CN117304651A - Polyurethane modified epoxy resin composition, application thereof and polyurethane modified epoxy resin - Google Patents
Polyurethane modified epoxy resin composition, application thereof and polyurethane modified epoxy resin Download PDFInfo
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- CN117304651A CN117304651A CN202310764731.2A CN202310764731A CN117304651A CN 117304651 A CN117304651 A CN 117304651A CN 202310764731 A CN202310764731 A CN 202310764731A CN 117304651 A CN117304651 A CN 117304651A
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- Prior art keywords
- epoxy resin
- polyurethane
- modified epoxy
- resin composition
- component
- Prior art date
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 256
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 256
- 239000000203 mixture Substances 0.000 title claims abstract description 76
- 239000004814 polyurethane Substances 0.000 title claims abstract description 53
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000004848 polyfunctional curative Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 229920005862 polyol Polymers 0.000 claims description 57
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 56
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000005056 polyisocyanate Substances 0.000 claims description 27
- 229920001228 polyisocyanate Polymers 0.000 claims description 27
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 25
- 229920000570 polyether Polymers 0.000 claims description 25
- 150000003077 polyols Chemical class 0.000 claims description 17
- 125000003700 epoxy group Chemical group 0.000 claims description 16
- 239000011342 resin composition Substances 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 13
- 239000003733 fiber-reinforced composite Substances 0.000 claims description 11
- 239000012783 reinforcing fiber Substances 0.000 claims description 11
- 239000004844 aliphatic epoxy resin Substances 0.000 claims description 9
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 7
- 238000005191 phase separation Methods 0.000 abstract description 26
- -1 polyol compound Chemical class 0.000 description 75
- 150000001875 compounds Chemical class 0.000 description 30
- 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 29
- 229920005989 resin Polymers 0.000 description 20
- 239000011347 resin Substances 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 16
- 238000001723 curing Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 239000004593 Epoxy Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 229920000049 Carbon (fiber) Polymers 0.000 description 10
- 239000004917 carbon fiber Substances 0.000 description 10
- 238000013016 damping Methods 0.000 description 10
- 239000000835 fiber Substances 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
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- 238000002156 mixing Methods 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 8
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 8
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 7
- 239000004744 fabric Substances 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 6
- 239000004970 Chain extender Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
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- 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 6
- 238000005266 casting Methods 0.000 description 6
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- 238000012986 modification Methods 0.000 description 6
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- 238000004448 titration Methods 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- USBHQTSMWCBZJE-UHFFFAOYSA-N [O-][N+]([Fe])=O Chemical compound [O-][N+]([Fe])=O USBHQTSMWCBZJE-UHFFFAOYSA-N 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 2
- KGYYLUNYOCBBME-UHFFFAOYSA-M 4-fluoro-2-phenyl-4-(4-propylcyclohexyl)cyclohexa-1,5-diene-1-carboxylate Chemical compound C1CC(CCC)CCC1C1(F)C=CC(C([O-])=O)=C(C=2C=CC=CC=2)C1 KGYYLUNYOCBBME-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004203 carnauba wax Substances 0.000 description 2
- 235000013869 carnauba wax Nutrition 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
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- 238000009826 distribution Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000004200 microcrystalline wax Substances 0.000 description 2
- 235000019808 microcrystalline wax Nutrition 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
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- 238000010079 rubber tapping Methods 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 description 1
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- BRXKVEIJEXJBFF-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)-3-methylbutane-1,4-diol Chemical compound OCC(C)C(CO)(CO)CO BRXKVEIJEXJBFF-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 1
- SUTCVRHWHOUKJP-UHFFFAOYSA-N 2-(7-oxabicyclo[4.1.0]heptan-4-yl)acetic acid Chemical compound C1C(CC(=O)O)CCC2OC21 SUTCVRHWHOUKJP-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- VMSIYTPWZLSMOH-UHFFFAOYSA-N 2-(dodecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCOCC1CO1 VMSIYTPWZLSMOH-UHFFFAOYSA-N 0.000 description 1
- ZCZCZLVSKGCRTD-UHFFFAOYSA-N 2-(tridecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCCOCC1CO1 ZCZCZLVSKGCRTD-UHFFFAOYSA-N 0.000 description 1
- HHRACYLRBOUBKM-UHFFFAOYSA-N 2-[(4-tert-butylphenoxy)methyl]oxirane Chemical compound C1=CC(C(C)(C)C)=CC=C1OCC1OC1 HHRACYLRBOUBKM-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- STHCTMWQPJVCGN-UHFFFAOYSA-N 2-[[2-[1,1,2-tris[2-(oxiran-2-ylmethoxy)phenyl]ethyl]phenoxy]methyl]oxirane Chemical compound C1OC1COC1=CC=CC=C1CC(C=1C(=CC=CC=1)OCC1OC1)(C=1C(=CC=CC=1)OCC1OC1)C1=CC=CC=C1OCC1CO1 STHCTMWQPJVCGN-UHFFFAOYSA-N 0.000 description 1
- UJWXADOOYOEBCW-UHFFFAOYSA-N 2-[[2-[bis[2-(oxiran-2-ylmethoxy)phenyl]methyl]phenoxy]methyl]oxirane Chemical compound C1OC1COC1=CC=CC=C1C(C=1C(=CC=CC=1)OCC1OC1)C1=CC=CC=C1OCC1CO1 UJWXADOOYOEBCW-UHFFFAOYSA-N 0.000 description 1
- PULOARGYCVHSDH-UHFFFAOYSA-N 2-amino-3,4,5-tris(oxiran-2-ylmethyl)phenol Chemical compound C1OC1CC1=C(CC2OC2)C(N)=C(O)C=C1CC1CO1 PULOARGYCVHSDH-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-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
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- ZXTHWIZHGLNEPG-UHFFFAOYSA-N 2-phenyl-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=CC=C1 ZXTHWIZHGLNEPG-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- 125000004189 3,4-dichlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(Cl)C([H])=C1* 0.000 description 1
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical class C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- FRPHFZCDPYBUAU-UHFFFAOYSA-N Bromocresolgreen Chemical compound CC1=C(Br)C(O)=C(Br)C=C1C1(C=2C(=C(Br)C(O)=C(Br)C=2)C)C2=CC=CC=C2S(=O)(=O)O1 FRPHFZCDPYBUAU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- 239000004163 Spermaceti wax Substances 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012164 animal wax Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 239000003480 eluent Substances 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 238000012933 kinetic analysis Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012184 mineral wax Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229960002715 nicotine Drugs 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 1
- 229920000090 poly(aryl ether) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 235000019385 spermaceti wax Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
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- 239000002023 wood Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Classifications
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- 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
- 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
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
-
- 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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- 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
- 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
- C08J2463/00—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
- C08J2463/02—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
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/08—Polyurethanes from polyethers
-
- 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
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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)
- Polyurethanes Or Polyureas (AREA)
- Epoxy Resins (AREA)
Abstract
The invention provides a polyurethane modified epoxy resin composition, application thereof and polyurethane modified epoxy resin. The polyurethane modified epoxy resin composition contains, as essential components, a polyurethane unmodified epoxy resin (A), a polyurethane modified epoxy resin (B) and a hardener (C), wherein the polyurethane modified epoxy resin (B) is contained in an amount of 20 to 70% by weight relative to the total amount (solid content) of the epoxy resin composition, and the component (A) is compatible with the component (B), and the polyurethane modified epoxy resin composition is characterized in that the component (A) and the component (B) form a phase separation structure as a hardened product after the hardening reaction, and the loss factor (tan delta) measured using a dynamic viscoelasticity device is 0.03 or more in a temperature range of-40 to 40 ℃ under the conditions of a frequency of 10Hz and a heating rate of 2 ℃/min, and the viscosity at 25 ℃ measured by an E-type viscometer is 50 Pa.s or less.
Description
Technical Field
The present invention relates to an epoxy resin composition having excellent properties such as impregnation into a fibrous base material, heat resistance and damping properties, a cured product using the epoxy resin composition, and the like, and more particularly, to a polyurethane-modified epoxy resin composition, an application thereof, and a polyurethane-modified epoxy resin.
Background
Epoxy resins are used in a large amount in various applications such as matrix resins for composite materials such as electric insulating materials (casting, impregnating, laminated sheets, sealing materials) and carbon fiber reinforced plastics (Carbon Fiber Reinforced Plastics, CFRP), structural adhesives, and heavy anticorrosive coatings, because they are excellent in processability and exhibit various cured product characteristics such as high heat resistance, high insulation reliability, high rigidity, high adhesion, and high corrosion resistance.
In contrast, epoxy resin cured products have low elongation at break, low fracture toughness, and low peel strength, and therefore, in matrix resin applications and structural adhesive applications of composite materials requiring these properties, the properties are improved by various modifications such as rubber modification and polyurethane modification.
Regarding polyurethane modification, for example, patent document 1 and patent document 2 disclose diglycidyl ether of bisphenol a-alkylene oxide adduct (a), and an epoxy resin/polyurethane mixture (B) containing an epoxy resin and a polyurethane dispersed in the epoxy resin, wherein the polyurethane is obtained by reacting a polyisocyanate compound with a curing agent capable of reacting with the polyisocyanate compound in the epoxy resin.
Patent document 3 discloses a resin composition containing a compound having an epoxy group and a polyurethane having a structural unit represented by the general formula (II) in the molecule.
Patent document 4 discloses a polyurethane-modified epoxy resin obtained by modifying a bisphenol-type epoxy resin (a) with a medium-high molecular weight polyol compound (b), a polyisocyanate compound (c) and a low molecular weight polyol compound (d) as a chain length extender, using a predetermined amount of the epoxy resin (a), reacting the medium-high molecular weight polyol compound (b) with the polyisocyanate compound (c) in a predetermined amount, and then adding a predetermined amount of the low molecular weight polyol compound (d).
Patent document 5 discloses a polycarbonate-modified epoxy resin in which a hydroxyl group-containing epoxy resin (a), a polyisocyanate compound (B), and a polycarbonate polyol (C) are used as necessary reaction raw materials, and the polycarbonate polyol (C) is a predetermined amount.
Patent document 6 discloses an epoxy resin composition for a fiber-reinforced composite material, which is obtained by blending an epoxy resin (a), a urethane prepolymer (B) having a structure derived from a polyether polyol and having isocyanate groups or hydroxyl groups at both ends of a molecular chain, and a hardener (C), wherein (a) and (B) are compatible before the hardening reaction, and after the hardening reaction, (a) forms a sea structure, and (B) forms an island structure, and a cured product of the obtained epoxy resin composition has a sea-island phase separation structure.
As another method, patent documents 7 to 9 disclose an epoxy resin composition containing a thermoplastic resin such as an epoxy resin or a polyethersulfone resin, and a hardener.
Patent document 10 discloses the following: a resin layer containing a thermoplastic resin having a polyarylether skeleton and particles containing a thermoplastic resin and a thermosetting resin is formed to improve impact characteristics.
However, even with these patent documents, the required characteristics may not be satisfied sufficiently. Disclosed is a polyurethane-modified epoxy resin which satisfies the requirements for physical properties and excellent damping properties in various applications. By providing the resin itself with damping properties, it is expected that the deterioration of mechanical properties, thermal properties, chemical resistance, and the like of a cured product due to the addition of an elastomer having poor heat resistance and solvent resistance can be suppressed, or that the formation of a stress relaxation layer (adhesive layer) is not required.
[ Prior Art literature ]
[ patent literature ]
[ patent document 1] Japanese patent laid-open No. 2007-284467
[ patent document 2] Japanese patent laid-open No. 2007-284474
Patent document 3 Japanese patent laid-open No. 2007-224144
[ patent document 4] Japanese patent laid-open publication 2016-11409
[ patent document 5] Japanese patent laid-open No. 2017-226717
[ patent document 6] Japanese patent laid-open No. 2017-82128
[ patent document 7] Japanese patent laid-open No. 2005-105151
[ patent document 8] Japanese patent laid-open No. 2007-284545
Patent document 9 Japanese patent laid-open No. 2008-144110
[ patent document 10] WO2019/098243
Disclosure of Invention
[ problem to be solved by the invention ]
The present invention is to provide a novel polyurethane-modified epoxy resin composition which has a high glass transition temperature, a lower viscosity, and excellent fiber impregnation properties, is suitable for Fiber Winding (FW) molding or drawing molding, and has a high damping property of the resin itself, among urethane-modified epoxy resins used for casting materials, composite materials, structural adhesives, and the like, and a cured product thereof.
[ means of solving the problems ]
The present invention provides a polyurethane modified epoxy resin composition comprising, as essential components, a polyurethane unmodified epoxy resin (A), a polyurethane modified epoxy resin (B) and a hardener (C), wherein the polyurethane modified epoxy resin (B) has a structure derived from a polyether polyol and a structure derived from a polyisocyanate and has a structure obtained by reacting a structure having an isocyanate group at the end of a molecular chain with hydroxyl groups of an epoxy resin having two or more epoxy groups on average in the molecule, and the polyurethane modified epoxy resin composition contains 20 to 70% by weight of the polyurethane modified epoxy resin (B) relative to the total amount (solid component) of the epoxy resin composition, and the component (A) is compatible with the component (B), and the polyurethane modified epoxy resin composition is characterized in that the component (A) and the component (B) form a phase-separated structure as a hardened product after the hardening reaction, and the loss coefficient (tan delta) measured by a dynamic viscoelastometer is in a viscosity range of 0.03 ℃ or more at a temperature range of-40 ℃ and a temperature rise rate of 2 ℃ per minute and a viscosity of 25 Pa.s or less measured by using a dynamic viscoelastometer.
The polyurethane modified epoxy resin composition of the present invention is desirably: in the polyurethane modified epoxy resin (B), 30 mol% or more of the structure derived from the polyether polyol is derived from polytetramethylene ether glycol (polytetramethylene ether glycol, PTMG).
In addition, it is desirable that: among the epoxy resins having two or more epoxy groups in the molecule on average, 1/3 or more of the mole number of the epoxy resin to be reacted is aliphatic epoxy resin.
In addition, it is preferable that: the weight average molecular weight of the polyurethane-modified epoxy resin (B) is 8000 or more, and the amount of a urethane component (B), that is, the blending amount of the polyol compound and the isocyanate compound, to be described later is 13.5 wt% or more with respect to the total amount of the component (a) and the component (B).
In addition, it is preferable that: in the polyurethane modified epoxy resin (B), the aliphatic epoxy resin is a polyglycidyl ether of trimethylolpropane.
The present invention also relates to a cured product obtained by curing the polyurethane-modified epoxy resin composition, a resin composition for a fiber-reinforced composite material obtained by impregnating reinforcing fibers with the composition, and a fiber-reinforced composite material obtained by the resin composition.
The present invention also provides a polyurethane-modified epoxy resin comprising a structure obtained by reacting a hydroxyl group of an epoxy resin having a structure derived from a polyether polyol and a structure derived from a polyisocyanate and having an isocyanate group at a terminal of a molecular chain with an average of two or more epoxy groups in a molecule, wherein 30 mol% or more of the structure derived from the polyether polyol is derived from a polytetramethylene ether glycol, and 1/3 or more of the number of moles of the epoxy resin having two or more epoxy groups in the molecule is an aliphatic epoxy resin.
[ Effect of the invention ]
The polyurethane-modified epoxy resin composition of the present invention has a viscosity of 50pa·s or less at 25 ℃ and a low viscosity, is excellent in fiber impregnation property, suppresses a decrease in glass transition temperature, and is excellent in a state where a cured product is phase-separated and has a high loss coefficient (tan δ), and therefore is suitable for a matrix resin for composite materials, an adhesive formulation resin, and the like, which require damping property for industrial use, sports and leisure use, civil engineering and construction use, and the like.
Drawings
Fig. 1 is a stereo microscope image showing the phase structure of a cured product (example 10).
Fig. 2 is a stereo microscope image showing the phase structure of a cured product (comparative example 3).
Detailed Description
The polyurethane modified epoxy resin composition of the present invention is characterized in that: the polyurethane-modified epoxy resin (B) contains, as essential components, a polyurethane-unmodified epoxy resin (a) and a hardener (C) as a regulator of the polyurethane concentration, and contains 20 to 70% by weight of the polyurethane-modified epoxy resin (B) relative to the total amount (solid content) of the epoxy resin composition.
The resin composition of the present invention may optionally contain a hardening accelerator (D), and further contain an inorganic filler such as calcium carbonate, talc, or titanium dioxide as an extender or a reinforcing material.
The polyurethane-modified epoxy resin (B) used in the present invention is an epoxy resin having an average of two or more epoxy groups in the molecule such as a liquid bisphenol-type epoxy resin (a-1) or an aliphatic epoxy resin (a-2) [ hereinafter, these may be collectively referred to as an epoxy resin (a) ], a polyether polyol compound such as polytetramethylene ether glycol (PTMG) (B-1), and a polyisocyanate compound (c) as essential components. From the viewpoints of optimization of physical properties and viscosity, fine adjustment of compatibility, molecular weight control, and the like, polyol compound (b-2) having a number average molecular weight of 500 or more including compounds other than PTMG, and low molecular weight polyol compound (d) having a number average molecular weight of less than 500 as a chain extender can be suitably used. The number average molecular weight described herein is a value converted from a hydroxyl value (hydroxyl value), and the hydroxyl value is usually measured by a measurement method based on japanese industrial standard (Japanese Industrial Standards, JIS) K1557. The following is the same.
The components of the polyurethane-modified epoxy resin (B) will be described below.
As the epoxy resin (a) having two or more epoxy groups on average in the molecule, the use of the above-mentioned (a-1) or (a-2) is preferable. It is preferable in terms of having two or more epoxy groups in the molecule on average, and exhibiting various physical properties in the reaction with the subsequent curing agent.
The epoxy resin (a-1) is a preferable component for exhibiting heat resistance and mechanical properties, and is preferably in a liquid state at ordinary temperature, and in this respect, it has an epoxy equivalent of 300g/eq or less. Further preferred are epoxy resins having an epoxy equivalent of 150g/eq to 300g/eq and a hydroxyl equivalent of 800g/eq to 3600 g/eq. Specifically, a bisphenol type epoxy resin containing a secondary hydroxyl group having an epoxy equivalent of 150g/eq to 200g/eq and a hydroxyl equivalent of 2000g/eq to 3000g/eq represented by the following general formula (1) is preferable.
Wherein R is 1 Each independently represents H or alkyl, and a is a number from 0 to 10. At R 1 In the case of an alkyl group, the carbon number is preferably in the range of 1 to 3, more preferably 1.
Particularly preferred epoxy resins (a-1) are bisphenol A type epoxy resins represented by the formula (1 a) and/or bisphenol F type epoxy resins represented by the formula (1 b).
Wherein a1 and a2 are numbers of 0 to 10.
In the formulas (1), (1 a) and (1 b), the average value (number average) of the repetition numbers a, a1 and a2 is in the range of 1 to 5, preferably in the range of 1 to 3.
The epoxy resin (a-2) is a preferable component for reducing the viscosity of the polyurethane-modified epoxy resin and the composition using the same, and the viscosity at 25 ℃ is preferably 100 mPas to 5000 mPas. The epoxy resin having a hydroxyl group in the structure may have either a primary hydroxyl group or a secondary hydroxyl group, and either of them may be used for the reaction, or the hydroxyl group of the epoxy resin whose terminal glycidation is not completed at all may be used. From the viewpoint of reducing the viscosity of the polyurethane-modified epoxy resin and the composition using the same, it is preferable to use the aliphatic epoxy resin (a-2) having 1/3 or more of the total mole number of the epoxy resin (a) to be reacted with the epoxy resin (a). More preferably 1/2 or more of the mole number, and still more preferably 2/3 or more of the mole number. Further, the "number of moles" mentioned herein is preferably a value obtained by dividing the amount (mass) of each epoxy resin to be used by the hydroxyl equivalent to convert it into a unit of functional group. In the present invention, it is assumed that one of the secondary hydroxyl groups of the epoxy resin (a-1) and the polymer of the epoxy resin (a-2) (for example, in the case of a=1 or more of the above formula (1)) reacts with an isocyanate group to form a urethane prepolymer in the form of an end-capped urethane structure, but it is also assumed that the end of the urethane structure is not end-capped and tends to contribute to the extension of a molecular chain or the gelation due to the increase of a molecular weight when a=2 or more. Therefore, since a=1 bodies account for most of the contents except for a=0 bodies, a case is envisaged in which the value divided by the hydroxyl equivalent generally shows the number of n1 bodies. Therefore, this number is expressed as a mole number, and the ratio of numbers is expressed as a mole ratio.
The aliphatic epoxy resin (a-2) is preferably polyglycidyl ether of a dibasic or more aliphatic alcohol, and may have an alicyclic skeleton. Examples of the dibasic aliphatic alcohol include: 1, 4-butanediol, 3-methyl-1, 5-pentanediol, diethylene glycol, neopentyl glycol, 1, 6-hexanediol, 1, 9-nonanediol, cyclohexanedimethanol, propylene glycol, and the like. Further, as the aliphatic alcohol having three or more members, there may be mentioned: glycerol, trimethylol propane, trimethylol ethane, tetramethylol propane, sorbitol, pentaerythritol, and the like. Among them, polyglycidyl ethers of trimethylolpropane are preferable in terms of viscosity, compatibility, mechanical properties and the like.
As the polyether polyol compound (contained in the polyol compound described later), a compound having a primary hydroxyl group at the terminal as in the following (b-1) and (b-2) or the like can be preferably used. For example, polytetramethylene ether glycol (PTMG) (b-1) is a linear polyether glycol having primary hydroxyl groups represented by the following formula (2 a) at both ends, and has a number average molecular weight of about 200 to, for example, more than 4000. In addition, the polyether polyol compound is contained in the polyol compound.
HO-(CH 2 CH 2 CH 2 CH 2 O)n-H (2a)
In the present invention, the number average molecular weight is preferably about 500 to 4000, and is preferably 2000 to 4000 in terms of compatibility with the resin, damping performance, and the like.
Examples of the polyether polyol compound (b-2) other than PTMG include compounds represented by the following formulas (2 b) to (2 d): polyethylene glycol (polyethylene glycol, PEG), polypropylene glycol (polypropylene glycol, PPG), polyethylene glycol (polyethylene propylene glycol, PEPG), copolymers of two or more alkylene oxides (e.g., ethylene oxide-propylene oxide copolymers), and the like. As the (b-2), a polyol compound such as a lactone-modified polyol, a polyester polyol, a polycarbonate polyol or the like may be used within a range that does not hinder the object of the present invention, and one or two or more of them may be used in combination. As for these (b-2) components, those having the same number average molecular weight as (b-1) are preferable.
Here, R is 2 And b1, b2 and b3 are independently a number of 1 to 50, and c is a number of 0 or 1.
Here, q1, q2, q3, q4 are independently a number of 1 to 20.
Here, r, s, t are independently a number of 1 to 20, and n is a number of 1 to 50.
The number of NCO groups of the polyisocyanate compound (c) is not less than 2, but is preferably not less than 2. Also preferably represented by the general formula (3) and R 4 A compound which is a divalent group selected from the group consisting of the formulas (i) to (vi). Among these, a compound excellent in compatibility with the epoxy resin (a) can be preferably selected.
Specifically, there may be mentioned: toluene diisocyanate (tolylene diisocyanate, TDI), diphenylmethane diisocyanate (diphenyl methane diisocyanate, MDI), xylylene diisocyanate (xylylene diisocyanate, XDI), hydrogenated xylylene diisocyanate (hydrogenated xylylene diisocyanate, HXDI), isophorone diisocyanate (isophorone diisocyanate, IPDI), naphthalene diisocyanate, and the like. Each of which may be any one of the isomers or a mixture of the isomers.
OCN-R 4 -NCO
(3)
Here, R is 4 Preferably a divalent group selected from the group consisting of formulas (i) to (vi). In formula (ii) and formula (v), the methyl group is omitted.
In particular, 4' -diphenylmethane diisocyanate (MDI) represented by formula (3 a) is more preferable from the viewpoints of low molecular weight, no thickening, low cost, safety, and the like. In addition, toluene Diisocyanate (TDI) (2, 4-TDI and/or 2, 6-TDI), meta-Xylene Diisocyanate (XDI) as exemplified in examples described later can also be more preferably used.
The low molecular weight polyol compound (d) is a polyol compound having a number average molecular weight of less than 500. Preferably less than 200. It is used as chain extender. The diol compound represented by the formula (4) and having two primary hydroxyl groups is preferable.
HO-R 5 -OH (4)
Here, R is 5 The alkylene group represented by the formula (vii) is represented by the formula (vii), and g is a number of 1 to 10.
The low molecular weight polyol compound (d) includes, for example, polyols such as 1, 4-butanediol and 1, 6-pentanediol. In particular, 1, 4-butanediol is more preferable in terms of easy availability and balance of price and characteristics.
Next, a description will be given of a reaction mechanism by using any or all of the components (a-1), (a-2), (b-1), (b-2), (c) and (d) exemplified above together with a polyurethane-modified epoxy resin. The components may be used singly or in combination.
The OH groups in the epoxy resin (a) (e.g., (a-1), (a-2)) are mainly secondary OH groups. On the other hand, the OH groups of polytetramethylene glycol (PTMG) (b-1) and polyether polyol compound (b-2) other than PTMG are mainly primary OH groups. Therefore, when the epoxy resin (a), the polytetramethylene ether glycol (PTMG) (b-1) and/or the polyether polyol compound (b-2) other than PTMG, the polyisocyanate compound (c) and the like are charged and reacted, the primary OH group of the (b-1) or (b-2) and the NCO group of the polyisocyanate compound (c) react preferentially.
Typically, it is considered that the primary OH groups in (b-1) and (b-2) react with the NCO groups in (c) first to form a urethane prepolymer (P1) having their NCO group ends bonded thereto. That is, the urethane prepolymer (P1) has a structure derived from the polyether polyol and a structure derived from the polyisocyanate compound bonded thereto. The structure derived from polyether polyol means the remaining structure of the polyether polyol compound after at least one hydroxyl group (which may be partially) at the molecular end is removed. The structure derived from the polyisocyanate compound means a residual structure of the polyisocyanate compound after at least one isocyanate group (may include a part) at the molecular end is removed. It is preferably produced as a urethane prepolymer (P1) having NCO groups at both terminals after the reaction. Thereafter, the OH group (preferably, a secondary OH group) in the epoxy resin (a) reacts with the terminal NCO group of the urethane prepolymer (P1) to form a urethane bond, and the urethane prepolymer (P2) is formed by adding the epoxy resin (a) to both ends or one end of the urethane prepolymer (P1).
That is, the urethane prepolymer (P) is considered to be a mixture of an NCO group-terminated urethane prepolymer (P1) and a urethane prepolymer (P2) having an epoxy resin (a) [ structure derived from the epoxy resin (a) ] added to both ends or one end of P1, but since the molar ratio of NCO groups is large, and the epoxy resin is excessively used in addition, it is considered that the urethane prepolymer (P2) having an epoxy resin added to both ends of P1 is mainly produced. The structure derived from the epoxy resin means a residual structure after removing at least one hydroxyl group (which may include a part) in the epoxy resin.
The epoxy resin (a) is preferably incorporated in an amount of 50 to 85% by weight based on the total amount of the components (a), (b-1), (b-2), (c) and (d). As the loading ratio of the epoxy resin (a) increases, both ends or one end of the urethane prepolymer (P1) are sealed with the epoxy resin (a), terminal NCO groups are consumed, the amount of the urethane prepolymer (P2) which does not react with the low molecular weight polyol compound (d) as a chain extender also increases, the proportion of the initial urethane prepolymer (P1) which is terminal NCO groups decreases, and the amount of the produced polyurethane by the reaction of the terminal NCO groups of P1 with the OH groups of the low molecular weight polyol compound (d) as a chain extender decreases, so that the molecular weight distribution of the polyurethane-modified epoxy resin also shifts to the low molecular weight side.
Conversely, when the loading ratio of the epoxy resin (a) is reduced, the amount of the urethane prepolymer (P2) having both ends or one end sealed with the epoxy resin (a) is reduced, and the ratio of the initial urethane prepolymer (P1) having the terminal NCO group maintained therein is increased. Therefore, the amount of polyurethane formed by the reaction of the terminal NCO groups of P1 with the OH groups of the low molecular weight polyol compound (d) as a chain extender increases, and thus the molecular weight distribution of the polyurethane-modified epoxy resin also shifts to the high molecular weight side.
The epoxy resin (a) is, for example, a mixture of a single-unit compound having a repetition number a of 0 and a polymer having a repetition number a of 1 or more, and the polymer has a secondary OH group formed by ring-opening of an epoxy group. The secondary OH group is reactive with the NCO group of the polyisocyanate compound (c) or the NCO group at the end of the urethane prepolymer (P), and thus, when the epoxy resin (a-1) or the epoxy resin (a-2) has a secondary OH group (for example, a=1 or more of the formula (1)). In addition, in the case where the epoxy resin (a) does not have a secondary OH group (for example, a=0 body in the formula (1), etc.), the reaction is not involved. As described above, the polyurethane-modified epoxy resin (B) of the present invention is understood to have a complex structure in which any or all of the above-described components (a-1), (a-2), (B-1), (B-2), (c) and (d) are reacted, and is in the form of a mixture containing the above-described epoxy resin (a) having no OH group in a state that is considered not directly involved in the reaction or the expression of the function but is difficult to be completely distinguished or excluded, and therefore, there are some cases where the component (B) cannot be directly determined by the structure or characteristics thereof, or is substantially not practical (so-called impossible/not practical cases).
The polyurethane modified epoxy resin composition of the present invention exhibits damping properties because the polyurethane modified epoxy resin portion undergoes phase separation in the epoxy resin composition. When phase separation is mentioned, it is generally reported that a sea-island structure is formed, but in the present invention, a state in which island portions are connected to each other is obtained instead of a sea-island structure in which island portions exist in a spherical shape. Such a phase separation structure is called a mutually invasive structure, a mutually connecting structure, or the like, and in the present invention, it is desirable to have a phase separation structure having a mutually invasive structure or a mutually connecting structure at least partially. When a polyurethane-modified epoxy resin having a structure derived from a polyether polyol and containing at least 30 mol% of a polyether polyol compound which is polytetramethylene ether glycol (PTMG) is used, the island portion (polyurethane-modified epoxy resin portion) after phase separation has a gentle peak in the range of-40 ℃ to 40 ℃, and the island portion and the sea portion (epoxy resin portion) are hardly compatible with each other to be separated from each other, and a structure in which the island portions are mutually connected to each other is obtained, whereby a high loss coefficient (tan delta) can be exhibited in the temperature range of-40 ℃ to 40 ℃ and the temperature range before and after. Therefore, in order to form the phase separation structure of the present invention, it is necessary to control the size or number of island portions, compatibility with sea portions, and the like.
As one of the control factors of the phase separation structure, the amount of the urethane moiety can be cited. The urethane part is a part of the polyurethane-modified epoxy resin in which the polyether polyol compound and the polyisocyanate compound react, and the size, number, shape, and the like of the island part greatly vary depending on the amount of the urethane part in the composition. Fig. 1 to 2 show examples of the phase-separated state as images, and it can be seen that: in the present invention, if the amount of the urethane component described later in the polyurethane-modified epoxy resin (B), that is, the blending amount of the polyol compound and the polyisocyanate compound, is 17% by weight relative to the total amount of the component (a) and the component (B), phase separation occurs at a level where the island structure is clearly visible as shown in fig. 1, but if it is 13% by weight, the island structure is fine as shown in fig. 2. In a state where the island structure is completely formed and the island portion exists alone in a size of several nanometers to several tens of nanometers, tan δ is low, and if the island portion is aggregated in a size of several hundred nanometers to several micrometers and a shade starts to appear in the island structure, a behavior in which tan δ rises is confirmed. Further, when the phase separation is further performed, the island portion is connected to a phase separation structure having a size of several tens to several hundreds of micrometers, and more preferable tan δ is shown. However, if the phase separation size is too large, the mechanical properties are lowered. In order to form the phase separation structure of the present invention, the island size of the phase separation is preferably 10nm to 200. Mu.m, more preferably 100nm to 100. Mu.m, particularly preferably 1 μm to 100. Mu.m.
The size of the islands that govern phase separation is not only the molecular weight of the polyurethane-modified epoxy resin, but also the compatibility with the sea becomes important. If the compatibility is high, the island portion and the sea portion are compatible with each other at the time of hardening the epoxy resin composition, and a desired phase separation structure cannot be formed without phase separation. Thus, in order to form the preferred size and number of islands, the polyurethane modified epoxy resin of the islands needs to have a certain degree of molecular weight size and be incompatible with the unmodified epoxy resin of the sea. Further, as the time passes at the time of phase separation, the incompatible islands gradually link each other to form a large domain (domain), which causes a decrease in mechanical properties and the like. Therefore, it is necessary to select an optimum molecular weight or composition of the polyurethane-modified epoxy resin according to the viscosity of the resin composition or the curing conditions (curing temperature, curing time, and heating rate) corresponding to the use.
The polyurethane-modified epoxy resin (B) preferably has a structure derived from a polyether polyol compound in which 30 mol% or more is a structure derived from polytetramethylene ether glycol (PTMG) so that Tg of the island portion after phase separation has a gentle peak in a range of-40 ℃ to 40 ℃. More preferably 50 mol% or more, still more preferably 75 mol% or more, and most preferably 100 mol% can be used. The term "mole" as used herein means a value obtained by dividing the weight of each component by the number average molecular weight.
Since the island portion after phase separation is incompatible with the sea portion, the polyurethane modified epoxy resin (B) is preferably: the weight average molecular weight is 8000 or more, and the amount of urethane component (B), that is, the amount of polyol compound and polyisocyanate compound blended in the component (B) is 13.5 wt% or more relative to the total amount of the component (a) and the component (B). The weight average molecular weight may be more preferably 10000 or more, still more preferably 12000 or more and 45000 or less, still more preferably 12000 or more and 35000 or less. In order to form a desired phase separation structure, the amount of the urethane component (B), that is, the blending amount of the polyol compound and the polyisocyanate compound, to be described later, may be more preferably 13.5% by weight or more and 19% by weight or less relative to the total amount of the component (a) and the component (B).
As a method for producing the polyurethane-modified epoxy resin (B) used in the present invention, for example, a method is used in which (a-1) and (a-2) are used as the epoxy resin (a) in an amount of 50 to 85% by weight based on the total amount of the polytetramethylene ether glycol (PTMG) (B-1) as the polyether polyol compound, (B-2) other than PTMG, (c) the polyisocyanate compound and the low molecular weight polyol compound (d) having a number average molecular weight of less than 500 as the chain extender, and (B-1), (B-2) and the polyisocyanate compound (c) are reacted in the presence of the epoxy resin (a) (reaction 1). In the above reaction 1, the reaction of (b-1), (b-2) with the polyisocyanate compound (c) preferentially occurs to produce the urethane prepolymer (P1). Thereafter, the urethane prepolymer (P1) and the epoxy resin (a) are reacted to mainly produce a urethane prepolymer (P2) having both ends of P1 epoxidized.
The reaction of the urethane prepolymer (P1) with the epoxy resin (a) requires that the OH groups (mainly, low-reactivity secondary OH groups) in the epoxy resin (a) react with the NCO groups of P1 to form urethane bonds, and thus the reaction temperature is preferably in the range of 80 to 150 ℃, and the reaction time is preferably in the range of 1 to 5 hours.
Thereafter, the molar ratio (P1) of NCO groups in the urethane prepolymer (P1) to OH groups in the low molecular weight polyol compound (d) is optionally: (d) becomes 0.9:1.0 to 1.0: the low molecular weight polyol compound (d) was added in a range of 0.9 to carry out the polyurethane reaction (reaction 2). Further, the epoxy group of the epoxy resin and the OH group of the polyol compound (d) are alcoholic OH groups, and thus do not react.
The reaction temperature of the reaction 2 is preferably in the range of 80℃to 150℃and the reaction time is preferably in the range of 1 hour to 5 hours, but the reaction between the NCO groups and the OH groups in the low molecular weight polyol compound (d) is preferably under milder conditions than the reaction 1.
In the course of the reactions (reactions 1 and 2), a catalyst may be used as necessary. The catalyst is used for the purpose of sufficiently completing the formation of urethane bonds, and examples thereof include amine compounds such as ethylenediamine, tin compounds, and zinc compounds.
In reaction 2, the remaining urethane prepolymer (P1) having NCO at both ends or one end is reacted with the low molecular weight polyol compound (d), the chain length is extended and polyurethane is formed, and the urethane prepolymer (P2) having an adduct of epoxy resin (a) at both ends is left unreacted with the component (d).
When the low molecular weight polyol compound (d) is not used, the terminal NCO reacts with each hydroxyl group to form the urethane prepolymer (P2) when the polyisocyanate compound (c) is added.
The polyurethane-modified epoxy resin used in the present invention preferably has an epoxy equivalent of 180g/eq to 1000g/eq and a viscosity of 0.1 Pa.s to 30 Pa.s at 120 ℃.
By increasing or decreasing the blending amount of the polyurethane unmodified epoxy resin (a), the polyurethane concentration in the polyurethane modified epoxy resin composition can be increased or decreased. Here, if the above-exemplified components are used, the polyurethane concentration in the epoxy resin composition is calculated by the following equation, but the kind of each component is not limited thereto.
Polyurethane concentration = { (B-1) + (B-2) + (C) + (d) } ×100/{ (a) + (B) + (C) }
In this case, (B) = (a-1) + (a-2) + (B-1) + (B-2) + (c) + (d).
Here, (a-1), (a-2), (B-1), (B-2), (C), (d), (A), (B) and (C) are the weights of the respective components used. In addition, when other components, for example, the hardening accelerator (D) and the like are blended, these other components are added to the denominator.
In the present invention, the concentration of the polyurethane in the epoxy resin composition is preferably 5 to 30% by weight, more preferably 10 to 20% by weight.
In the polyurethane-modified epoxy resin (B), the concentration of the urethane component is preferably 20 to 50% by weight. Here, in the above-exemplified case, the urethane component concentration means { (b-1) + (b-2) + (c) + (d) }/{ (a-1) + (a-2) + (b-1) + (b-2) + (c) + (d) }.
As the polyurethane unmodified epoxy resin (a) used in the polyurethane modified epoxy resin composition of the present invention, (a-1), (a-2) and the like of the epoxy resin (a) used as a raw material of the polyurethane modified epoxy resin (B) can be preferably used. That is, an epoxy resin which is liquid at 30 ℃ without polyurethane modification is preferable. Among them, bisphenol a type epoxy resins and/or bisphenol F type epoxy resins are preferable in terms of easy availability, and balance of price and characteristics. As (a-2), polyglycidyl ethers of trimethylolpropane are preferable from the viewpoints of viscosity, compatibility, mechanical properties and the like.
In the polyurethane-modified epoxy resin composition of the present invention, as the polyurethane-unmodified epoxy resin (a), a trifunctional or higher-functional epoxy resin may be used for the purpose of adjusting viscosity or increasing Tg. When a multifunctional epoxy resin is used, the crosslinking density increases, and the phase separation state changes or the fracture toughness is lost, so that the content is preferably 0.1 to 10% by weight based on the total weight of the composition. Examples of the trifunctional or higher-functional epoxy resin include: phenol novolac type epoxy resins, cresol novolac type epoxy resins, glycidyl amine type epoxy resins such as tetraglycidyl diaminodiphenylmethane, glycidyl phenyl ether type epoxy resins such as tetra (glycidyl oxyphenyl) ethane or tris (glycidyl oxyphenyl) methane, glycidyl amine type and glycidyl phenyl ether type epoxy resins such as triglycidylaminophenol. Examples of the epoxy resin include an epoxy resin obtained by modifying such an epoxy resin, and a brominated epoxy resin obtained by brominating such an epoxy resin.
In this case, it is preferable to use an epoxy resin having a viscosity of 5000 mPas or less at 25 ℃. As a result, the composition has a reduced viscosity and improved impregnation into carbon fibers, and can be applied to a tow prepreg (tow pre) and drawing. Examples include: glycidyl ether type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, alicyclic epoxy resins, and the like. These epoxy resins may be used alone or in combination of two or more.
Examples of the glycidyl ether type epoxy resin include: a glycidyl ether type epoxy resin, a butyl glycidyl ether type epoxy resin, a phenyl glycidyl ether type epoxy resin, a (poly) ethylene glycol diglycidyl ether type epoxy resin, a (poly) propylene glycol diglycidyl ether type epoxy resin, a neopentyl glycol diglycidyl ether type epoxy resin, a 1, 4-butanediol diglycidyl ether type epoxy resin, a 1, 6-hexanediol diglycidyl ether type epoxy resin, a trimethylolpropane polyglycidyl ether type epoxy resin, a diglycidyl polyglycidyl ether type epoxy resin, an allyl glycidyl ether type epoxy resin, a 2-ethylhexyl glycidyl ether type epoxy resin, a p- (tert-butyl) phenyl glycidyl ether type epoxy resin, a dodecyl glycidyl ether type epoxy resin, a tridecyl glycidyl ether type epoxy resin, and the like. These glycidyl ether type epoxy resins may be used alone or in combination of two or more.
Examples of the glycidyl ester type epoxy resin include: hexahydrophthalic anhydride diglycidyl ester type epoxy resin, tetrahydrophthalic anhydride diglycidyl ester type epoxy resin, tertiary fatty acid monoglycidyl ester type epoxy resin, phthalic acid diglycidyl ester type epoxy resin, dimer acid glycidyl ester type epoxy resin, and the like. These glycidyl ester type epoxy resins may be used alone or in combination of two or more.
Examples of the glycidylamine-type epoxy resin include: meta- (glycidoxyphenyl) diglycidyl amine type epoxy resins, N-diglycidyl aminobenzene type epoxy resins, ortho- (N, N-diglycidyl amino) toluene type epoxy resins, and the like. These glycidylamine-type epoxy resins may be used alone or in combination of two or more.
Examples of the alicyclic epoxy resin include: alicyclic diepoxy adipate type epoxy resin, 3, 4-epoxycyclohexylmethyl carboxylate type epoxy resin, vinylcyclohexene dioxide type epoxy resin, hydrogenated bisphenol A diglycidyl ether type epoxy resin, and the like.
As the hardener (C), dicyandiamide (dic) or a derivative thereof can be used in terms of achieving a liquefaction excellent in storage stability and being easily obtainable.
In the case where the curing agent is DICY, the blending amount of the curing agent (C) is preferably from the viewpoint of the cured product characteristics: the ratio of the number of moles of epoxy groups of the total epoxy resins including the polyurethane modified epoxy resin (B) and the polyurethane unmodified epoxy resin (a) to the number of moles of active hydrogen groups of dic was set to 1:0.3 to 1:1.2, preferably 1:0.9 to 1:1.1.
The urethane-modified epoxy resin composition of the present invention may further contain a hardening accelerator (D). The hardening accelerator (D) is preferably used for suppressing an increase in impregnation into the reinforcing fiber and viscosity when the imidazole-based hardening aid is mixed, and is also preferably used for satisfying heat resistance at the time of hardening. As the imidazole-based curing assistant, 2-methylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4 ',5' -dihydroxymethylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole and the like are preferably used. Further, an imidazole compound containing a triazine ring is preferable, and examples of such a compound include: 2, 4-diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -ethyl-4 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -undecylimidazolyl- (1 ') ] -ethyl-s-triazine, and the like. Among them, 2, 4-diamino-6- [2 '-methylimidazolyl- (1') ] -ethyl-s-triazine may be more preferably used from the viewpoint of being curable in a short time. The triazine ring-containing imidazole compounds may be used either alone or in combination of two or more.
On the other hand, depending on the application and the method, hardening in a short time as described above may not be required. In this case, crystalline imidazole compounds such as 2, 4-diamino-6- [2 '-methylimidazolyl- (1') ] -ethyl-s-triazine isocyanurate (2 MA-OK) and urea compounds such as 3- (3, 4-dichlorophenyl) -1,1-dimethylurea (3- (3, 4-dichlorophenyl) -1, 1-dimethyllurea, DCMU) can be used. The amount of the hardening accelerator (D) is preferably in the range of 0.1 to 5wt% based on the total of the entire epoxy resin including the polyurethane modified epoxy resin (B) and the polyurethane unmodified epoxy resin (a) and the hardening agent (C).
The epoxy resin composition of the present invention may optionally contain a release agent (E) according to the use or the working method. The release agent may be a liquid release agent, a solid (powder) release agent, or the like, and may be a liquid release agent at ordinary temperature (10 to 30 ℃) so that even in a low-viscosity composition, the release agent can be uniformly mixed. In addition, by mixing a release agent into the resin, the drawing formability is improved. This improves the orientation of the fibers in the molded article, and therefore, the mechanical properties such as compression strength of the molded article are increased, and the adhesion to the adhesive is increased due to the smooth surface.
The amount of the release agent to be blended is preferably 0.1 to 6 parts by mass based on 100 parts by mass of the entire epoxy resin. More preferably 0.1 to 4 parts by mass. If the amount is less than 0.1 part by mass, sufficient releasability may not be obtained. If the amount exceeds 6 parts by mass, the strength of the molded article may be lowered, or the adhesion or adhesiveness may be lowered. The release agents may be used singly or in combination of two or more kinds.
The liquid release agent is not particularly limited as long as it does not phase separate from the epoxy resin composition and does not evaporate or decompose at the temperature of the mold. Specific dominant products include: modovetate (MOLDWIZ INT) -1324, 1324B, 1836, 1846, 1850, 1854, 1882, etc. manufactured by Baindustrial Co., ltd.
Examples of solid (powder) mold release agents include shellac wax (shellac wax), beeswax, and spermaceti wax, carnauba wax (carnauba wax) and wood wax (haze wax) as animal waxes, paraffin wax (paramffin wax) and microcrystalline wax (microcrystalline wax) as mineral waxes, and Fischer-Tropsch wax (Fischer-Tropsch wax), polyethylene wax, polypropylene wax, and the like as synthetic waxes, and it is desirable that the wax be in a powder form that can be uniformly dispersed in an epoxy resin composition, and that the wax be melted and dissolved at a temperature at the time of molding and hardening.
The cured product of the present invention is obtained by curing the epoxy resin composition. The method for obtaining the cured product may be a curing method based on a general curable resin composition, and for example, the heating temperature condition may be appropriately selected according to the type, use, and the like of the curing agent to be combined. For example, a method of heating the epoxy resin composition at a temperature ranging from room temperature to about 250 ℃. General methods of the curable resin composition can also be used, such as molding methods.
The cured product of the present invention has excellent heat resistance and excellent damping properties, and therefore, the glass transition temperature (Tg) of the cured product is preferably 120℃or higher, and the loss coefficient (tan. Delta.) is preferably 0.03 or higher in the temperature range of-40℃to 40 ℃.
The fiber-reinforced composite material of the present invention can be obtained by impregnating reinforcing fibers with the epoxy resin composition of the present invention to obtain a composition for a fiber-reinforced composite material and curing the composition by molding. Here, the reinforcing fiber may be any of twisted yarn, untwisted yarn, and the like, but untwisted yarn or untwisted yarn is preferable because it has excellent moldability in the fiber-reinforced composite material. Further, as the form of the reinforcing fiber, a form in which the fiber direction is aligned in one direction or a fabric may be used. The fabric may be freely selected from plain weave fabrics, satin weave fabrics, and the like according to the site of use or use. Specifically, carbon fibers, glass fibers, aramid fibers, boron fibers, alumina fibers, silicon carbide fibers, and the like may be used alone or in combination of two or more of them, for example, for excellent mechanical strength and durability. Among these, carbon fibers are preferable in terms of the strength of molded articles, and various carbon fibers such as polyacrylonitrile-based carbon fibers, pitch-based carbon fibers, and rayon-based carbon fibers can be used.
The method for obtaining the fiber-reinforced composite from the epoxy resin composition of the present invention is not particularly limited, and examples thereof include the following methods: a method of producing a varnish by uniformly mixing the components constituting the epoxy resin composition, wherein the varnish obtained in the above step is impregnated with unidirectional reinforcing fibers in which reinforcing fibers are aligned in one direction (a state before curing in a pultrusion method or a filament winding method, a strand prepreg), and a method of producing a varnish by impregnating a resin in a substrate such as a material in which continuous carbon fibers are arranged in one direction and formed into a sheet shape or a carbon fiber woven fabric, a material in which a resin layer is disposed on at least one surface of a carbon fiber substrate, and a material in which a fiber layer is further disposed on the surface; and a method (a state before hardening in a resin transfer molding (resin transfer molding, RTM) method) in which a sheet or a fabric of reinforcing fibers is placed in a mold in a superimposed manner, and then resin is injected into the mold and pressure is applied to impregnate the sheet or the fabric or the inside is depressurized to impregnate the sheet or the fabric.
In the fiber-reinforced composite material of the present invention, the volume content of the reinforcing fibers is preferably 40 to 85% based on the total volume of the molded article, and more preferably 50 to 75% in terms of strength. When the volume content is less than 40%, the content of the epoxy resin composition may be too large, and the elastic modulus or strength of the cured product obtained may be insufficient or may not satisfy various properties required. If the volume content exceeds 85%, the resin in the reinforcing fiber is insufficient, resulting in insufficient adhesion, void generation, or the like, and the cured product may have insufficient elastic modulus or strength, or reduced interfacial adhesion.
Examples (example)
Next, the present invention will be specifically described based on examples. The present invention is not limited to the specific examples described above, and any modifications and alterations can be made without departing from the gist of the present invention.
The evaluation methods of the physical properties are as follows.
(1) Determination of the presence or absence of residual NCO groups by means of Infrared (IR): after 0.05g of the obtained polyurethane-modified epoxy resin was dissolved in 10ml of tetrahydrofuran, the solution was applied to KBr plate using a micro-spatula plate portion, and dried at room temperature for 15 minutes to evaporate the tetrahydrofuran, thereby preparing a sample for IR measurement. This was set on a Fourier transform infrared Spectrum (Fourier transform infrared Spectrum, FT-IR) device Spectrum-1 (Spectrum-One) manufactured by Perkin Elmer, inc., 2270cm in a characteristic absorption band as an NCO group -1 When the extensional vibration absorption spectrum of (c) was lost, it was determined that no residual NCO groups were present.
(2) Epoxy equivalent: quantification was performed according to JISK 7236.
(3) Hydroxyl equivalent: 25ml of dimethylformamide was taken out in a 200ml Erlenmeyer flask with a glass stopper, and a sample containing 11 mg/equivalent or less of hydroxyl group was precisely weighed and added thereto to dissolve the same. 20ml of 1 mol/L-phenylisocyanate toluene solution and 1ml of dibutyltin maleate catalyst solution are added by a pipette respectively, and the mixture is fully stirred and mixed by shaking and tightly covered, so that the mixture is reacted for 30 to 60 minutes. After the completion of the reaction, 20ml of a 2 mol/L-dibutylamine toluene solution was added and mixed by stirring with sufficient shaking, and the mixture was left for 15 minutes to react with an excessive amount of phenyl isocyanate. Next, 30ml of methyl cellosolve and 0.5ml of bromocresol green indicator were added, and the excess amine was titrated with a calibrated methyl cellosolve solution. Since the indicator changes from blue to green and then to yellow, the initial point of the change to yellow is set as the end point, and the hydroxyl equivalent is determined using the following formulas i and ii.
Hydroxyl equivalent weight (g/eq) = (1000×w)/C (S-B) … (i)
C: concentration (mol/L) of methyl Cellosolve perchlorate solution
W: sample amount (g)
S: titration amount (ml) of methyl cellosolve perchlorate solution
B: titration amount (ml) of methyl cellosolve perchlorate solution required for blank test at the time of titration
C＝(1000×W)/{121×(s-b)}…(ii)
w: the amount of tris- (hydroxymethyl) -aminomethane taken (g) for calibration
s: titration amount (ml) of methyl cellosolve perchlorate solution required for titration of tris- (hydroxymethyl) -aminomethane
b: titration amount (ml) of methyl cellosolve perchlorate solution required for blank test at the time of calibration
(4) Hydroxyl number: the measurement was performed by the measurement method referring to JISK 1557.
(5) Viscosity: the viscosity values at 25℃were measured using an E-type viscometer cone plate type. The epoxy resin composition of the present invention was prepared, and 0.8mL thereof was used for measurement, and the value after 60 seconds from the start of measurement was taken as the viscosity value.
(6) Glass transition temperature (Tg): the intersection of the baseline and the tangent at the inflection point was derived as the glass transition temperature (Tg) using a differential scanning calorimeter (differential scanning calorimeter, DSC) at a heating rate of 10 ℃/min.
(7) Tensile test: the cured product molded into the shape of JIS K7161 by die casting was used as a test piece, and tensile test was performed at room temperature of 23℃using a universal tester, and the tensile strength, tensile elongation, and tensile elastic modulus were measured, respectively.
(8) Weight average molecular weight (Mw): the measurement was performed by gel permeation chromatography (gel permeation chromatography, GPC) under the following conditions.
Measurement device: HLC-8420GPC manufactured by Tosoh Co., ltd
And (3) pipe column: TSKgel SuperMultipore HZ-Mx2
Measurement conditions: temperature 40 ℃, eluent Tetrahydrofuran (THF), flow rate 0.35mL/min
Sample: polystyrene SRM706a
(9) Loss coefficient (tan delta): a test piece obtained by casting and processing a resin cured product or molded product into a shape of 50mmL×10mmW×2mmt was subjected to measurement of a loss coefficient (tan delta) using a dynamic viscoelasticity apparatus under conditions of a frequency of 10Hz and a heating rate of 2 ℃/min, and a value in a temperature range of-40 ℃ to 40 ℃ was calculated.
(10) The evaluation method of the phase separation structure of the cured product: the resin compositions obtained in examples and comparative examples were subjected to vacuum degassing, and a casting plate having a spacer 4mm thick sandwiched between metal plates was used, and when a system other than a rapid hardening system such as 2MA-OK was used as the hardening accelerator (D), a hardened product was obtained at 120℃for 1 hour and then at 150℃for 1 hour. In the case of using a rapid hardening system such as 2MZA-PW as the hardening accelerator (D), a hardened product was obtained at 130℃for 15 minutes. Thereafter, the cured product was cut out and trimmed by a microtome (microtome), and the surface was observed by a stereomicroscope or an atomic force microscope (AFM: atomic Force Microscope).
Stereo microscope:
the device is a lycra (Leica) stereo microscope M205C
The illumination being coaxial
AFM：
The device is Dimension Icon (Dimension Icon) AFM (manufactured by Bruker-AXS)
The probe was NCHV (Bruker) -AXS)
Radius of curvature of front end 10nm
Spring constant 42N/m (nominal)
Mode: tapping Mode (Tapping Mode)
The judgment criteria are as follows.
X: sea-island structure. The island is spherical, the island size is tens to hundreds nanometers, and tan delta is low (0.01 to 0.02 level).
O: phase separation structure of local mutually invasive connection. Island aggregation occurs, the island size is on the order of several micrometers to tens of micrometers, and tan delta is 0.03 or more.
The raw materials used are as follows.
Component A
Ebolet (Epotohto) YD-128, bisphenol A type epoxy resin, epoxy equivalent 187g/eq, liquid, manufactured by Nitro iron chemistry & Material (NIPPON STEEL Chemical & Material)
Ebolet (Epotohto) YDF-170, bisphenol F type epoxy resin, epoxy equivalent 170g/eq, liquid, manufactured by Nitro iron chemistry & Material (NIPPON STEEL Chemical & Material)
Ebolter (Epotohto) YH-300, polyglycidyl ether of trimethylolpropane, epoxy equivalent 142g/eq, liquid manufactured by Nitro iron chemistry & Material (NIPPON STEEL Chemical & Material)
Component B
Epoxy resin (a-1):
ebolet (Epotohto) YDF-170, bisphenol F type epoxy resin, epoxy equivalent 170g/eq, hydroxyl equivalent 2600g/eq and liquid form manufactured by Nicotine chemical & Material (NIPPON STEEL Chemical & Material)
Epoxy resin (a-2):
ebolter (Epotohto) YH-300, polyglycidyl ether of trimethylolpropane, epoxy equivalent 142g/eq, hydroxyl equivalent 837g/eq, liquid, manufactured by Nitro iron chemistry & Material (NIPPON STEEL Chemical & Material)
Polytetramethylene ether glycol (b-1) represented by the following formula (2 a):
PTMG2000 manufactured by Mitsubishi chemical, number average molecular weight 2000, hydroxyl equivalent 1000g/eq PTMG3000 manufactured by Mitsubishi chemical, number average molecular weight 3000, hydroxyl equivalent 1450g/eq
Polyol compound (b-2):
ai Dike Polyether (Adeka Polymer) P-3000, polypropylene glycol, number average molecular weight 3000, hydroxyl equivalent 1500g/eq manufactured by ADEKA Ai Dike
Polyisocyanate compound (c):
(c-1) Costumotet (Cosmonate) PH, 4' -diphenylmethane diisocyanate (MDI) manufactured by Mitsui chemistry
( c-2) Costumotet (Cosmonate) T-80, toluene Diisocyanate (TDI) (mass ratio of 2, 4-toluene diisocyanate to 2, 6-toluene diisocyanate about 8:2, a mixture of )
(c-3) Takanet (Takenate) 500, meta-Xylene Diisocyanate (XDI) manufactured by Mitsui chemical
Low molecular weight polyol compound (d):
1,4-Butanediol (BD) (reagent), molecular weight 90
Component C:
gemciron Ai Kusi (DICIYANEX) 1400F, dicyandiamide component D, manufactured by EVONIK:
crystalline imidazole, solid azole (Curezol) 2MZA-PW, 2, 4-diamino-6- [2 '-methylimidazolyl- (1') ] -ethyl-s-triazine manufactured by four-national chemical industry
Example 1
Ebolet (Epotohto) YDF-170 was used as the epoxy resin (a-1), ebolet (Epotohto) YH-300 was used as the epoxy resin (a-2), mitsubishi chemical PTMG3000 was used as the polytetramethylene ether glycol, cosmerate (Cosmonate) PH (MDI) was used as the polyisocyanate (c-1), and 1,4-Butanediol (BD) was used as the low molecular weight polyol compound (d). The amounts (unit: parts by weight) of these used are shown in Table 1.
A1000 ml four-port separable flask including a nitrogen inlet pipe, a stirrer and a temperature regulator was charged with Ebolet (Epotohto) YDF-170, ebolet (Epotohto) YH-300 and PTMG3000, heated to 120℃and stirred and mixed for 120 minutes. Then, coomassie Monte (Cosmonate) PH was added thereto and reacted at 120℃for 2 hours. Then, 1,4-butanediol was added and reacted at 120℃for 2 hours to obtain a polyurethane-modified epoxy resin (example 1, UE 1).
The completion of the reaction was confirmed by disappearance of the absorption spectrum of NCO groups by IR measurement. The obtained polyurethane-modified epoxy resin (example 1) had an epoxy equivalent of 226g/eq and a weight average molecular weight of 14000.
Examples 2 to 9 and comparative examples 1 to 2
Polyurethane modified epoxy resins (UE 2 to UE 9) were obtained by performing the reaction in the same procedure as in example 1, except that the raw material charge composition was as shown in table 1. Regarding the epoxy equivalent, UE 2 was 241g/eq, UE 3 was 273g/eq, UE 4 was 237g/eq, UE 5 was 219g/eq, UE 6 was 234g/eq, UE 7 was 262g/eq, UE 8 was 212g/eq, UE 9 was 251g/eq, UE 10 was 251g/eq, and UE 11 was 258g/eq.
Next, examples of the epoxy resin compositions and cured epoxy resin products using the polyurethane-modified epoxy resins obtained in examples 1 to 9 and comparative examples 1 to 2 are shown. The results are summarized in Table 2.
Example 10
The polyurethane-modified epoxy resin UE 1 obtained in example 1 as the polyurethane-modified epoxy resin (B), ebolter (Epotohto) YD-128 as the polyurethane-unmodified epoxy resin (A), ebolter (Epotohto) YH-300, dicyandiamide as the hardener (C), and 2MZA-PW as the hardening accelerator (D) were each placed in a 200ml dedicated disposable cup (disposable cup) in the formulations described in Table 2, and vacuum defoamation was performed for 5 minutes using a vacuum planetary mixer in a autorotation-revolution laboratory while stirring and mixing to obtain a liquid resin composition. Here, the molar ratio of epoxy groups to dicyandiamide is set to 1.0:0.5, 140g of a polyurethane-modified epoxy resin composition was prepared.
Next, the liquid resin composition was cast into a mold having a groove shape of the test piece size of JISK 7161. The test piece for tensile test was used by pouring a solution into a mold or a frame made of silicon having a dumbbell-type test piece size, a fracture toughness test piece size of 100mmL×10mmW×4mmt and a kinetic analysis (dynamic mechanical analysis, DMA) test piece size of 100mmL×10mmW×2mmt, and cutting into a size suitable for measurement. The casting property at this time is a level at which sufficient casting can be performed with a margin. Next, the resin composition was poured into a mold heated at 130 ℃ in advance, and then placed into a hot air oven, and heat-cured at 130 ℃ for 5 minutes to prepare an epoxy resin cured product test piece. The test results using the test pieces are shown in table 2.
Examples 11 to 19 and comparative examples 3 to 7
The reaction was carried out in the same manner as in example 10 except that the amounts of the raw materials were as shown in Table 2, to obtain a resin composition and a cured product. The test results using these test pieces are shown in table 2.
By using the polyurethane-modified epoxy resin composition of the present invention, curing is completed under such a short curing condition as 130℃for 5 minutes, and a resin composition having low viscosity, excellent impregnation properties, sufficient mechanical properties, and excellent damping properties can be obtained.
TABLE 1
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[ Industrial applicability ]
The polyurethane-modified epoxy resin composition of the present invention has a low viscosity, excellent fiber impregnation properties, suppressed lowering of glass transition temperature, and an optimal phase separation structure of a cured product, and a high loss coefficient (tan δ), and is therefore useful as a matrix resin for composite materials, adhesive formulated resin, etc. for industries, sports and leisure, civil engineering and construction, etc. requiring damping properties.
Claims (9)
1. A polyurethane-modified epoxy resin composition comprising, as essential components, a polyurethane-unmodified epoxy resin (A), a polyurethane-modified epoxy resin (B) and a hardener (C), wherein the polyurethane-modified epoxy resin (B) has a structure derived from a polyether polyol and a structure derived from a polyisocyanate and wherein the structure having an isocyanate group at the end of the molecular chain is reacted with hydroxyl groups of an epoxy resin having two or more epoxy groups on average in the molecule, the polyurethane-modified epoxy resin (B) is contained in an amount of 20 to 70% by weight relative to the total amount of solid components of the epoxy resin composition, the component (A) is compatible with the component (B), and the polyurethane-modified epoxy resin composition is characterized in that the component (A) and the component (B) form a phase-separated structure as a hardened product after the hardening reaction, and the loss coefficient tan delta measured using a dynamic viscoelastometer is 0.03 viscosity or more in a temperature range of-40 to 40 ℃ and a viscosity of 50 Pa.s or less measured using a type E meter under conditions of a frequency of 10Hz and a heating rate of 2 ℃/min.
2. The polyurethane-modified epoxy resin composition according to claim 1, wherein 30 mol% or more of the structures derived from the polyether polyol in the polyurethane-modified epoxy resin (B) are derived from polytetramethylene ether glycol.
3. The polyurethane-modified epoxy resin composition according to claim 1, wherein in the polyurethane-modified epoxy resin (B), 1/3 or more of the number of moles of the epoxy resin having two or more epoxy groups in the molecule on average is an aliphatic epoxy resin.
4. The polyurethane-modified epoxy resin composition according to claim 1, wherein the polyurethane-modified epoxy resin (B) has a weight average molecular weight of 8000 or more and a urethane component content of 13.5% by weight or more.
5. The polyurethane-modified epoxy resin composition according to claim 3, wherein in the polyurethane-modified epoxy resin (B), the aliphatic epoxy resin is a polyglycidyl ether of trimethylolpropane.
6. A cured product obtained by curing the polyurethane-modified epoxy resin composition according to any one of claims 1 to 5.
7. A resin composition for fiber-reinforced composite materials, which is obtained by impregnating the reinforcing fibers with the polyurethane-modified epoxy resin composition according to any one of claims 1 to 5.
8. A fiber-reinforced composite material obtained from the resin composition for a fiber-reinforced composite material according to claim 7.
9. A polyurethane modified epoxy resin comprising a structure obtained by reacting a hydroxyl group of an epoxy resin having a structure derived from a polyether polyol and a structure derived from a polyisocyanate and having an isocyanate group at a terminal of a molecular chain and having an average of two or more epoxy groups in a molecule, characterized in that,
more than 30 mole% of the structure derived from the polyether polyol is derived from polytetramethylene ether glycol,
more than 1/3 of the number of moles of the epoxy resin having two or more epoxy groups in the molecule is aliphatic epoxy resin.
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