CN115960017A - Modified acrylate monomer and photocurable resin thereof - Google Patents
Modified acrylate monomer and photocurable resin thereof Download PDFInfo
- Publication number
- CN115960017A CN115960017A CN202111170051.5A CN202111170051A CN115960017A CN 115960017 A CN115960017 A CN 115960017A CN 202111170051 A CN202111170051 A CN 202111170051A CN 115960017 A CN115960017 A CN 115960017A
- Authority
- CN
- China
- Prior art keywords
- acrylate
- methacrylate
- modified
- butyl
- monoisocyanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000000178 monomer Substances 0.000 title claims abstract description 68
- 239000011347 resin Substances 0.000 title claims abstract description 52
- 229920005989 resin Polymers 0.000 title claims abstract description 52
- 150000001252 acrylic acid derivatives Chemical class 0.000 title claims abstract description 49
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 4
- -1 3, 5-dichlorophenyl Chemical group 0.000 claims description 20
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims description 13
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 12
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 12
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 12
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 11
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 11
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 10
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 claims description 9
- 150000003254 radicals Chemical class 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 6
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 6
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 6
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 6
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- VEPKQEUBKLEPRA-UHFFFAOYSA-N VX-745 Chemical compound FC1=CC(F)=CC=C1SC1=NN2C=NC(=O)C(C=3C(=CC=CC=3Cl)Cl)=C2C=C1 VEPKQEUBKLEPRA-UHFFFAOYSA-N 0.000 claims description 6
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 6
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 6
- ZNAOFAIBVOMLPV-UHFFFAOYSA-N hexadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(C)=C ZNAOFAIBVOMLPV-UHFFFAOYSA-N 0.000 claims description 6
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 6
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 6
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims description 6
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 claims description 6
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 claims description 6
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 claims description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 6
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 6
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 6
- ATZHWSYYKQKSSY-UHFFFAOYSA-N tetradecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C(C)=C ATZHWSYYKQKSSY-UHFFFAOYSA-N 0.000 claims description 6
- XZHNPVKXBNDGJD-UHFFFAOYSA-N tetradecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C=C XZHNPVKXBNDGJD-UHFFFAOYSA-N 0.000 claims description 6
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 5
- FZSHSWCZYDDOCK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;oxolane Chemical compound C1CCOC1.CC(=C)C(O)=O FZSHSWCZYDDOCK-UHFFFAOYSA-N 0.000 claims description 5
- MGYGFNQQGAQEON-UHFFFAOYSA-N 4-tolyl isocyanate Chemical compound CC1=CC=C(N=C=O)C=C1 MGYGFNQQGAQEON-UHFFFAOYSA-N 0.000 claims description 5
- JRWNODXPDGNUPO-UHFFFAOYSA-N oxolane;prop-2-enoic acid Chemical compound C1CCOC1.OC(=O)C=C JRWNODXPDGNUPO-UHFFFAOYSA-N 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- ADAKRBAJFHTIEW-UHFFFAOYSA-N 1-chloro-4-isocyanatobenzene Chemical compound ClC1=CC=C(N=C=O)C=C1 ADAKRBAJFHTIEW-UHFFFAOYSA-N 0.000 claims description 4
- MGOLNIXAPIAKFM-UHFFFAOYSA-N 2-isocyanato-2-methylpropane Chemical compound CC(C)(C)N=C=O MGOLNIXAPIAKFM-UHFFFAOYSA-N 0.000 claims description 4
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims description 4
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 4
- XEFUJGURFLOFAN-UHFFFAOYSA-N 1,3-dichloro-5-isocyanatobenzene Chemical compound ClC1=CC(Cl)=CC(N=C=O)=C1 XEFUJGURFLOFAN-UHFFFAOYSA-N 0.000 claims description 3
- OGBWMWKMTUSNKE-UHFFFAOYSA-N 1-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CCCCCC(OC(=O)C(C)=C)OC(=O)C(C)=C OGBWMWKMTUSNKE-UHFFFAOYSA-N 0.000 claims description 3
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 3
- CZQIJQFTRGDODI-UHFFFAOYSA-N 1-bromo-4-isocyanatobenzene Chemical compound BrC1=CC=C(N=C=O)C=C1 CZQIJQFTRGDODI-UHFFFAOYSA-N 0.000 claims description 3
- HHIRBXHEYVDUAM-UHFFFAOYSA-N 1-chloro-3-isocyanatobenzene Chemical compound ClC1=CC=CC(N=C=O)=C1 HHIRBXHEYVDUAM-UHFFFAOYSA-N 0.000 claims description 3
- GFNKTLQTQSALEJ-UHFFFAOYSA-N 1-isocyanato-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(N=C=O)C=C1 GFNKTLQTQSALEJ-UHFFFAOYSA-N 0.000 claims description 3
- PJVRNNRZWASOIT-UHFFFAOYSA-N 1-isocyanato-4-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(N=C=O)C=C1 PJVRNNRZWASOIT-UHFFFAOYSA-N 0.000 claims description 3
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 claims description 3
- JFZBUNLOTDDXNY-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)propoxy]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)OCC(C)OC(=O)C(C)=C JFZBUNLOTDDXNY-UHFFFAOYSA-N 0.000 claims description 3
- UKTKKMZDESVUEE-UHFFFAOYSA-N 2-chloro-4-isocyanato-1-methylbenzene Chemical compound CC1=CC=C(N=C=O)C=C1Cl UKTKKMZDESVUEE-UHFFFAOYSA-N 0.000 claims description 3
- SFPNZPQIIAJXGL-UHFFFAOYSA-N 2-ethoxyethyl 2-methylprop-2-enoate Chemical compound CCOCCOC(=O)C(C)=C SFPNZPQIIAJXGL-UHFFFAOYSA-N 0.000 claims description 3
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 claims description 3
- 125000004189 3,4-dichlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(Cl)C([H])=C1* 0.000 claims description 3
- MFUVCHZWGSJKEQ-UHFFFAOYSA-N 3,4-dichlorphenylisocyanate Chemical compound ClC1=CC=C(N=C=O)C=C1Cl MFUVCHZWGSJKEQ-UHFFFAOYSA-N 0.000 claims description 3
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 claims description 3
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 3
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 3
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000004386 diacrylate group Chemical group 0.000 claims description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 3
- BUZRAOJSFRKWPD-UHFFFAOYSA-N isocyanatosilane Chemical compound [SiH3]N=C=O BUZRAOJSFRKWPD-UHFFFAOYSA-N 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- HNHVTXYLRVGMHD-UHFFFAOYSA-N n-butyl isocyanate Chemical compound CCCCN=C=O HNHVTXYLRVGMHD-UHFFFAOYSA-N 0.000 claims description 3
- RZFODFPMOHAYIR-UHFFFAOYSA-N oxepan-2-one;prop-2-enoic acid Chemical compound OC(=O)C=C.O=C1CCCCCO1 RZFODFPMOHAYIR-UHFFFAOYSA-N 0.000 claims description 3
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 claims description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 3
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 claims 2
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 claims 1
- GCNKJQRMNYNDBI-UHFFFAOYSA-N [2-(hydroxymethyl)-2-(2-methylprop-2-enoyloxymethyl)butyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(CC)COC(=O)C(C)=C GCNKJQRMNYNDBI-UHFFFAOYSA-N 0.000 claims 1
- CSVRUJBOWHSVMA-UHFFFAOYSA-N oxolan-2-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCO1 CSVRUJBOWHSVMA-UHFFFAOYSA-N 0.000 claims 1
- FEUIEHHLVZUGPB-UHFFFAOYSA-N oxolan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC1CCCO1 FEUIEHHLVZUGPB-UHFFFAOYSA-N 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000004814 polyurethane Substances 0.000 description 7
- 229920002635 polyurethane Polymers 0.000 description 7
- 238000001723 curing Methods 0.000 description 6
- 239000012974 tin catalyst Substances 0.000 description 6
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920001228 polyisocyanate Polymers 0.000 description 5
- 239000005056 polyisocyanate Substances 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 238000010146 3D printing Methods 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OWPUOLBODXJOKH-UHFFFAOYSA-N 2,3-dihydroxypropyl prop-2-enoate Chemical compound OCC(O)COC(=O)C=C OWPUOLBODXJOKH-UHFFFAOYSA-N 0.000 description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 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
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- HSOOIVBINKDISP-UHFFFAOYSA-N 1-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(CCC)OC(=O)C(C)=C HSOOIVBINKDISP-UHFFFAOYSA-N 0.000 description 1
- BONVROUPOZRCDU-UHFFFAOYSA-N 2-hydroxyprop-2-enamide Chemical class NC(=O)C(O)=C BONVROUPOZRCDU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 1
- SBVKVAIECGDBTC-UHFFFAOYSA-N 4-hydroxy-2-methylidenebutanamide Chemical compound NC(=O)C(=C)CCO SBVKVAIECGDBTC-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- TUOBEAZXHLTYLF-UHFFFAOYSA-N [2-(hydroxymethyl)-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(CC)COC(=O)C=C TUOBEAZXHLTYLF-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention relates to a modified acrylic resinThe modified acrylate monomer contains an acrylate structure and a carbamate structure, and the molecular structure is as follows:
Description
Technical Field
The invention relates to a modified acrylic monomer and a photocurable resin thereof, belongs to the field of high polymer materials, and particularly relates to a modified acrylic monomer and a preparation method thereof, a photocurable resin containing the modified acrylic monomer and application thereof.
Background
Photocuring printing is a process of processing a photocurable resin into a three-dimensional object using a digital file as a model. At present, the Stereolithography (SLA) and Digital Light Processing (DLP) photocuring printing technologies are mainly classified according to the forming principle. The method has the advantages of flexible object form design, high printing speed, high precision, wide application and the like, and the development has been developed from model manufacturing to batch production and manufacturing of final consumer products.
The light curing material mainly comprises oligomer, diluent, photoinitiator and other auxiliary agents, and is prepared by ultraviolet light initiated polymerization curing, and the chemical reaction mechanism is divided into free radical light curing, cationic light curing or dual curing. The most common free radical photo-curing system is acrylate resin, which has excellent optical characteristics, but the material is generally brittle, has poor toughness and is not impact-resistant, so that the popularization and the use of the resin are limited. At present, the method is more common to compound acrylate with materials such as polyesters, polyethers and polyurethanes to prepare modified acrylate resin so as to improve the performance of the modified acrylate resin, wherein the polyurethane modified acrylate oligomer is a more conventional modification mode at present, and is mainly to prepare a polyurethane prepolymer through the reaction of polyisocyanate and polymer polyol, and then to obtain a final oligomer through the end capping of hydroxyl-containing propionate.
Therefore, the development of a photo-curable printing material with excellent mechanical strength, good stability, good toughness, chemical resistance, abrasion resistance and the like is a key technical problem to be solved urgently.
Disclosure of Invention
The technical problem is as follows: in order to solve the technical defects, the invention aims to provide a modified acrylate monomer and a photocurable resin thereof.
The technical scheme is as follows: the modified acrylate monomer contains an acrylate structure and a carbamate structure, and the molecular structure is as follows:
wherein the content of the first and second substances,
r1 is selected from hydrogen, C1-C10 branched chain or straight chain alkyl;
r2 is selected from C1-C20 branched chain or straight chain or cyclic alkyl;
r3 is selected from C1-C20 linear chain or branched chain (substituted) or cyclic aliphatic alkyl, C6-C30 (substituted) alkyl aromatic, C1-C30 (substituted) siloxane group, and does not contain isocyanate group.
Wherein, the first and the second end of the pipe are connected with each other,
r1 is one or more of hydrogen, methyl, ethyl, propyl and isopropyl.
R2 is one or more of methyl, ethyl, propyl and butyl.
R3 is one or more of methyl, n-butyl, tert-butyl, phenyl, p-chlorophenyl, 3, 4-dichlorophenyl, 3, 5-dichlorophenyl, p-methylphenyl, 3-chloro-4-methylphenyl, p-isopropylphenyl, p-nitrophenyl, p-bromophenyl, propyltrimethoxysilyl and propyltriethoxysilane.
The modified acrylate monomer is obtained by reacting hydroxyl acrylate with monoisocyanate;
the hydroxy acrylate comprises one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, caprolactone acrylate, caprolactone methacrylate and hydroxyethyl caprolactone acrylate.
The monoisocyanate comprises one or more of n-butyl isocyanate, tert-butyl isocyanate, p-chlorophenyl isocyanate, silyl monoisocyanate, 3-chlorophenyl monoisocyanate, 3, 4-dichlorophenyl monoisocyanate, 3, 5-dichlorophenyl monoisocyanate, p-methylphenyl monoisocyanate, 3-chloro-4-methylphenyl monoisocyanate, p-isopropylphenyl monoisocyanate, p-nitrophenyl monoisocyanate, p-bromophenyl monoisocyanate, isocyanatopropyltrimethoxysilane and isocyanatopropyltriethoxysilane.
The photocurable resin containing the modified acrylate monomer specifically comprises the following raw material components in parts by weight:
20-40 parts of modified acrylate monomer;
30-70 parts of oligomer;
5 to 30 portions of non-modified acrylic monomer.
Wherein, the first and the second end of the pipe are connected with each other,
the photocurable resin also comprises 0.1-5 parts of photoinitiator, wherein the photoinitiator comprises one or more of photoinitiator 369, TPO, 819, 907, 651, 2959, 1173, 184, BP, MK, ITX and 2-EA.
The oligomer is one or more of polyurethane acrylate, epoxy acrylate, polyether acrylate, polyester acrylate, polysiloxane acrylate and hybrid oligomer, and has a molecular weight of 200-5000.
The non-modified acrylic monomer contains at least one radical polymerizable group and at least one radical polymerizable group, and comprises one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, n-octyl acrylate, isooctyl acrylate, dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, octadecyl acrylate, tetrahydrofuran acrylate, isobornyl acrylate, ethoxyethyl acrylate, ethylene glycol diacrylate, butanediol diacrylate, hexanediol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, tetrahydrofuran methacrylate, isobornyl methacrylate, acryloyl morpholine, ethoxyethyl methacrylate, ethylene glycol dimethacrylate, butylene glycol dimethacrylate, hexanediol dimethacrylate, dipropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and trimethylolpropane trimethacrylate.
Preferably, the non-modified acrylic monomer contains only one radical polymerizable group, including one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, n-octyl acrylate, isooctyl acrylate, dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, octadecyl acrylate, tetrahydrofuran acrylate, isobornyl acrylate, ethoxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, tetrahydrofuran methacrylate, isobornyl methacrylate, acryloyl morpholine, and ethoxyethyl acrylate.
Has the advantages that: the modified acrylic monomer is introduced into the photocurable resin, so that the cohesive energy of the material can be effectively increased. In addition, the hardness of the obtained light-cured resin product has a wide adjustable range, and the mechanical properties of the product, particularly the flexibility and the storage stability, can be greatly improved. The product obtained by the light-curable resin through the light-curing technology can be used for three-dimensional printing of buffering and shock-absorbing products, three-dimensional printing of handheld samples, three-dimensional printing of medical models, three-dimensional printing of industrial models and the like.
Detailed Description
The modified acrylate monomer contains an acrylate structure and a carbamate structure, and the molecular structure is as follows:
wherein R1 is selected from hydrogen, C1-C10 branched chain or straight chain alkyl;
r2 is selected from C1-C20 branched chain or straight chain or cyclic alkyl;
r3 is selected from C1-C20 linear or branched (substituted) aliphatic alkyl, C6-C30 (substituted) alkyl aromatic and C1-C30 (substituted) siloxane, and does not contain isocyanate group;
preferably, R1 is one or more of hydrogen, methyl, ethyl, propyl and isopropyl;
preferably, R2 is one or more of methyl, ethyl, propyl and butyl;
preferably, R3 is one or more of methyl, n-butyl, tert-butyl, phenyl, p-chlorophenyl, 3, 4-dichlorophenyl, 3, 5-dichlorophenyl, p-methylphenyl, 3-chloro-4-methylphenyl, p-isopropylphenyl, p-nitrophenyl, p-bromophenyl, propyltrimethoxysilyl and propyltriethoxysilane;
the modified acrylate monomer is obtained by the reaction of hydroxyl acrylate and monoisocyanate;
the hydroxyl acrylate comprises one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, caprolactone acrylate, caprolactone methacrylate and hydroxyethyl caprolactone acrylate;
the monoisocyanate comprises one or more of n-butyl isocyanate, tert-butyl isocyanate, p-chlorophenyl isocyanate, silyl monoisocyanate, 3-chlorophenyl monoisocyanate, 3, 4-dichlorophenyl monoisocyanate, 3, 5-dichlorophenyl monoisocyanate, p-methylphenyl monoisocyanate, 3-chloro-4-methylphenyl monoisocyanate, p-isopropylphenyl monoisocyanate, p-nitrophenyl monoisocyanate, p-bromophenyl monoisocyanate, isocyanatopropyltrimethoxysilane and isocyanatopropyltriethoxysilane.
The photocurable resin contains the modified acrylic monomer, and specifically comprises the following raw material components in parts by weight:
20-40 parts of modified acrylate monomer;
30-70 parts of an oligomer;
5-30 parts of non-modified propylene monomer;
the photocurable resin also comprises 0.1-5 parts of photoinitiator;
the oligomer is one or more of polyurethane acrylate, epoxy acrylate, polyether acrylate, polyester acrylate and polysiloxane acrylate, and has a molecular weight of 200-5000;
the oligomer is polyurethane acrylate, and the polyurethane acrylate can be obtained by adding hydroxyl acrylic acid with reactivity to NCO and hydroxyl acrylic acid derivatives thereof for blocking after a polyurethane prepolymer with NCO blocking end is obtained by reacting polymer polyol and polyisocyanate;
the polymer polyol comprises polyester polyol and polyether polyol; polyisocyanates include aliphatic polyisocyanates, aromatic polyisocyanates, such as TDI, MDI, PPDI, NDI, IPDI, HMDI, HDI, and the like; hydroxyacrylic acid and hydroxyacrylic acid derivatives thereof include hydroxyacrylic acid, hydroxyacrylamides such as hydroxyethyl acrylate, hydroxyethyl methacrylate, methylolacrylamide, hydroxyethylacrylamide, trimethylolpropane diacrylate, pentaerythritol triacrylate, and the like;
some urethane acrylates are also commercially available.
The non-modified acrylic monomer at least one radical polymerizable group comprises one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, tert-butyl acrylate, n-octyl acrylate, isooctyl acrylate, dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, octadecyl acrylate, tetrahydrofuran acrylate, isobornyl acrylate, ethoxyethyl acrylate, ethylene glycol diacrylate, butanediol diacrylate, hexanediol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, tetrahydrofuran methacrylate, isobornyl methacrylate, acryloylmorpholine, ethoxyethyl methacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, hexanediol dimethacrylate, polyethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, trimethylolpropane trimethacrylate.
Preferably, the non-modified acrylic monomer contains only one radical polymerizable group, including one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, n-octyl acrylate, isooctyl acrylate, dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, octadecyl acrylate, tetrahydrofuran acrylate, isobornyl acrylate, ethoxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, tetrahydrofuran methacrylate, isobornyl methacrylate, morpholine, ethoxyethyl acrylate;
the photoinitiator comprises one or more of photoinitiators 369, TPO, 819, 907, 651, 2959, 1173, 184, BP, MK, ITX and 2-EA;
optionally, the photocurable resin can be added with additives commonly used in the field, including one or more of color paste, defoaming agent, antioxidant, light stabilizer and ultraviolet absorbent;
the addition amount of the auxiliary agent is not particularly required, and the auxiliary agent can be added according to actual requirements.
The preparation method of the modified acrylate monomer and the photocurable resin is not specifically limited, and sufficient reaction of the reaction raw materials is ensured.
As an example, the modified acrylate monomer may be specifically prepared according to the following steps:
adding a hydroxyl acrylate monomer into a heating and stirring container, heating to 40-65 ℃, and then, adding a monomer according to the molar ratio of hydroxyl acrylate to monoisocyanate of 1: (0.8-1.2) adding monoisocyanate, controlling the reaction temperature at 70-80 ℃ and reacting for 1-5 h, and optionally adding a catalyst to improve the reaction rate to obtain the modified acrylate monomer.
In some embodiments of the invention, the hydroxyl acrylate to monoisocyanate molar ratio is 1.
As an example, the photocurable resin may be specifically prepared according to the following steps:
and sequentially adding the oligomer, the modified acrylate monomer and the non-modified acrylate monomer into a reaction kettle, heating to 40-60 ℃, stirring for 0.5-2 h, optionally adding an auxiliary agent, continuously stirring for 0.5-2 h, and defoaming in vacuum for 0.5-1 h until no bubbles exist, thereby obtaining the light-curable resin.
Wherein the photoinitiator can be added into the resin during the preparation process of the photocurable resin; the resin containing the photoinitiator can be prepared and stored in a dark place, and the resin without the photoinitiator can be prepared and stored in a dark place.
The technical solution of the present invention is further explained below according to specific embodiments. The scope of protection of the invention is not limited to the following examples, which are set forth for illustrative purposes only and are not intended to limit the invention in any way.
Modified acrylate monomer 1: r1 is hydrogen, R2 is ethyl, and R3 is n-butyl;
the preparation method of the modified acrylate monomer 1 comprises the following steps: adding hydroxyethyl acrylate into a heating stirring container, heating to 50 ℃, and then adding a mixture of hydroxyl acrylate and monoisocyanate according to a molar ratio of 1:1, adding tert-butyl isocyanate and an organic tin catalyst, and controlling the reaction temperature at 70 ℃ to react for 3h to obtain the modified acrylate monomer 1.
Modified acrylate monomer 2: r1 is methyl, R2 is ethyl, and R3 is p-chlorophenyl;
the preparation method of the modified acrylate monomer 2 comprises the following steps: adding hydroxyethyl methacrylate into a heating stirring container, heating to 50 ℃, and then adding a mixture of hydroxyl acrylate and monoisocyanate according to a molar ratio of 1:1, adding p-chlorophenyl isocyanate, adding an organic tin catalyst, and controlling the reaction temperature to react for 3 hours at 70 ℃ to obtain a modified acrylate monomer 2.
Modified acrylate monomer 3: r1 is methyl, R2 is propyl, and R3 is p-methylphenyl;
the preparation method of the modified acrylate monomer 3 comprises the following steps: adding hydroxypropyl methacrylate into a heating stirring container, heating to 50 ℃, and then adding a mixture of hydroxyl acrylate and monoisocyanate according to a molar ratio of 1:1, adding p-methylphenyl monoisocyanate and an organic tin catalyst, and controlling the reaction temperature to react for 3 hours at 70 ℃ to obtain a modified acrylate monomer 3.
Modified acrylate monomer 4: r1 is hydrogen, R2 is propyl, and R3 is propyltriethoxysilane;
the preparation method of the modified acrylate monomer 4 comprises the following steps: adding hydroxypropyl acrylate into a heating stirring container, heating to 50 ℃, and then, according to the molar ratio of 1:1 adding isocyanatopropyl triethoxysilane, adding an organic tin catalyst, and controlling the reaction temperature to react for 3 hours at 70 ℃ to obtain a modified acrylate monomer 4.
The preparation method of the modified acrylate monomer 5 comprises the following steps: adding hydroxypropyl methacrylate into a heating stirring container, heating to 50 ℃, and then mixing according to the molar ratio of hydroxyl group molar weight to NCO molar weight of 1:1, adding 4, 4-diphenylmethane diisocyanate, adding an organic tin catalyst, and controlling the reaction temperature at 70 ℃ to react for 3 hours to obtain a modified acrylate monomer 5.
The preparation method of the modified acrylate monomer 6 comprises the following steps: adding 2, 3-dihydroxy propyl acrylate into a heating stirring container, heating to 50 ℃, and then adding a mixture of 2, 3-dihydroxy propyl acrylate and diisocyanate according to the molar ratio of the hydroxyl in hydroxyl acrylate to the NCO in monoisocyanate of 1:1. adding p-methyl phenyl monoisocyanate, adding an organic tin catalyst, and controlling the reaction temperature at 70 ℃ to react for 3h to obtain the modified acrylate monomer 6.
Example 1
The photocurable resin comprises the following raw material components in parts by weight:
example 2
The photocurable resin comprises the following raw material components in parts by weight:
example 3
The photocurable resin comprises the following raw material components in parts by weight:
example 4
The photocurable resin comprises the following raw material components in parts by weight:
example 5
The photocurable resin comprises the following raw material components in parts by weight:
example 6
The photocurable resin comprises the following raw material components in parts by weight:
example 7
The photocurable resin comprises the following raw material components in parts by weight:
example 8
The photocurable resin comprises the following raw material components in parts by weight:
comparative example 1
The difference from the example 1 is that the modified acrylate monomer 1 is replaced by hydroxyethyl acrylate, and the types and contents of other raw material components are not changed.
Comparative example 2
The difference from example 3 is that urethane acrylate is replaced with polyurethane of the same molecular weight, and the kinds and contents of other raw material components are unchanged.
Comparative example 3
The difference from the example 8 is that the modified polyacrylic acid monomer 3 is replaced by the modified acrylate monomer 5, and the types and contents of other raw material components are not changed.
Comparative example 4
The difference from the example 8 is that the modified polyacrylic acid monomer 3 is replaced by the modified acrylate monomer 6, and the types and contents of other raw material components are not changed.
The photocurable resin is prepared by the following steps:
sequentially adding the oligomer, the modified acrylate monomer and the non-modified acrylic monomer into a reaction kettle, heating to 55 ℃, stirring for 1h, then weighing the photoinitiator in proportion, continuously stirring for 0.5h in a dark place, defoaming for 1h in a vacuum way until no bubbles exist, obtaining the photocurable resin, and storing in the dark place.
Preparation of photocurable resin article:
the photocurable resins of the above examples and comparative examples were added to a DLP type printer, matched printing parameters were adjusted, test specimens of the corresponding specifications were printed according to the test standards, alcohol-washed, and post-exposed to an ultraviolet lamp for 1 to 10 minutes to obtain resin articles for testing.
The resins of the above examples, comparative examples and their articles were recorded for the relevant performance tests, as shown in tables 1 and 2 below:
(1) The hardness test method comprises the following steps: GB/T531.1.
(2) The test method of tensile strength and elongation at break comprises the following steps: GB/T528.
(3) Impact strength test method: GB/T1043.1.
(5) Resin storage stability test method: the photocurable resin was stored in a light-shielding, sealed environment at room temperature for one month, and the physical state was observed.
Table 1:
table 2:
among them, the modified acrylic monomers of comparative examples 3 and 4 were not soluble and difficult to be uniformly mixed with other raw materials during the preparation of photocurable resins, and resin products could not be prepared during the photocuring process, and thus performance tests could not be performed.
As can be seen from the above table, the photocurable resin containing the modified acrylic monomer of the present invention has a wide hardness range, which is from 81A to 72D, and the photocurable resin has good mechanical properties such as tensile strength; the resin product also has excellent toughness, the low-hardness product has good toughness, and the impact strength is 52-58J/cm 2 The impact strength of the 50D-72D high-hardness product is also 26J/cm 2 The aboveThe highest high-hardness product can reach 43J/cm 2 . The conventional non-modified acrylic photocurable resin article of comparative example 1 not only showed a significant change in hardness as compared with example 1, but also exhibited significantly inferior tensile strength and impact strength to those of example 1. The comparative example 2 also showed a significant change in hardness as compared with example 3, which was significantly inferior to example 3 in terms of tensile strength, elongation at break, impact strength, and resin storage stability.
Claims (10)
1. A modified acrylate monomer is characterized by comprising an acrylate structure and a carbamate structure, wherein the molecular structure is as follows:
wherein the content of the first and second substances,
r1 is selected from hydrogen, C1-C10 branched chain or straight chain alkyl;
r2 is selected from C1-C20 branched chain or straight chain or cyclic alkyl;
r3 is selected from C1-C20 linear chain or branched chain (substituted) or cyclic aliphatic alkyl, C6-C30 (substituted) alkyl aromatic, C1-C30 (substituted) siloxane group, and does not contain isocyanate group.
2. The modified acrylate monomer of claim 1, wherein R1 is one or more of hydrogen, methyl, ethyl, propyl, and isopropyl.
3. The modified acrylate monomer of claim 1 wherein R2 is one or more of methyl, ethyl, propyl, and butyl.
4. The modified acrylate monomer according to claim 1, wherein R3 is one or more of methyl, n-butyl, t-butyl, phenyl, p-chlorophenyl, 3, 4-dichlorophenyl, 3, 5-dichlorophenyl, p-methylphenyl, 3-chloro-4-methylphenyl, p-isopropylphenyl, p-nitrophenyl, p-bromophenyl, propyltrimethoxysilyl, and propyltriethoxysilane.
5. The modified acrylate monomer of claim 1, wherein the modified acrylate monomer is obtained by reacting a hydroxy acrylate with a monoisocyanate; the hydroxyl acrylate comprises one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, caprolactone acrylate, caprolactone methacrylate and hydroxyethyl caprolactone acrylate; the monoisocyanate comprises one or more of n-butyl isocyanate, tert-butyl isocyanate, p-chlorophenyl isocyanate, silyl monoisocyanate, 3-chlorophenyl monoisocyanate, 3, 4-dichlorophenyl monoisocyanate, 3, 5-dichlorophenyl monoisocyanate, p-methylphenyl monoisocyanate, 3-chloro-4-methylphenyl monoisocyanate, p-isopropylphenyl monoisocyanate, p-nitrophenyl monoisocyanate, p-bromophenyl monoisocyanate, isocyanatopropyltrimethoxysilane and isocyanatopropyltriethoxysilane.
6. A photocurable resin containing the modified acrylate monomer of claim 5, which comprises the following raw material components in parts by weight:
20-40 parts of modified acrylate monomer;
30-70 parts of an oligomer;
5-30 parts of non-modified acrylic monomer.
7. The photocurable resin of claim 6 further comprising 0.1-5 parts of a photoinitiator, wherein the photoinitiator comprises one or more of photoinitiator 369, TPO, 819, 907, 651, 2959, 1173, 184, BP, MK, ITX, and 2-EA.
8. A photocurable resin in accordance with claim 6, wherein the oligomer is one or more of urethane acrylate, epoxy acrylate, polyether acrylate, polyester acrylate, and polysiloxane acrylate, and has a molecular weight of 200 to 5000.
9. The photocurable resin of claim 6 wherein the non-modified acrylic monomer contains at least one free radical polymerizable group and includes at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, n-octyl acrylate, isooctyl acrylate, dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, octadecyl acrylate, tetrahydrofuryl acrylate, isobornyl acrylate, ethoxyethyl acrylate, ethylene glycol diacrylate, butanediol diacrylate, hexanediol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, tetrahydrofuryl methacrylate, isobornyl methacrylate, acryloyl morpholine, ethoxyethyl methacrylate, butylene glycol methacrylate, diethylene glycol dimethacrylate, hexanediol dimethacrylate, dipropylene glycol dimethacrylate, trimethylolpropane dimethacrylate, and trimethylolpropane trimethacrylate.
10. The photocurable resin of claim 6 wherein the non-modified acrylic monomer contains only one free radical polymerizable group selected from the group consisting of hydroxyethyl acrylate, hydroxypropyl acrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, n-octyl acrylate, isooctyl acrylate, dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, octadecyl acrylate, tetrahydrofuran acrylate, isobornyl acrylate, acryloylmorpholine, ethoxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, tetrahydrofuran methacrylate, isobornyl methacrylate, and ethoxyethyl acrylate.
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