CN105237955B - Epoxy-resin systems and preparation method thereof - Google Patents
Epoxy-resin systems and preparation method thereof Download PDFInfo
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- CN105237955B CN105237955B CN201510745459.9A CN201510745459A CN105237955B CN 105237955 B CN105237955 B CN 105237955B CN 201510745459 A CN201510745459 A CN 201510745459A CN 105237955 B CN105237955 B CN 105237955B
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 53
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- -1 aliphatic cyclic amine Chemical class 0.000 claims abstract description 25
- 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 claims abstract description 17
- 239000003085 diluting agent Substances 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 229940106691 bisphenol a Drugs 0.000 claims abstract description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 238000004383 yellowing Methods 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 8
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 6
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 5
- 150000002118 epoxides Chemical class 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- 229920002545 silicone oil Polymers 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical class CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 claims description 3
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 claims description 3
- 239000009261 D 400 Substances 0.000 claims description 3
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 3
- UAEPNZWRGJTJPN-UHFFFAOYSA-N Methylcyclohexane Natural products CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 claims description 3
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 claims description 3
- 229940070765 laurate Drugs 0.000 claims description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical group C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 claims description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 2
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 2
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical class C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 claims description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 claims description 2
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 claims description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 2
- LVACOMKKELLCHJ-UHFFFAOYSA-N 3-trimethoxysilylpropylurea Chemical class CO[Si](OC)(OC)CCCNC(N)=O LVACOMKKELLCHJ-UHFFFAOYSA-N 0.000 claims description 2
- AXLQHDAOEKLQPW-UHFFFAOYSA-N C1(CCCCC1)NCCC[SiH](OC(OCC)(OCC)OCC)OC Chemical compound C1(CCCCC1)NCCC[SiH](OC(OCC)(OCC)OCC)OC AXLQHDAOEKLQPW-UHFFFAOYSA-N 0.000 claims description 2
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 claims description 2
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 2
- VSOBWDFEQVDDMY-UHFFFAOYSA-N 3-[heptoxy(dimethoxy)silyl]propan-1-amine Chemical compound CCCCCCCO[Si](OC)(OC)CCCN VSOBWDFEQVDDMY-UHFFFAOYSA-N 0.000 claims 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical class CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 claims 1
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 claims 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 12
- 239000004917 carbon fiber Substances 0.000 abstract description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 238000006253 efflorescence Methods 0.000 abstract description 6
- 206010037844 rash Diseases 0.000 abstract description 6
- 238000009736 wetting Methods 0.000 abstract description 6
- 238000005470 impregnation Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 description 12
- 238000005452 bending Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 4
- 235000013527 bean curd Nutrition 0.000 description 4
- 239000011157 advanced composite material Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- 230000007480 spreading Effects 0.000 description 3
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- HBGPNLPABVUVKZ-POTXQNELSA-N (1r,3as,4s,5ar,5br,7r,7ar,11ar,11br,13as,13br)-4,7-dihydroxy-3a,5a,5b,8,8,11a-hexamethyl-1-prop-1-en-2-yl-2,3,4,5,6,7,7a,10,11,11b,12,13,13a,13b-tetradecahydro-1h-cyclopenta[a]chrysen-9-one Chemical compound C([C@@]12C)CC(=O)C(C)(C)[C@@H]1[C@H](O)C[C@]([C@]1(C)C[C@@H]3O)(C)[C@@H]2CC[C@H]1[C@@H]1[C@]3(C)CC[C@H]1C(=C)C HBGPNLPABVUVKZ-POTXQNELSA-N 0.000 description 1
- PFRGGOIBYLYVKM-UHFFFAOYSA-N 15alpha-hydroxylup-20(29)-en-3-one Natural products CC(=C)C1CCC2(C)CC(O)C3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 PFRGGOIBYLYVKM-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- SOKRNBGSNZXYIO-UHFFFAOYSA-N Resinone Natural products CC(=C)C1CCC2(C)C(O)CC3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 SOKRNBGSNZXYIO-UHFFFAOYSA-N 0.000 description 1
- 206010039203 Road traffic accident Diseases 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 230000003698 anagen phase Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical class OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Abstract
The present invention relates to a kind of epoxy-resin systems and preparation method thereof.The epoxy-resin systems include component A and B component, and the component A includes epoxy resin 80% 85%, diluent 14 19%, function additive 0.1% 3%；The B component includes aliphatic cyclic amine 40% 60%, polyetheramine 20% 45%, toughening type is modified 10% 30%, wherein, the epoxy resin is the one or more in bisphenol-A D-ring oxygen tree fat, hydrogenated bisphenol A D-ring oxygen tree fat, bisphenol-A epoxy resin, A Hydrogenated Bisphenol A F type epoxy resin.The epoxy-resin systems, fast to the wetting speed of carbon fiber, effect of impregnation is good；Rapid curing can be realized and there is good heat resistance；Process operability is excellent, and has excellent mechanical property；Solidfied material toast at high temperature or outdoor use without efflorescence, without xanthochromia situation, performance requirement of the unmanned plane to composite can be met applied to the making of unmanned plane.
Description
Technical field
The present invention relates to chemical industry and field of material technology, more particularly to a kind of epoxy-resin systems and preparation method thereof.
Background technology
Unmanned plane have passed through the very long evolution of 20th century, along with electronic industry, material science, control, communication skill
Making rapid progress for art, has welcome the fast growth phase of its industry development finally.Into after 21 century, the development input of unmanned plane
Explosive increase is presented with procurement demand.For example, the input in 20th century whole American UAV nineties field total only 34
Hundred million dollars, but 2010 then this numeral just reached 4,400,000,000 dollars, average annual growth rate was up to 44% between past 10 years.Specially
Industry is engaged in the Teal groups last-period forecast of aircraft industry market survey, and the capacity in coming 10 years whole world unmanned plane market is up to
89000000000 dollars.At present unmanned plane just progressively by defence and military move towards business it is civilian, take photo by plane, plant protection, geological prospecting, high voltage power transmission
Line data-logging, the inspection of oil gas pipeline, expressway traffic accident management, forest fire protection inspection, the prospecting of pollution environment, anti-terrorism stability maintenance, public affairs
Peace law enforcement, emergency management and rescue and rescue, rescue and relief work, coastline inspection etc. are provided for wide application market.
Advanced composite material is widely used in the manufacture of the fuselage, spare and accessory parts of unmanned plane because of its excellent performance, particularly
Fibre reinforced advanced composite material.
One of the matrix resin of epoxy resin as fibre reinforced advanced composite material, epoxy resin thing because its have it is excellent
The advantages that performance is good under different process operability and its solidfied material high/low temperature, shrinkage factor is small, resistant to chemical etching, is largely applied
In making unmanned plane.
But the epoxy-resin systems for being currently used in unmanned plane production largely have certain defect, such as carbon fiber is infiltrated and imitated
Fruit is not good enough；Higher heat resistance is difficult to take into account with easier curing process condition；Excellent mechanical property and excellent technique
Operability is difficult to take into account, in addition the solidfied material of existing epoxy-resin systems also easy xanthochromia and powder after high temperature or direct sunlight
Change.
The content of the invention
Based on this, it is necessary to provide a kind of epoxy-resin systems.
A kind of epoxy-resin systems, including component A and B component,
The component A, by weight percentage, including following component：
Epoxy resin 80%-85%
Diluent 14-19%
Function additive 0.1%-3%；
The B component, by weight percentage, including following component：
Aliphatic cyclic amine 40%-60%
Polyetheramine 20%-45%
Toughening type modifying agent 10%-30%, wherein,
The epoxy resin is bisphenol-A D-ring oxygen tree fat, hydrogenated bisphenol A D-ring oxygen tree fat, hydrogenated bisphenol A type asphalt mixtures modified by epoxy resin
One or more in fat, A Hydrogenated Bisphenol A F type epoxy resin.
In one of the embodiments, the purity of the epoxy resin is 98.5%-99.8%, viscosity 1500-
4500mpa.s(25℃)。
In one of the embodiments, the viscosity (25 DEG C) of the component A is 700-900mpa.s, epoxide number 0.60-
0.85；The viscosity (25 DEG C) of the B component is 10-60mpa.s, amine value 450-750mgKOH/g.
In one of the embodiments, the polyetheramine is one kind or more in D-230, D-400, D-2000, T-403
Kind.
In one of the embodiments, the aliphatic cyclic amine is methyl cyclohexane diamines, cyclohexanediamine, cyclohexylamine, hydrogenation isophthalic
One or more in diamines, hydrogenation 2,2- amino -4,4- diphenyl methane, IPD.
In one of the embodiments, the toughening type modifying agent is polyethyleneglycol diglycidylether, polypropylene glycol two
One or more in glycidol ether, allyl glycidyl ether (AGE), butyl glycidyl ether (BGE).
In one of the embodiments, the diluent is hydroresorcinol diglycidyl ether, BDO two
One or more in glycidol ether, 1,6- hexanediol diglycidyl ethers, benzyl glycidyl ether；The function additive is
3- (2,3- the third oxygen of epoxy) propyl trimethoxy silicane, γ-thiopropyl triethoxysilane, 3- ureido-propyl triethoxysilicanes
Alkane, 3- ureido-propyl trimethoxy silanes, diphenyl diethoxy silane, phenyltrimethoxysila,e, double amino silanes are oligomeric
Thing, 3- aminopropyl triethoxysilanes, double (3- trimethoxy-silylpropyls) amine, N- cyclohexyl-γ-aminopropyl trimethoxy
Base silane, N- cyclohexyl-γ-aminopropyltriethoxy dimethoxysilane, N- (β-aminoethyl)-gamma-aminopropyl-triethoxy-silane,
N- (β aminoethyls)-γ-aminopropyltriethoxy-dimethoxysilane, 3- aminopropyl triethoxysilanes, γ-methacryloxy
Propyl trimethoxy silicane, γ-methacryloyloxypropyl methyl dimethoxysilane, γ-methacryloxypropyl
Triethoxysilane, γ-methacryloyloxypropyl methyl diethoxy silane, methyl-silicone oil, multi-hydroxy silicone oil, laurate
One or more combinations in glycidyl ethers, dodecylamino epoxy ethyl ether etc., preferably 3- (2,3- the third oxygen of epoxy)
Propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloyloxypropyl methyl
Dimethoxysilane, γ-methacryloxypropyl, laurate glycidyl ethers are one or more.
In one of the embodiments, the weight ratio of the component A and B component is 100：(30-45), the epoxy resin
The viscosity of system is 150-250mpa.s.
In one of the embodiments, the B component also include percentage by weight be 2%-5% age resister and/or
Anti-yellowing agent, wherein, the anti-yellowing agent is the one or more in hindered phenol type compound, phosphite ester type compound；Institute
Age resister is stated as in styrenated phenol, decoyl salicylic acid, p-aminobenzoic acid, 2,6- di-tert-butyl-4-methy phenols etc.
One or more.
The present invention also provides the preparation method of described epoxy-resin systems, comprises the following steps：
The epoxy resin, diluent are mixed after being heated to 40-45 DEG C in vacuum reaction kettle, with 150-350r/min
Mixing speed stirring, while react 2-3h with the function additive is spread with 10-20 grams/min spray velocity, obtain the A groups
Point；
The 30-60% of the aliphatic cyclic amine gross weight is added into reactor and is warming up to 30-45 DEG C, is stirred with 150-350r/min
Mix, then add the toughening type modifying agent in the reactor with 0.5-1.5kg/h rate of addition, and control the highest temperature
Degree is no more than 75 DEG C, without being warming up to 60-80 DEG C after obvious blunt temperature, reacts 1-3h, then adds remaining aliphatic cyclic amine, be eventually adding
The polyetheramine, age resister and anti-yellowing agent are added after insulation reaction 2-4h, then 150-200r/min stirs, and produces
Described B component.
The principle and advantage of the present invention is as follows：
Epoxy-resin systems of the present invention, with high-purity, bisphenol-A D-ring oxygen tree fat, the hydrogenated bisphenol A D of ultra-low viscosity
One or more in type epoxy resin, bisphenol-A epoxy resin, A Hydrogenated Bisphenol A F type epoxy resin are matrix resin, drop
The viscosity and binding function auxiliary agent of low system carry out wellability of the optimization system to carbon fiber；
Hydroresorcinol diglycidyl ether, BDDE, 1,6- hexylene glycols two is coordinated to shrink
One or more in glycerin ether, benzyl glycidyl ether further reduce system viscosity and improve system as diluent
Heat resistance, above-mentioned epoxy resin is cooperateed with to obtain excellent mechanical property；
In terms of curing agent, based on aliphatic cyclic amine, it is aided with polyetheramine D-230, D-400, D-2000, T-403, coordinates simultaneously
Using one kind in polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether, AGE, BGE, butyl glycidyl ether
Or it is a variety of as toughening type modifying agent, it can make system that there is excellent stretching, bending, compression, impact property after hardening, simultaneously
The process operability of raising system, and in a short time can be with rapid curing.
The epoxy-resin systems viscosity that is consequently formed is low, fast to the wetting speed of carbon cloth or carbon fiber bundle, infiltration effect
Fruit is good；Rapid curing and there can be good heat resistance in easier curing process condition；With it is excellent stretch, it is curved
Bent, compression, impact property, and process operability is excellent.
In addition, epoxy-resin systems of the present invention can also add percentage by weight be 2%-5% age resister and/
Or anti-yellowing agent, thus obtained solidfied material toast at high temperature or outdoor use without efflorescence, without xanthochromia situation.
Compared with prior art, the invention has the advantages that：
Epoxy-resin systems of the present invention, system viscosity is low, fast to the wetting speed of carbon cloth or carbon fiber bundle, leaching
Moisten that effect is good, and multi-storey up-down and translation or multi-beam carbon-fiber yarn beam can be impregnated with completely in a short time, bubble-free, without shredded dried bean curd；Can be
Rapid curing and there is good heat resistance in 80 DEG C × 2h or 70 DEG C × 5h；Component A and B component press 100：After 30-45 mixing
System has very low mixing viscosity, relatively low exothermic peak temperature, and longer heat release peak time, and process operability is excellent,
It, which solidifies solidify afterwards thing, has excellent stretching, bending, compression, impact property；Solidfied material toasts at high temperature or outdoor use
Without efflorescence, without xanthochromia situation, the making of unmanned plane can be applied to, meet performance requirement of the unmanned plane to composite.
Embodiment
Further details of theory is made to epoxy-resin systems of the present invention and preparation method thereof below in conjunction with specific embodiment
It is bright.
Embodiment
Three kinds of epoxy-resin systems of the present embodiment, by weight percentage, including component as described in Table 1：
Table 1
The preparation method of epoxy resin, comprises the following steps described in embodiment 1：
(1) 45 DEG C are heated in vacuum reaction kettle after mixing the epoxy resin, diluent, functional form auxiliary agent is with 20
Gram/with 200r/min mixing speed stirring reaction 3h, component A is made, viscosity (25 DEG C) is with spreading in min spray velocity
870mpa.s, epoxide number 0.74, colourless transparent liquid；
(2) hydrogenation m-phenylene diamine (MPD) and methyl cyclohexane diamines are added into reactor first and is warming up to 35 DEG C, with 350r/min
Stirring, then toughening type modifying agent is added in reactor with 1.5kg/h at the uniform velocity rate of addition, and control maximum temperature not surpass
Cross 75 DEG C；Then to without being warming up to 60-80 DEG C after obvious blunt temperature, 2h is reacted；Then remaining aliphatic cyclic amine is added, is eventually adding poly-
Ether amines, after insulation reaction 4h, age resister and anti-yellowing agent are added, then 150r/min stirs, and produces described B groups
Point, the viscosity (25 DEG C) of wherein B agent is 42mpa.s, amine value 578mgKOH/g, colourless transparent liquid.
Component A and B component are pressed 100：After 42 mixing, it is 210mpa.s that it, which mixes viscosity, and its 100g mixture is in 150ml
Heat release peak time in disposable cup is 135min, 115 DEG C of exothermic peak temperature；Its 70 DEG C × 5h solidification solidify afterwards thing Tg be
115 DEG C, its tensile strength is 68Mpa, stretch modulus 2.89GPa, tension fracture elongation rate 6.8%, and its bending strength is
115Mpa, bending modulus 2.92GPa, its compressive strength is 93.5Mpa, its impact strength is 63KJ/m2；High temperature (140-160
DEG C) under baking or outdoor use without efflorescence, without xanthochromia situation.
Its carbon fiber yarn with 24K tensile strength of diameter 22mm bar after drawing and twining technological forming curing molding is
2352MPa, stretch modulus 127GPa, fast to the wetting speed of carbon fiber yarn in forming process, effect of impregnation is good, and 5min interior energies are complete
It is impregnated with entirely, bubble-free, without shredded dried bean curd.
The preparation method of epoxy resin, comprises the following steps described in embodiment 2：
(1) 50 DEG C are heated in vacuum reaction kettle after mixing the epoxy resin, diluent, functional form auxiliary agent is with 15
Gram/with 300r/min mixing speed stirring reaction 3h, component A is made, viscosity (25 DEG C) is with spreading in min spray velocity
830mpa.s, epoxide number 0.76, colourless transparent liquid；
(2) hydrogenation m-phenylene diamine (MPD) is added reactor with hydrogenation 2,2- amino -4,4- diphenyl methane and is warming up to first
40 DEG C, stirred with 350r/min, then add toughening type modifying agent in reactor with 1.5kg/h at the uniform velocity rate of addition, and
Maximum temperature is controlled to be no more than 75 DEG C；Then to without being warming up to 60-80 DEG C after obvious blunt temperature, 2h is reacted；Then add remaining
Aliphatic cyclic amine, is eventually adding polyetheramine, after insulation reaction 4h, adds age resister and anti-yellowing agent, and then 200r/min stirrings are equal
It is even, produce described B component, (25 DEG C) of viscosity is 55mpa.s amine value 545mgKOH/g, colourless transparent liquid.
Component A and B component are pressed 100：After 42 mixing, it is 233mpa.s that it, which mixes viscosity, and its 100g mixture is in 150ml
Heat release peak time in disposable cup is 145min, 106 DEG C of exothermic peak temperature；Its 70 DEG C × 5h solidification solidify afterwards thing Tg be
123 DEG C, its tensile strength is 66Mpa, stretch modulus 2.72GPa, tension fracture elongation rate 8.2%, and its bending strength is
112Mpa, bending modulus 2.84GPa, its compressive strength is 91.3Mpa, its impact strength is 78.2KJ/m2；Under high temperature
(140-160 DEG C) baking or outdoor use without efflorescence, without xanthochromia situation.
It is strong with the stretching of T700-24K carbon fiber yarn diameter 22mm bar after drawing and twining technological forming curing molding
Spend for 2433MPa, stretch modulus 135GPa, fast to the wetting speed of carbon fiber yarn in forming process, effect of impregnation is good, in 5min
It can be impregnated with completely, bubble-free, without shredded dried bean curd.
The preparation method of epoxy resin, comprises the following steps described in embodiment 3：
(1) 40 DEG C are heated in vacuum reaction kettle after mixing the epoxy resin, diluent, functional form auxiliary agent is with 10
Gram/with 150r/min mixing speed stirring reaction 2h, component A is made, viscosity (25 DEG C) is with spreading in min spray velocity
700mpa.s, epoxide number 0.78, colourless transparent liquid；
(2) first by cyclohexylamine：10% (the weight ratio for accounting for B component) and cyclohexanediamine：7% (the weight ratio for accounting for B component)
Add reactor and be warming up to 45 DEG C, stirred with 150r/min, then by toughening type modifying agent with 0.5kg/h at the uniform velocity dropwise addition speed
Degree is added in reactor, and controls maximum temperature to be no more than 75 DEG C；Then to without being warming up to 60-80 DEG C after obvious blunt temperature, react
1h；Then remaining aliphatic cyclic amine is added, is eventually adding polyetheramine, after insulation reaction 2h, adds age resister and anti-yellowing agent, so
200r/min stirs afterwards, produces described B component, and viscosity (25 DEG C) is 65mpa.s, amine value 525mgKOH/g, colourless
Prescribed liquid.
Component A and B component are pressed 100：After 30 mixing, it is 290mpa.s that it, which mixes viscosity, and its 100g mixture is in 150ml
Heat release peak time in disposable cup is 165min, 128 DEG C of exothermic peak temperature；Its 80 DEG C × 2h solidification solidify afterwards thing Tg be
129 DEG C, its tensile strength is 68Mpa, stretch modulus 2.97GPa, tension fracture elongation rate 6.75%, and its bending strength is
135Mpa, bending modulus 3.17GPa, its compressive strength is 98.2Mpa, its impact strength is 47.2KJ/m2；Under high temperature
(140-160 DEG C) baking or outdoor use without efflorescence, without xanthochromia situation.
It is strong with the stretching of T700-24K carbon fiber yarn diameter 22mm bar after drawing and twining technological forming curing molding
Spend for 2654MPa, stretch modulus 163GPa, fast to the wetting speed of carbon fiber yarn in forming process, effect of impregnation is good, 4.5min
Interior energy is impregnated with completely, bubble-free, without shredded dried bean curd.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope that this specification is recorded all is considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more specific and detailed, but simultaneously
Can not therefore it be construed as limiting the scope of the patent.It should be pointed out that come for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (9)
- A kind of 1. epoxy-resin systems, it is characterised in that including component A and B component,The component A, by weight percentage, including following component：Epoxy resin 80%-85%Diluent 14-19%Function additive 0.1%-3%；The B component, by weight percentage, including following component：Aliphatic cyclic amine 40%-60%Polyetheramine 20%-45%Toughening type modifying agent 10%-30%, wherein,The epoxy resin be bisphenol-A D-ring oxygen tree fat, hydrogenated bisphenol A D-ring oxygen tree fat, bisphenol-A epoxy resin, One or more in A Hydrogenated Bisphenol A F type epoxy resin；The aliphatic cyclic amine is the one or more in methyl cyclohexane diamines, cyclohexanediamine, cyclohexylamine, hydrogenation m-phenylene diamine (MPD).
- 2. epoxy-resin systems according to claim 1, it is characterised in that the purity of the epoxy resin is 98.5%- 99.8%, viscosity 1500-4500mpa.s.
- 3. epoxy-resin systems according to claim 1, it is characterised in that the viscosity of the component A is 700- 900mpa.s, epoxide number 0.60-0.85；The viscosity of the B component is 10-60mpa.s, amine value 450-750mgKOH/g.
- 4. epoxy-resin systems according to claim 1, it is characterised in that the polyetheramine is D-230, D-400, D- 2000th, the one or more in T-403.
- 5. epoxy-resin systems according to claim 1, it is characterised in that the toughening type modifying agent is polyethylene glycol two One kind or more in glycidol ether, polypropylene glycol diglycidyl ether, allyl glycidyl ether, butyl glycidyl ether Kind.
- 6. epoxy-resin systems according to claim 1, it is characterised in that the diluent is that hydroresorcinol two contracts One kind in water glycerin ether, BDDE, 1,6- hexanediol diglycidyl ethers, benzyl glycidyl ether It is or a variety of；The function additive be 3- (2,3- the third oxygen of epoxy) propyl trimethoxy silicane, γ-thiopropyl triethoxysilane, 3- ureidopropyltriethoxysilanes, 3- ureido-propyl trimethoxy silanes, diphenyl diethoxy silane, phenyl trimethoxy Silane, double amino silane oligomer, 3- aminopropyl triethoxysilanes, double (3- trimethoxy-silylpropyls) amine, N- rings Hexyl-γ-aminopropyltrimethoxysilane, N- cyclohexyl-γ-aminopropyltriethoxy dimethoxysilane, N- (β-aminoethyl)- Gamma-aminopropyl-triethoxy-silane, N- (β aminoethyls)-γ-aminopropyltriethoxy-dimethoxysilane, 3- aminopropyl-triethoxies Silane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloyloxypropyl methyl dimethoxysilane, γ-methacryloxypropyl, γ-methacryloyloxypropyl methyl diethoxy silane, methyl One or more combinations in silicone oil, multi-hydroxy silicone oil, laurate glycidyl ethers, dodecylamino epoxy ethyl ether.
- 7. according to the epoxy-resin systems described in claim any one of 1-6, it is characterised in that the weight of the component A and B component Amount is than being 100：(30-45), the viscosity of the epoxy-resin systems is 150-250mpa.s.
- 8. according to the epoxy-resin systems described in claim any one of 1-6, it is characterised in that the B component also includes weight Percentage is 2%-5% age resister and/or anti-yellowing agent, wherein, the anti-yellowing agent is hindered phenol type compound, phosphorous One or more in acid esters type compound；The age resister is styrenated phenol, decoyl salicylic acid, p-aminophenyl first One or more in acid, 2,6- di-tert-butyl-4-methy phenols.
- 9. the preparation method of the epoxy-resin systems described in claim any one of 1-8, it is characterised in that comprise the following steps：The epoxy resin, diluent are mixed after being heated to 40-50 DEG C in vacuum reaction kettle, with stirring for 150-350r/min Speed stirring is mixed, while reacts 2-3h with the function additive is spread with 10-20 grams/min spray velocity, obtains the component A；The 30-60% of the aliphatic cyclic amine gross weight is added into reactor and is warming up to 30-45 DEG C, is stirred with 150-350r/min, Then the toughening type modifying agent is added in the reactor with 0.5-1.5kg/h rate of addition, and controls maximum temperature No more than 75 DEG C, without being warming up to 60-80 DEG C after obvious blunt temperature, 1-3h is reacted, remaining aliphatic cyclic amine is then added, is eventually adding institute State polyetheramine, after insulation reaction 2-4h, add or be added without the age resister and anti-yellowing agent, 150-200r/min stirrings are equal It is even, produce described B component.
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| CN105925143B (en) * | 2016-06-27 | 2018-04-06 | 上海正欧实业有限公司 | High abrasion epoxy coating and preparation method thereof and coating |
| CN105969282A (en) * | 2016-07-18 | 2016-09-28 | 广州聚合新材料科技股份有限公司 | Epoxy resin system for inverter potting manufacturing and preparation method thereof |
| CN106433027A (en) * | 2016-08-03 | 2017-02-22 | 衡阳冠力塑胶有限公司 | Polyacrylonitrile carbon fiber reinforced epoxy resin composite material, preparation method and application thereof |
| CN106751472A (en) * | 2016-11-24 | 2017-05-31 | 广州本色环保工程有限公司 | A kind of carbon-fibre reinforced epoxy resin composite material and preparation method thereof |
| CN108485187B (en) * | 2018-03-29 | 2021-05-11 | 广州聚合新材料科技股份有限公司 | Modified epoxy resin material, preparation method and application thereof, and leaf |
| CN109880564B (en) * | 2019-01-23 | 2021-06-25 | 甘肃省交通规划勘察设计院股份有限公司 | Reinforced resin and preparation method and application thereof |
| CN109748542A (en) * | 2019-03-08 | 2019-05-14 | 重庆亲禾生态环境科技有限公司 | A kind of color inhibition sand base water-permeable brick and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101608105A (en) * | 2008-06-17 | 2009-12-23 | 上海得荣电子材料有限公司 | Adhesive for packaging smart card module |
| CN102382551A (en) * | 2011-09-09 | 2012-03-21 | 海洋化工研究院 | Green environment-friendly epoxy type weather-resistant coating composition as well as preparation method and application thereof |
| CN102675827A (en) * | 2012-05-17 | 2012-09-19 | 镇江育达复合材料有限公司 | Epoxy resin-based carbon fibre compound material formed by using high polymer (HP)-resin transfer molding (RTM) process quickly |
-
2015
- 2015-11-03 CN CN201510745459.9A patent/CN105237955B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101608105A (en) * | 2008-06-17 | 2009-12-23 | 上海得荣电子材料有限公司 | Adhesive for packaging smart card module |
| CN102382551A (en) * | 2011-09-09 | 2012-03-21 | 海洋化工研究院 | Green environment-friendly epoxy type weather-resistant coating composition as well as preparation method and application thereof |
| CN102675827A (en) * | 2012-05-17 | 2012-09-19 | 镇江育达复合材料有限公司 | Epoxy resin-based carbon fibre compound material formed by using high polymer (HP)-resin transfer molding (RTM) process quickly |
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