CN112119107B - 改善的固化剂组合物 - Google Patents
改善的固化剂组合物 Download PDFInfo
- Publication number
- CN112119107B CN112119107B CN201980032914.7A CN201980032914A CN112119107B CN 112119107 B CN112119107 B CN 112119107B CN 201980032914 A CN201980032914 A CN 201980032914A CN 112119107 B CN112119107 B CN 112119107B
- Authority
- CN
- China
- Prior art keywords
- resin
- epoxy
- curing
- hydroxy
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 64
- 239000004848 polyfunctional curative Substances 0.000 title description 5
- 229920005989 resin Polymers 0.000 claims abstract description 42
- 239000011347 resin Substances 0.000 claims abstract description 42
- 239000004593 Epoxy Substances 0.000 claims abstract description 21
- 229920003986 novolac Polymers 0.000 claims abstract description 20
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 239000003822 epoxy resin Substances 0.000 claims description 17
- 229920000647 polyepoxide Polymers 0.000 claims description 17
- 239000011342 resin composition Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- 239000011159 matrix material Substances 0.000 claims description 10
- 229920001187 thermosetting polymer Polymers 0.000 claims description 9
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical group NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- 239000003733 fiber-reinforced composite Substances 0.000 claims description 3
- 239000002657 fibrous material Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- 238000009472 formulation Methods 0.000 description 30
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 238000003860 storage Methods 0.000 description 10
- 239000004843 novolac epoxy resin Substances 0.000 description 9
- 230000009477 glass transition Effects 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 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 7
- 150000002989 phenols Chemical class 0.000 description 7
- 239000004609 Impact Modifier Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 239000005007 epoxy-phenolic resin Substances 0.000 description 6
- 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 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 4
- 239000011258 core-shell material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920003987 resole Polymers 0.000 description 4
- 230000000717 retained effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- -1 use Substances 0.000 description 3
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- YBBLOADPFWKNGS-UHFFFAOYSA-N 1,1-dimethylurea Chemical compound CN(C)C(N)=O YBBLOADPFWKNGS-UHFFFAOYSA-N 0.000 description 1
- ICLCCFKUSALICQ-UHFFFAOYSA-N 1-isocyanato-4-(4-isocyanato-3-methylphenyl)-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(C=2C=C(C)C(N=C=O)=CC=2)=C1 ICLCCFKUSALICQ-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- OWMNWOXJAXJCJI-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxymethyl)oxirane;phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1.C1OC1COCC1CO1 OWMNWOXJAXJCJI-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- BLXRNQQCVFDWIE-UHFFFAOYSA-N 3-[2,6-di(propan-2-yl)phenyl]-1,1-dimethylurea Chemical compound CC(C)C1=CC=CC(C(C)C)=C1NC(=O)N(C)C BLXRNQQCVFDWIE-UHFFFAOYSA-N 0.000 description 1
- ISAVYTVYFVQUDY-UHFFFAOYSA-N 4-tert-Octylphenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C=C1 ISAVYTVYFVQUDY-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 235000008495 Chrysanthemum leucanthemum Nutrition 0.000 description 1
- 244000192528 Chrysanthemum parthenium Species 0.000 description 1
- 235000000604 Chrysanthemum parthenium Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000008384 feverfew Nutrition 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011208 reinforced composite material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000646 scanning calorimetry Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
Classifications
-
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
-
- 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
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
-
- 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
- C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
-
- 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
- C08G59/4035—Hydrazines; Hydrazides
-
- 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
- C08J2363/02—Polyglycidyl ethers of bis-phenols
-
- 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
- C08J2363/04—Epoxynovolacs
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Reinforced Plastic Materials (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
公开了一种固化剂树脂,其包含至少50wt%环氧酚醛树脂且包含羧酸酰肼和有羟基取代的urone的混合物。
Description
技术领域
本发明涉及固化剂制剂,特别涉及用于使热固性树脂制剂、特别是包含线型酚醛环氧树脂的制剂固化的固化剂制剂。
背景技术
复合材料以很多形式制备。浸渍有可固化树脂基质制剂的纤维层称为预浸料。模塑混配物通常包含短切的各向同性或准各向同性形式的纤维材料与树脂基质制剂的组合。这些材料中的树脂基质制剂可以是线型酚醛环氧树脂,其可以是未固化的或部分固化的。
树脂基质制剂可以选自范围广泛的可聚合组分和添加剂。常见的可聚合组分包括环氧树脂,聚酯,乙烯基酯,多异氰酸酯,和酚醛树脂。包含这些组分的制剂通常分别称为环氧树脂制剂,聚酯制剂,乙烯基酯制剂,多异氰酸酯制剂,和酚醛树脂制剂。本发明涉及包含热固性树脂的制剂,其中树脂成分含有至少50wt%环氧酚醛树脂、特别是线型酚醛环氧树脂。
酚醛树脂通常通过苯酚和甲醛的反应制备。根据催化剂(酸性相对于碱性)以及甲醛与苯酚的摩尔比,苯酚线型酚醛树脂或甲阶碱性酚醛树脂可以由该反应形成。这些树脂可以进一步与表氯醇反应以分别形成苯酚线型酚醛环氧树脂(通常也称为“线型酚醛环氧树脂”)和甲阶碱性酚醛环氧树脂(epoxy phenol resol resins)(通常称为“甲阶酚醛环氧树脂”)形式的环氧酚醛树脂。
虽然本发明可以应用于包含至少50wt%任一类型树脂的树脂体系,其可特别应用于包含至少50wt%线型酚醛环氧树脂的树脂体系。
复合材料所需的性质是,当固化时,其具有所需的玻璃化转变温度(Tg),并且也具有根据其所要投放于的用途所需的机械性质。在某些应用中重要的是,Tg在微湿或潮湿的条件下保持。期望使用热固性材料用于结构部件,因为相比于热塑性材料具有较好的机械性能和抗蠕变性。对于这些应用,热固性基质具有的初始固化Tg必须足够高以允许在固化温度脱模。较高的固化Tg能力使得能够在较高的固化温度固化;较高的固化温度将使得当反应性随着温度升高而增加时具有较快的固化循环。
包含至少50wt%环氧酚醛树脂的热固性树脂制剂包括催化剂和/或固化剂,且它们根据树脂的性质、带制备的产品和所需的树脂的固化循环来选择。为支持高批量制造速率,复合材料的固化需要短的固化循环。2.5分钟的固化循环可以提供约166000个零件/模具/年的制造速率(假设30秒的携载-重新装载时间和95%的利用率)。
基于咪唑的固化剂广泛用于使树脂固化。遗憾的是,这些固化剂的反应性非常高,因此树脂和这些固化剂的混合溶液存在的问题是,它们显示出较早的固化起始,且无法用作在使用时制造然后交付的单组分环氧树脂组合物,因为这些组合物会在运输或储存过程中增稠、凝胶化和固化。
认为己二酸二酰肼和间苯二甲酸二酰肼是环氧树脂制剂的固化剂。已经提出,它们可以与促进剂如基于脲的材料一起使用,如公开于美国专利4404356和4507445。但是,仍然需要环氧酚醛树脂的固化剂,这些固化剂使树脂组合物快速固化(在3分钟以内、优选在2分钟以内或更快以达到至少95重量%的固化组合物)、并得到下述组合物,所述组合物具有至少120℃、优选至少130℃的玻璃化转变温度(Tg),并且特别是在升高温度特别是经受湿气时在一段时间内保持Tg。
发明内容
本发明旨在总地解决上述问题和/或提供改进。
根据本发明,提供了根据所附权利要求任一项的固化剂树脂、用途、组合物、复合材料和方法。
我们已经发现,如果己二酸二酰肼和/或间苯二甲酸二酰肼与羟基urone一起用作包含至少50重量%(wt%)环氧酚醛树脂的热固性树脂组合物的固化剂,可以得到具有快速固化性质、高玻璃化转变温度(Tg)与良好Tg保留率的制剂。
已经提出邻羟基非草隆可以用作环氧树脂的树脂固化剂,且提出其与二酰肼固化剂双氰胺组合使用。但是,已经发现邻羟基非草隆与酰肼组合用于使环氧酚醛树脂固化使得能够用环氧酚醛树脂偶的预料不到较快的固化和较高的玻璃化转变温度。
本发明因此提供包含己二酸二酰肼和/或间苯二甲酸二酰肼和羟基urone的组合的固化剂体系。
urone是包括下式的基于取代或未取代的脲的化合物的化合物
其中R是C1至C5烷基,x和y各自表示0或1,x和y的总和为1。
本发明进一步提供包含至少50wt%热固性环氧酚醛树脂各此类固化剂体系的树脂组合物或制剂。在一种优选的实施方式中,环氧酚醛树脂是线型酚醛环氧树脂。本发明也提供固化的树脂。
在进一步的实施方式中,本发明提供了此类树脂组合物或制剂作为纤维增强的复合材料的基质的用途,所述纤维增强的复合材料可以是预浸料或可以通过铺置在模具中的干燥纤维材料的树脂灌注来获得。本发明进一步提供通过使此类树脂基质固化获得的纤维增强的复合材料。
二酰肼和羟基urone可以按任何特定的比例使用,所述比例在下述范围内:0.50至2.00,优选为0.90至1.20,甚至更优选为1.00至1.15,最优选为1.08至1.12,基于二酰肼和羟基urone各自的重量。
固化剂在根据本发明的环氧酚醛树脂体系中的组合使用已经制得下述材料,所述材料当在150℃、特别是145至150℃经受5分钟固化、特别是当在150℃经受3分钟或2分钟固化(到至少95%固化,如本申请中所定义)时呈现出的E’Tg在140-150℃范围内。而用邻羟基非草隆和双氰胺的混合物固化的同等树脂呈现出的Tg为135℃。
使用本发明的固化剂体系连同双酚A环氧树脂代替根据本发明的线型酚醛环氧树脂体系将再次降低Tg,在一些情况中降低到低至115-120℃。此外,比起无羟基的urone,快速固化和高E’Tg的组合可用有羟基取代的urone得以较好的实现。
本发明的组合物在170℃在2分钟以内提供至少95%的固化,其中固化的Tg超过130℃,且保留的Tg超过100℃,同时提供具有用于结构应用所需的机械性能的固化树脂。
在组合物在170℃固化2分钟之后,固化的Tg根据ASTM D7028(通过动态力学分析(DMA)测量聚合物基质复合材料的玻璃化转变温度(DMA Tg)的标准测试方法)测量;保留的或湿法Tg在无掺杂树脂制剂(组合物)在170℃等温固化2分钟并使固化的制剂在70℃暴露于水14天之后测量,然后使用相同的测量标准ASTM D7028测量样品的Tg。
耗损模量E"根据ASTM E1640使用动态力学分析(DMA)以5℃/min的斜变速率测量。热湿法耗损模量E"w使用相同标准以5℃/min的斜变速率在将固化的组合物在70℃温度浸没于水14天之后测量。
储能模量E'根据ASTM E1640使用动态力学分析(DMA)以5℃/min的斜变速率测量。热湿法耗损模量E'w使用相同标准以5℃/min的斜变速率在将固化组合物在70℃的温度浸没于水14天之后测量。对于干燥样品和热湿处理的样品两者,对应的Tg值可以从储能模量和耗损模量推导出,如ASTM E1640中概述和本申请所阐明。
在动态力学分析(DMA)中,使待探讨的树脂组合物样品经受时变变形,测量样品响应。在DMA实验中,将正弦时变应变(受控变形)应用于样品:
γ=γ0sin(ωt) (I)
其中γ是所施加的应变,γο是应变振幅,t是时间,ω是频率。
DMA仪器测量所得应力:σ=σ0sin(ωt+δ) (II)
其中σ是所得应力,σο是应力振幅,δ是相角。
对于大多数树脂组合物,由于粘弹性性质(粘性组分和弹性组分两者),由于称为相角的粘性组分的作用,存在相位滞后。相角是重要的,因为其用于计算动态模量。
对于小应变振幅和时间独立的聚合物(线性粘弹性体系),所得应力可以用(动态)储能模量(Ε')和(动态)耗损模量(E")来表示:
σ=γ0[E'sin(ωt)+E"cos(ωt)] (III)
储能模量(Ε')和耗损模量(E")因此可以使用从(III)推导出的以下方程计算:
E’=σ0/γ0cosδ和E”=σ0/γ0sinδ (IV)
使得相角定义为
tanδ=E”/E’ (V)
通过DMA指认玻璃化转变温度Tg的标准试验可见于ASTM E1640,且从储能模量、耗损模量和从tanδ推导出。从通过DMA推导出的相应模量和tanδ图,可容易指认与储能模量(E'Tg)、耗损模量(E"Tg)和tanδ(tanδTg)关联的不同玻璃化转变温度。
如ASTM标准E1640中定义和说明,可以使用以下参数标记DMA树脂组合物样品的Tg:
E'Tg:发生在最低温度,并且通过相交的切线确定,所述相交的切线对应于以下两条切线:低于转变温度的储能模量曲线的切线;和在与转变相关的正弦变化的大约中途的拐点处储能模量曲线的切线。
E"Tg:发生在中间温度,且确认为E"曲线中的最大值。
TanδTg:发生在最高温度,且确认为tanδ曲线的最大值。
使用数字扫描量热法,在固化反应过程中释放的热量与完全固化的总热量有关。
将参比树脂样品以10℃/min的速率从10℃加热到250℃以完全固化(100%),记录产生的热量ΔHi。与参比树脂样品相同的组合物的特定树脂样品的固化程度可以如下测量:以所需速率将样品固化至所需温度并保持所需时间,在这些条件下加热样品,并测量由该固化反应产生的热量ΔHe。固化程度(固化%)然后通过(VI)定义:
固化%=[(ΔHi-ΔHe)/ΔHi]×100[%] (VI)
其中ΔHi是由未固化树脂从10℃加热到250℃完全固化所产生的热量,ΔHe是由加热至所需温度和速率的一定程度固化的树脂所产生的热量。
本发明的环氧酚醛树脂组分可以包含苯酚和苯酚衍生物与甲醛的已知缩合产物。适宜的苯酚衍生物是取代的苯酚,特别是烷基取代的苯酚如甲酚、二甲酚和其它烷基酚如对叔丁基苯酚、辛基苯酚和壬基苯酚,以及芳基苯酚例如苯基苯酚、萘酚和2元酚例如间苯二酚和双酚A以及上述苯酚和苯酚衍生物的混合物与甲醛的缩合产物。为优化特定性质,所提及的环氧酚醛树脂可以用不饱和的天然或合成化合物例如桐油、松香或苯乙烯改性。环氧酚醛树脂也可以是烃线型酚醛环氧树脂,例如作为Tactix购自Huntsman的二环戊二烯线型酚醛树脂。
用于本发明的可固化树脂材料包含50重量%的环氧酚醛树脂。树脂材料可以是100%环氧酚醛树脂,或者其可以为环氧酚醛树脂与其它可固化树脂例如环氧树脂或聚酯树脂的共混物。当树脂材料包含环氧树脂时,其可以是广泛用于复合材料的任何环氧树脂。环氧树脂可以是固体、液体或半固体,并且特征在于它们的官能度和环氧当量。环氧树脂的官能度是针对每分子中的可用于反应和固化以形成固化结构的反应性环氧位点的数目。树脂材料可以包含至少一种二官能环氧树脂。优选地,组合物包含一种或多种二官能环氧树脂组分,其含量范围为20至45重量%、优选为25至32重量%、更优选为28至41重量%,基于树脂的总重量。
我们已经发现,二酰肼固化剂、基于羟基urone的固化剂、和包含至少50wt%环氧酚醛树脂的树脂体系的组合得到快速固化组合物,其当在超过170℃的温度固化时具有超过130℃的固化Tg、以及超过100℃的保留的Tg(或湿法Tg),同时固化耗损模量E”是在超过130℃处的值,热湿耗损模量E”w是在超过120℃处的值。
在一种优选的实施方式中,组合物中不存在咪唑固化剂。
在本发明的另一种实施方式中,提供了包含如上文所述的树脂组合物与纤维增强材料的组合的模塑材料。纤维增强材料可以如下提供:提供为机织织物或多轴织物以形成预浸料,提供为单独的纤维丝束以用于用树脂组合物浸渍从而形成丝束预浸料,或提供为短切纤维、短纤维或长丝以形成模塑混配物。优选的纤维材料选自碳纤维、玻璃纤维、芳纶及其混合物。
在本发明进一步的实施方式中,提供了包含本申请所述的树脂组合物与至少一种填料的组合的粘合剂。
本发明的组合物能够快速固化,而同时Tg、保留的Tg和机械性质确保固化的树脂组合物可用于工业结构应用,特别是汽车和航空航天结构应用以及体育用品和风力涡轮机部件。
本发明的组合物可以包括用于热固性树脂的其它典型的添加剂,例如抗冲改性剂、填料、抗氧化剂等;但是,存在于根据本发明的组合物中的环氧酚醛树脂的量是基于不包括其它添加剂的量的组合物的总树脂含量的量。
抗冲改性剂
组合物可以包含抗冲改性剂。抗冲改性剂广泛用于改善固化的树脂组合物的冲击强度,旨在补偿它们的固有脆性和裂纹扩展。抗冲改性剂可以包括橡胶粒子例如CTBN橡胶(羧基封端的丁二烯-丙烯腈)或包含封装在聚合物壳中的橡胶或其它弹性化合物的核壳粒子。核壳粒子超过橡胶粒子的优势在于,它们具有受控的橡胶核粒度以用于有效增韧,接枝的聚合物壳确保与环氧树脂组合物的粘合力和相容性。此类核壳橡胶的实例公开于EP0985692和WO 2014062531。
可替代的抗冲改性剂可以包括基于丙烯酸甲酯的聚合物、聚酰胺、丙烯酸类、聚丙烯酸酯、丙烯酸酯共聚物、基于苯氧基的聚合物、和聚醚砜。
填料
另外,组合物可以包含一种或多种填料以增强组合物的流动性质。适宜的填料可以包括滑石,微球体,软棉填料(flock),玻璃珠,二氧化硅,煅烧二氧化硅,炭黑,纤维,细丝和回收的衍生物,和二氧化钛。
参照以下实施例说明本发明,其中使用以下材料。
己二酸二酰肼(ADH/ADH-J)AC催化剂
邻羟基非草隆(OHFU)-Urone固化剂
YDPN 638(苯酚线型酚醛环氧树脂)-Kukdo
SCT150三苯基甲烷线型酚醛环氧树脂-ShinAT&C
Epikote 828-二缩水甘油醚双酚A,平均EEW 187
MY721–基于三缩水甘油醚的环氧树脂,平均EEW113
GT6071-二缩水甘油醚双酚A-环氧树脂,平均EEW457
DICY-双氰胺
U52 2,4甲苯双(二甲基)脲和2,6甲苯双(二甲基)脲的共混物
MX153分散在双酚A中的核壳橡胶-Kaneka
TODI 3,31二甲基-4-41双酚酮双(二甲基脲)
DIPPI 3-(2,6二异丙基苯基)1,1二甲基脲
PDI N,N11–1,4亚苯基双(N,N1二甲基脲)
NDI N,N11–1,5-萘二基双(N,N1二甲基脲)
UR500–3,3'-(4-甲基-1,3-亚苯基)双(1,1-二甲基脲)
XD1000–DCPD(二环戊二烯)线型酚醛树脂,EEW=245-260
DLS 1840-半固体双酚A
苯氧基–热塑性增韧剂
Aerosil R202–亲水性二氧化硅填料
Pat 656/B3R–脱模剂(Wurtz)
进行以下测量:
固化速度(s)ASTM D2471-达到峰值的时间和达到95%固化的时间,使用介电分析(DEA);
Tg(℃)固化的树脂基质组合物的玻璃化转变温度,从DMA根据标准ASTM D7028测量
湿法Tg(℃),使固化的树脂组合物在水中在70℃浸没2周,从DMA根据ASTM D7028测量的Tg
E'Tg(℃),干燥样品和热湿处理的样品的Tg,其根据ASTM E1640以5℃/min的斜变速率确定且从储能模量E'推导出
干燥样品和热湿处理的样品的E"Tg(℃),其根据ASTM E1640以5℃/min的斜变速率确定且从耗损模量E"推导出
E"保留率(%)=E"湿法Tg/E"Tg*100
E'保留率(%)=E'湿法Tg/E'Tg*100
实施例1至5
制备以下制剂。
表3.实施例1至5的制剂
使实施例1至5的制剂暴露于150℃的温度,测量达到95%固化的时间和E’Tg,其结果如下。
表4.实施例1至5的结果。
以下实施例显示固化剂对达到95%固化的时间和E’Tg的组合的影响。
实施例3和6至10
制备以下制剂。
表5.实施例3和6至10的制剂
使实施例3和6至10的制剂暴露于150℃的温度,测量达到95%固化的时间和E’Tg,其结果如下(表6)。
表6.实施例3和6至10的结果
实施例11至13
最后,制备以下实施例11至13的制剂。
表7.实施例11至13的制剂
组分 | 实施例11 | 实施例12 | 实施例13 |
SCT150 | 34.2 | 20 | 33.8 |
XD1000 | |||
YDPN638 | 27.60 | ||
GT6071 | 16.4 | 16 | 15.50 |
Epikote 828 | 16.4 | 16 | 15.50 |
MY721 | 15 | ||
Phenoxy | |||
MX153 | 19 | 19.00 | |
Aerosil R202 | |||
PAT656/83R | 1 | 1 | 1.00 |
ADH-J | 6.80 | 6.8 | |
OHFU | 6.2 | 6.2 | 6.2 |
U52 | |||
UR500 | |||
DICY | 9.0 |
使实施例11、12和13的制剂暴露于150℃的温度,测量达到95%固化的时间和E’Tg,其结果如下。
表4.实施例15至17的结果。
测量 | 实施例11 | 实施例12 | 实施例13 |
达到95%固化的时间(分钟) | 2.4 | 1.9 | 1.7 |
E’Tg(℃) | 142 | 140 | 138 |
这些实施例表明,对于羧酸酰肼和有羟基取代的urone的固化剂组合、特别是邻羟基非草隆和酰肼的组合,实现了减少的达到95%固化的时间和提高的E’Tg的有利组合。
Claims (3)
1.一种环氧树脂组合物,其包含热固性树脂和固化剂,所述热固性树脂包含至少50wt%的环氧酚醛树脂;所述固化剂包含羧酸酰肼和有羟基取代的urone的混合物;其中所述羧酸酰肼是己二酸二酰肼,且其中所述有羟基取代的urone是邻-羟基非草隆。
2.一种纤维增强的复合材料,其包含浸渍有根据权利要求1所述的环氧树脂组合物的纤维增强丝束。
3.制造可固化的纤维增强的复合材料的方法,所述可固化的纤维增强的复合材料能够固化以形成Tg为145至150℃的固化材料,所述方法包括以下步骤:将纤维材料与包含至少50wt%环氧酚醛树脂的树脂组合物的基质组合,所述基质包含羧酸酰肼和有羟基取代的urone,使所述基质经受140℃至180℃的温度达不多于3分钟;其中所述羧酸酰肼是己二酸二酰肼,且其中所述有羟基取代的urone是邻-羟基非草隆。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP18172983.1 | 2018-05-17 | ||
EP18172983 | 2018-05-17 | ||
PCT/EP2019/062889 WO2019219953A1 (en) | 2018-05-17 | 2019-05-17 | Improved curative composition |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112119107A CN112119107A (zh) | 2020-12-22 |
CN112119107B true CN112119107B (zh) | 2023-11-28 |
Family
ID=62528235
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201980032914.7A Active CN112119107B (zh) | 2018-05-17 | 2019-05-17 | 改善的固化剂组合物 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20210246276A1 (zh) |
EP (1) | EP3794053B1 (zh) |
JP (1) | JP7386810B2 (zh) |
CN (1) | CN112119107B (zh) |
WO (1) | WO2019219953A1 (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112851553A (zh) * | 2021-01-29 | 2021-05-28 | 江苏泰仓农化有限公司 | 一种低温聚氨酯交联剂di-dma及其制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59174617A (ja) * | 1983-03-25 | 1984-10-03 | Toshiba Corp | エポキシ樹脂組成物 |
US4507445A (en) * | 1982-10-12 | 1985-03-26 | Ciba-Geigy Corporation | Heat-curable epoxide resin compositions |
JPS6140317A (ja) * | 1984-08-01 | 1986-02-26 | Toho Rayon Co Ltd | プリプレグの製法 |
US4714648A (en) * | 1984-08-01 | 1987-12-22 | Toho Rayon Co., Ltd. | Prepregs and method for production thereof |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4404356A (en) | 1981-09-09 | 1983-09-13 | Ciba-Geigy Corporation | Heat-curable epoxide resin compositions |
JPS5853916A (ja) * | 1981-09-09 | 1983-03-30 | チバ−ガイギ−・アクチエンゲゼルシヤフト | 熱硬化性エポキシド樹脂組成物 |
JPS5991117A (ja) * | 1982-10-12 | 1984-05-25 | チバ−ガイギ−・アクチエンゲゼルシヤフト | 熱硬化性エポキシ樹脂組成物 |
JPS6143616A (ja) * | 1984-08-08 | 1986-03-03 | Toho Rayon Co Ltd | エポキシ樹脂組成物 |
JPH0645672B2 (ja) * | 1987-03-30 | 1994-06-15 | サンアプロ株式会社 | エポキシ樹脂の硬化促進剤 |
JP3543613B2 (ja) * | 1998-04-10 | 2004-07-14 | 株式会社スリーボンド | 一液加熱硬化型水性エポキシ樹脂組成物 |
DE69923267T2 (de) | 1998-09-09 | 2006-03-30 | Rohm And Haas Co. | Verbesserte MBS schlagzähe Modifiziermittel |
US9701851B2 (en) | 2012-10-17 | 2017-07-11 | Dow Global Technologies Llc | Core shell rubber modified solid epoxy resins |
GB201411586D0 (en) * | 2014-06-30 | 2014-08-13 | Hexcel Composites Ltd | Adhesive composition |
-
2019
- 2019-05-17 CN CN201980032914.7A patent/CN112119107B/zh active Active
- 2019-05-17 EP EP19723830.6A patent/EP3794053B1/en active Active
- 2019-05-17 JP JP2020560441A patent/JP7386810B2/ja active Active
- 2019-05-17 US US17/049,869 patent/US20210246276A1/en not_active Abandoned
- 2019-05-17 WO PCT/EP2019/062889 patent/WO2019219953A1/en active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4507445A (en) * | 1982-10-12 | 1985-03-26 | Ciba-Geigy Corporation | Heat-curable epoxide resin compositions |
JPS59174617A (ja) * | 1983-03-25 | 1984-10-03 | Toshiba Corp | エポキシ樹脂組成物 |
JPS6140317A (ja) * | 1984-08-01 | 1986-02-26 | Toho Rayon Co Ltd | プリプレグの製法 |
US4714648A (en) * | 1984-08-01 | 1987-12-22 | Toho Rayon Co., Ltd. | Prepregs and method for production thereof |
Also Published As
Publication number | Publication date |
---|---|
EP3794053B1 (en) | 2024-03-13 |
WO2019219953A1 (en) | 2019-11-21 |
EP3794053A1 (en) | 2021-03-24 |
JP2021522391A (ja) | 2021-08-30 |
JP7386810B2 (ja) | 2023-11-27 |
US20210246276A1 (en) | 2021-08-12 |
CN112119107A (zh) | 2020-12-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Thakur et al. | Natural fibres-based polymers: Part I—Mechanical analysis of Pine needles reinforced biocomposites | |
US8220821B2 (en) | Fiber reinforced resin assembly | |
JPH02502101A (ja) | 低温硬化性用途に用いるエポキシ樹脂組成物 | |
CN110172228A (zh) | 一种木质素环氧树脂/碳纤维增强的抗老化复合材料 | |
TW202033659A (zh) | 樹脂組成物、纖維強化塑膠成形用材料及成形物 | |
CN112119107B (zh) | 改善的固化剂组合物 | |
JP5099998B2 (ja) | 繊維強化複合材料用エポキシ樹脂組成物 | |
CN115109385A (zh) | 一种预浸料用环氧树脂组合物及制备方法 | |
CN109554069B (zh) | 一种尼龙结晶增强的环氧树脂涂层及其制备方法 | |
JP7361678B2 (ja) | 樹脂組成物および樹脂組成物を含有する材料 | |
JP2020526635A (ja) | 樹脂組成物 | |
Ugoamadi | Comparison of cashew nut shell liquid (CNS) resin with polyester resin in composite development | |
EP4051723A1 (en) | Epoxy resin compositions | |
Santos et al. | Phenolic resin and its derivatives | |
CN108250396A (zh) | 一种环保型高强度抗冲击模塑料及其制备方法 | |
JP5143652B2 (ja) | エポキシ樹脂 | |
Ku et al. | Development of polymer network of phenolic and epoxies resins mixed with linseed oil: pilot study | |
RU2718831C1 (ru) | Эпоксидное связующее, препрег на его основе и изделие, выполненное из него | |
CN109642031B (zh) | 颗粒固化组分 | |
Kushwaha | Thermoset Polymer Matrix–Based Natural Fiber Composites | |
JPH11166101A (ja) | ガラス繊維含有フェノール系樹脂成形材料の製造方法 | |
EP3844203A1 (en) | Improvements in or relating to curing agents | |
CN114686004A (zh) | 增韧型氰酸酯及其制备方法 | |
JPH01165628A (ja) | 繊維強化プラスチック製造用基材 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |