compound shown in a structural formula 2 as a second component.
Mixing the first component and the second component at a ratio of 80:20 at 80 deg.C, and cooling to 25 deg.C to obtain composition 1.
After 30 days of storage at ambient temperature, composition 1 above was not yet cross-linked and cured.
The composition 1 was put into an oven at 120 ℃ for 2 hours and then taken out, and it was found that it was crosslinked and cured.
Example 2
90 parts of low-molecular-weight bisphenol A epoxy resin with the epoxy equivalent of 180-190 and 10 parts of phenolic epoxy resin (NPPN-638S, available from south Asia epoxy resin (Kunshan) Co., Ltd.) are taken and put into a reaction kettle, 30 parts of bisphenol A is added, the mixture is heated to 80 ℃, and the mixture is stirred to dissolve the bisphenol A. Cooling to 40 deg.c, adding 1 part of triphenyl phosphine and stirring to obtain the first component.
Mixing the micromolecule compounds shown in the structural formulas 2 and 3 according to the ratio of 1:1 to obtain a second component.
The first component and the second component are mixed evenly according to the mixture ratio of 70:30 at 60 ℃ to obtain the composition 2.
After 30 days of storage at ambient temperature, composition 2, described above, had an increase in viscosity but was not cross-linked and cured.
The composition 2 was placed in an oven at 120 ℃ for 2 hours and then taken out, and it was found to be crosslinked and cured.
Example 3
The composition 2 prepared in example 2 was impregnated into a carbon fiber cloth at 60 ℃ to prepare a prepreg. When the prepreg is thickened at 40-45 ℃ for 24 hours, the viscosity of the resin is increased and the fluidity is deteriorated.
And (3) paving the prepreg on a metal mould, pressing by using a hydraulic press, and keeping the temperature at 150 ℃ for 5 minutes. And demolding to obtain the carbon fiber reinforced composite plate.
Example 4
Taking 80 parts of low molecular weight bisphenol A epoxy resin with the epoxy equivalent of 180-190, sequentially adding 20 parts of bisphenol F epoxy resin, 40 parts of mixture of micromolecule compounds and oligomers shown in structural formulas 2 and 4 and 5 parts of monoethanolamine at normal temperature, and uniformly stirring to obtain the composition 3.
After the composition 3 is prepared, the chopped glass fibers are quickly impregnated at normal temperature to prepare the prepreg. When the resin is thickened at normal temperature for 24 hours, the viscosity of the resin increases and the fluidity is deteriorated.
And (3) paving the prepreg on a metal mould, pressing by using a hydraulic press, and keeping the temperature at 140 ℃ for 10 minutes. And demolding to obtain the glass fiber reinforced composite plate.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A curable resin composition comprising the following components:
a first component: a mixture of an epoxy resin and an oligomer having both an epoxy functional group and a hydroxyl functional group in its molecular structure;
a second component: small molecules and/or oligomers having a molecular structure comprising one or more structural units represented by formula 1;
in the formula 1, R1、R2、R3、R4、R5Each is independently any one of hydrogen, carbon, methyl, methylene, methine, ethyl, propyl, butyl and halogen;
the first component contains a molar ratio of hydroxyl functional groups to functional groups represented by formula 1 of 0.3:1 to 3: 1.
2. The curable resin composition of claim 1, wherein the oligomers containing both epoxy and hydroxyl functional groups comprise oligomers of low molecular weight epoxy resins produced by chain extension of one or more of amine compounds, polyphenolic compounds, polycarboxylic acids, polyisocyanates, and mixtures thereof.
3. The curable resin composition of claim 1, wherein the epoxy resin is one or more of (hydrogenated) bisphenol a/F epoxy resin, novolac epoxy resin, glycidylamine epoxy resin, and glycidylester epoxy resin.
4. The curable resin composition of claim 1, wherein the representative structure of the second component comprises:
5. the curable resin composition of claim 1, further comprising an accelerator added in an amount of 0-3%.
6. The curable resin composition of claim 5, wherein the accelerator comprises one or more of a tertiary phosphine, a quaternary phosphonium salt, a blocked tertiary amine, and a blocked imidazole.
7. A composite material comprising a curable resin composition according to any one of claims 1 to 6.
8. A composite material according to claim 7, further comprising reinforcing components, fillers and auxiliaries.
9. A method of making the composite material of claim 7, comprising: the preparation method comprises the steps of firstly preparing prepreg, then thermally curing to prepare a final product, and firstly preparing prepolymer and then impregnating glue when preparing the prepreg.
10. The production method according to claim 9, wherein the prepreg is produced by chemical thickening using a chain extension reaction of the first component while impregnating with glue.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111337321.7A CN113980246A (en) | 2021-11-12 | 2021-11-12 | Curable resin composition, composite material and preparation method thereof |
| PCT/CN2021/132257 WO2023082322A1 (en) | 2021-11-12 | 2021-11-23 | Curable resin composition, and composite material and preparation method therefor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111337321.7A CN113980246A (en) | 2021-11-12 | 2021-11-12 | Curable resin composition, composite material and preparation method thereof |
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| CN113980246A true CN113980246A (en) | 2022-01-28 |
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| CN202111337321.7A Pending CN113980246A (en) | 2021-11-12 | 2021-11-12 | Curable resin composition, composite material and preparation method thereof |
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| WO (1) | WO2023082322A1 (en) |
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|---|---|---|---|---|
| CN118421244B (en) * | 2024-07-02 | 2024-09-20 | 株洲和诚科技有限责任公司 | Solvent-free high-temperature-resistant epoxy adhesive for prepreg, and preparation method and application thereof |
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| US4683283A (en) * | 1986-06-23 | 1987-07-28 | Ashland Oil, Inc. | Latent accelerators for epoxide curing |
| CN101161721A (en) * | 2006-10-10 | 2008-04-16 | 聚鼎科技股份有限公司 | Heat-conducting and electrically insulating polymer materials and heat-dissipating substrates containing them |
| CN101711262A (en) * | 2007-05-29 | 2010-05-19 | 陶氏环球技术公司 | Isocyanate-epoxy formulations for improved cure control |
| CN105566854A (en) * | 2015-12-04 | 2016-05-11 | 常州百思通复合材料有限公司 | Epoxy resin composition with special curing characteristics and composite thereof |
| CN106010321A (en) * | 2016-08-10 | 2016-10-12 | 苏州赛伍应用技术有限公司 | Conductive adhesive film |
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| US9309381B2 (en) * | 2011-06-24 | 2016-04-12 | Air Products And Chemicals, Inc. | Epoxy resin compositions using solvated solids |
| WO2017044359A1 (en) * | 2015-09-10 | 2017-03-16 | Dow Global Technologies Llc | High modulus, toughened one-component epoxy structural adhesives with high aspect ratio fillers |
| JP2017071706A (en) * | 2015-10-08 | 2017-04-13 | 日本化薬株式会社 | Epoxy resin composition, curable resin composition and cured product thereof |
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2021
- 2021-11-12 CN CN202111337321.7A patent/CN113980246A/en active Pending
- 2021-11-23 WO PCT/CN2021/132257 patent/WO2023082322A1/en not_active Ceased
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| US4683283A (en) * | 1986-06-23 | 1987-07-28 | Ashland Oil, Inc. | Latent accelerators for epoxide curing |
| CN101161721A (en) * | 2006-10-10 | 2008-04-16 | 聚鼎科技股份有限公司 | Heat-conducting and electrically insulating polymer materials and heat-dissipating substrates containing them |
| CN101711262A (en) * | 2007-05-29 | 2010-05-19 | 陶氏环球技术公司 | Isocyanate-epoxy formulations for improved cure control |
| CN105566854A (en) * | 2015-12-04 | 2016-05-11 | 常州百思通复合材料有限公司 | Epoxy resin composition with special curing characteristics and composite thereof |
| CN106010321A (en) * | 2016-08-10 | 2016-10-12 | 苏州赛伍应用技术有限公司 | Conductive adhesive film |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023082322A1 (en) | 2023-05-19 |
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