CN105440252B - 一种紫外光固化的水性聚氨酯改性环氧衣康酸树脂及其制备方法 - Google Patents
一种紫外光固化的水性聚氨酯改性环氧衣康酸树脂及其制备方法 Download PDFInfo
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- CN105440252B CN105440252B CN201510946752.1A CN201510946752A CN105440252B CN 105440252 B CN105440252 B CN 105440252B CN 201510946752 A CN201510946752 A CN 201510946752A CN 105440252 B CN105440252 B CN 105440252B
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- itaconic acid
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- epoxy
- epoxy resin
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- 229920005989 resin Polymers 0.000 title claims abstract description 43
- 239000011347 resin Substances 0.000 title claims abstract description 43
- OYBSKKHHESSJOP-UHFFFAOYSA-N 2-methylidene-3-oxobutanedioic acid Chemical class OC(=O)C(=C)C(=O)C(O)=O OYBSKKHHESSJOP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000004814 polyurethane Substances 0.000 title claims abstract description 34
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000007711 solidification Methods 0.000 title description 7
- 230000008023 solidification Effects 0.000 title description 7
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 32
- 239000003822 epoxy resin Substances 0.000 claims abstract description 30
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 16
- 239000006184 cosolvent Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 239000003112 inhibitor Substances 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- -1 organic acid tin salt Chemical group 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- 229920001228 polyisocyanate Polymers 0.000 claims description 7
- 239000005056 polyisocyanate Substances 0.000 claims description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- 238000003848 UV Light-Curing Methods 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 4
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 150000002009 diols Chemical class 0.000 claims description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 3
- 150000004714 phosphonium salts Chemical group 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 229940005561 1,4-benzoquinone Drugs 0.000 claims description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims 1
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pent-2-ene Chemical group CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 238000000576 coating method Methods 0.000 abstract description 10
- 239000011248 coating agent Substances 0.000 abstract description 9
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- 239000010695 polyglycol Substances 0.000 abstract 2
- 239000012948 isocyanate Substances 0.000 abstract 1
- 150000007530 organic bases Chemical class 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 12
- 239000000523 sample Substances 0.000 description 11
- 229920001451 polypropylene glycol Polymers 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000003556 assay Methods 0.000 description 4
- 238000000205 computational method Methods 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
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- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- PKKGKUDPKRTKLJ-UHFFFAOYSA-L dichloro(dimethyl)stannane Chemical compound C[Sn](C)(Cl)Cl PKKGKUDPKRTKLJ-UHFFFAOYSA-L 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QMOKQVPITLXHJM-UHFFFAOYSA-N n,n-dimethylpent-3-en-1-amine Chemical class CC=CCCN(C)C QMOKQVPITLXHJM-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- IQQVCMQJDJSRFU-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO IQQVCMQJDJSRFU-UHFFFAOYSA-N 0.000 description 1
- BJEMXPVDXFSROA-UHFFFAOYSA-N 3-butylbenzene-1,2-diol Chemical compound CCCCC1=CC=CC(O)=C1O BJEMXPVDXFSROA-UHFFFAOYSA-N 0.000 description 1
- JTFYLWDSSRMXHW-UHFFFAOYSA-N 6-butan-2-yl-2,6-dinitrocyclohexa-2,4-dien-1-ol Chemical class [N+](=O)([O-])C=1C(C(C=CC=1)(C(C)CC)[N+](=O)[O-])O JTFYLWDSSRMXHW-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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 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 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical group CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical class CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 1
- 125000005525 methide group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- CSHCPECZJIEGJF-UHFFFAOYSA-N methyltin Chemical compound [Sn]C CSHCPECZJIEGJF-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6407—Reaction products of epoxy resins with at least equivalent amounts of compounds containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
本发明公开了一种紫外光固化水性聚氨酯改性环氧衣康酸树脂及其制备方法。所得物脂产物由环氧树脂、衣康酸、聚二醇、二异氰酸酯制得。本发明首先采用环氧树脂和衣康酸反应，制得可UV固化环氧衣康酸树脂A，另以聚二醇和二异氰酸酯反应制得‑NCO封端的聚氨酯半加成物B，然后产物A，B反应，后加有机碱中和，制得紫外光（UV）固化水性聚氨酯改性环氧衣康酸树脂。该树脂具有良好的柔韧性，绿色环保，稳定性好，成膜性能好等优点，可以广泛的应用于环保涂料中。
Description
技术领域
本发明涉及一种紫外光固化的水性聚氨酯改性环氧衣康酸树脂及其制备方法。
背景技术
紫外光固化技术是上个世纪60年代末由德国拜耳公司开发的一种新型固化技术。具有丙烯酰氧基的树脂在受到紫外光照射后，发生光化学反应，使涂层快速聚合、交联，从而达到涂层的固化。近几年来，环境问题日益突出，为满足全球性的环境保护的要求，必须限制涂料中VOC的排放，这使得紫外光固化技术的研究开发和应用发展较快。紫外光固化水性涂料以水为溶剂，无VOC排放，安全环保，是一种新型“绿色涂料”，是未来涂料发展的重要方向。
环氧树脂是UV固化水性涂料的主要原料，价格便宜，来源广泛，但本身不具有光敏性和水溶性。现有工艺合成的水性UV树脂具有固化膜硬度高、光泽度高、固化速率快、工艺简单等优势，然而仍存在固化膜脆性高、柔韧性差等缺陷，严重限制了水性UV环氧衣康酸树脂的应用领域。
发明内容
为了解决上述存在的问题，本发通过聚氨酯对衣康酸和环氧树脂生成的产物进行改性，得到柔韧性良好的UV水性聚氨酯改性环氧衣康酸涂料，具有重要的经济和社会意义。
本发明的目的在于提供一种紫外光固化的水性聚氨酯改性环氧衣康酸树脂及其制备方法。
本发明所采取的技术方案是：
一种水性聚氨酯改性环氧衣康酸树脂的制备方法，包括以下步骤：
1)环氧衣康酸树脂的合成：将衣康酸、环氧树脂、助溶剂、阻聚剂和催化剂a混匀，升温至90～110℃，直到酸值不再变化，停止反应，制得产物A；
2)-NCO封端聚氨酯半加成物的合成：按照基团-NCO和-OH的摩尔比为(1.9～2.5)：1的比例加入聚二元醇和多异氰酸酯，搅拌均匀，测量初始-NCO含量，然后加入催化剂b，升温至60～75℃并搅拌，直至-NCO含量变为初始的0.4～0.6倍时，停止反应，制得产物B；
3)将产物A降温至40～60℃后，将产物B加入到产物A中，混匀，当-NCO反应完全时，加碱中和，即得到紫外光固化的水性聚氨酯改性环氧衣康酸树脂。
进一步的，所述衣康酸和环氧树脂的用量为使衣康酸中羧基和环氧树脂中环氧基的摩尔比为(1.5～1.8)：1。
进一步的，所述环氧树脂选自双酚A型环氧树脂E51、E44中的至少一种。
进一步的，所述助溶剂用量为环氧树脂和衣康酸总质量的5％～20％；所述助溶剂选自丙烯酸酯单体、甲基丙烯酸酯单体中的至少一种。
进一步的，所述阻聚剂用量为环氧树脂、助溶剂和衣康酸总质量的0.05％～0.2％；所述阻聚剂选自对羟基苯甲醚、对苯二酚、对苯醌、2,6-二硝基-2-仲丁基苯酚、对叔丁基邻苯二酚、2-6-二叔丁基对乙基苯酚或2，6-二叔丁基对甲酚中的至少一种。
进一步的，所述催化剂a选自路易斯碱类、季胺盐类、季磷盐类中的至少一种。
进一步的，所述聚二元醇为分子量为400～2000的聚醚二元醇、聚酯二元醇中的至少一种。
进一步的，所述多异氰酸酯为二异氰酸酯。
进一步的，所述中和剂选自三乙胺、三乙醇胺、2-(二甲氨基)乙基丙烯酸酯、甲基丙烯酸二甲氨基乙酯中的至少一种。
进一步的，所述催化剂b为有机酸锡盐。
本发明的有益效果是：
1)本发明针对水性UV环氧衣康酸树脂固化膜脆性差、柔韧性差等缺陷，利用-NCO封端的聚氨酯与环氧衣康酸树脂中的-OH反应，从而对环氧衣康酸树脂进行改性增加其固化膜柔韧性，合成了综合性能较好的水性UV聚氨酯改性环氧衣康酸树脂。
2)本发明采用衣康酸和环氧基团进行开环酯化反应，通过控制衣康酸羧基与环氧基的摩尔比，来控制树脂中羧基的含量，从而调节树脂的耐水性。
3)本发明所得树脂具有良好的柔韧性，绿色环保，稳定性好，成膜性能好等优点，可以广泛的应用于环保涂料中。
附图说明
图1为环氧树脂E51(A曲线)、环氧衣康酸树脂(B曲线)和聚氨酯改性环氧衣康酸树脂(C曲线)的红外光谱图。
具体实施方式
一种UV固化水性聚氨酯改性环氧衣康酸树脂的制备方法，包括以下步骤：
1)环氧衣康酸树脂的合成：将衣康酸、环氧树脂、助溶剂、阻聚剂和催化剂a混匀，升温至80～120℃，并搅拌测酸值，直到酸值不再变化，停止反应，制得产物A；
2)-NCO封端聚氨酯半加成物的合成：按照基团-NCO和-OH的摩尔比为(1.9～2.5)：1的比例加入聚二元醇和多异氰酸酯，搅拌均匀，测量初始-NCO含量，然后加入催化剂b，升温至60～75℃并搅拌，直至-NCO含量变为初始的0.4～0.6倍时，停止反应，制得产物B；
3)将产物A降温至40～60℃后，将产物B加入到产物A中，混匀，当-NCO反应完全时，加碱中和，即得到紫外光固化的水性聚氨酯改性环氧衣康酸树脂。
优选的，上述衣康酸和环氧树脂的用量为使衣康酸中羧基和环氧树脂中环氧基的摩尔比为(1.5～1.8)：1。
优选的，上述环氧树脂选自双酚A型环氧树脂E51、E44中的至少一种。
优选的，上述助溶剂用量为环氧树脂、和衣康酸总质量的5％～20％。
优选的，上述助溶剂选自丙烯酸酯单体、甲基丙烯酸酯单体中的至少一种。
优选的，上述丙烯酸酯单体选自丙烯酸异葵酯、丙烯酸月桂酯、丙烯酸苯氧基乙酯、二乙二醇而丙烯酸酯、三乙二醇二丙烯酸酯、三羟甲基三丙烯酸酯、季戊四醇四丙烯酸酯、二缩三羟甲基丙烷四丙烯酸酯、季戊四醇六丙烯酸酯、丙烯酸甲酯、丙烯酸丁酯、丙烯酸异辛酯中的至少一种。
优选的，上述甲基丙烯酸酯单体选自甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸异冰片酯、甲基丙烯酸四氢呋喃甲酯中的至少一种。
优选的，上述阻聚剂用量为环氧树脂、助溶剂和衣康酸总质量的0.05％～0.2％。
优选的，上述阻聚剂选自对羟基苯甲醚、对苯二酚中的至少一种。
优选的，上述催化剂a用量为环氧树脂、助溶剂和衣康酸总质量的0.5％～2％。
优选的，上述催化剂a选自路易斯碱类、季胺盐类、季磷盐类中的至少一种。
更优选的，上述催化剂a选自三乙胺、三苯基膦、N，N-二甲基苄胺中的至少一种。
优选的，上述聚二元醇为分子量为400～2000的聚醚二元醇、聚酯二元醇中的至少一种。
更优选的，上述聚二元醇选自PPG1000、PPG2000中的至少一种。
优选的，上述多异氰酸酯为二异氰酸酯。
优选的，上述二异氰酸酯选自脂肪族二异氰酸酯、芳香族二异氰酸酯中的至少一种。
更优选的，上述二异氰酸酯为异佛尔酮二异氰酸酯，
优选的，上述中和剂用量为衣康酸摩尔数的70％～90％。
优选的，上述中和剂选自三乙胺、三乙醇胺、2-(二甲氨基)乙基丙烯酸酯、甲基丙烯酸二甲氨基乙酯中的至少一种。
优选的，上述催化剂b为有机酸锡盐。
优选的，上述有机酸锡盐选自二月桂酸二丁基锡、二醋酸二甲基锡、顺丁烯二酸二甲基锡、二氯化二甲基锡、环烷酸锌、辛酸锌、三亚乙基二胺中的至少一种。
优选的，上述催化剂b用量为聚二元醇和多异氰酸酯总质量的0.5％～1％。
优选的，上述酸值的测定方法为：
1)准确称取0.5～1.0g待测树脂于250ml锥形瓶中，加入20ml丙酮或无水乙醇将其完全溶解，滴加2～3滴酚酞指示剂，用0.1mol/L的KOH-乙醇溶液滴定至粉红色且30s不褪色，即为滴定终点；
2)酸值计算方法：
式中：A为酸值，mgKOH/g；C为KOH-乙醇溶液的浓度，mol/L；V为样品消耗KOH-乙醇溶液的体积，mL：M为所测样品的质量，g；
3)根据酸值可计算反应的转化率，计算方法如下：
式中：P为转化率，％；A为实时酸值，mgKOH/g；A0为初始理论酸值，mgKOH/g值。
优选的，上述聚合物中异氰酸酯基含量的测定方法为：
1)准确称取约1g低聚物样品加入250ml碘瓶中，加入无水甲苯25ml，加塞并溶解，用移液管加入0.1mol/L的二正丁胺溶液25ml，加塞摇匀，15min后加入异丙醇100ml，溴甲酚绿指示剂4～6滴，用1mol/L盐酸溶液滴定至黄色终点，同时做空白试验。
2)异氰酸酯基(NCO)含量的计算：
NCO(％)＝(V0—V)×N×4.2/m
式中V0——空白样所用盐酸的体积，mL；
V——滴定样品所用盐酸的体积，mL；
N——盐酸精确浓度，mol/L；
M——样品质量，g。
本发明紫外光(UV)固化水性聚氨酯改性环氧衣康酸树脂的合成路线
第一步：紫外光(UV)固化环氧衣康酸树脂的合成
其中R为：
第二步：-NCO封端聚氨-酯的合成
第三步：紫外光(UV)固化水性聚氨酯环氧衣康酸树脂的合成
下面结合具体实施例对本发明做进一步的说明，但并不局限于此。
实施例1
1)向装有搅拌桨、冷凝管、温度计的四口烧瓶中加入13.1g衣康酸、20g环氧E51、4g助溶剂甲基丙烯酸丁酯、0.0334g对羟基苯甲醚和0.334g催化剂三苯基膦，升温至95℃，恒温搅拌，每隔一段时间测量一次酸值，直到酸值不再变化，停止反应，制得产物A。
上述酸值的测定方法为：
准确称取0.5～1.0g待测树脂于250ml锥形瓶中，加入20ml丙酮或无水乙醇将其完全溶解，滴加2～3滴酚酞指示剂，用0.1mol/L的KOH-乙醇溶液滴定至粉红色且30s不褪色，即为滴定终点；
酸值计算方法：
式中：A为酸值，mgKOH/g；C为KOH-乙醇溶液的浓度，mol/L；V为样品消耗KOH-乙醇溶液的体积，mL：M为所测样品的质量，g；
根据酸值可计算反应的转化率，计算方法如下：
式中：P为转化率，％；A为实时酸值，mgKOH/g；A0为初始理论酸值，mgKOH/g值。
2)向装有搅拌桨、冷凝管、温度计的三口烧瓶中加入10g聚丙二醇(PPG1000)、4.66g异佛尔酮二异氰酸酯(IPDI)升温至65℃，搅拌10分钟后测量初始-NCO值、后加入0.1g催化剂二月桂酸二丁基锡，恒温反应并搅拌，每隔20分钟测量一次-NCO浓度，直至-NCO含量变为原来的一半，停止反应，制得产物B。
3)将四口烧瓶中的产物A降温至60℃后，将产物B加入到产物A中，恒温反应，每隔一段时间测量-NCO含量，当-NCO反应完全时，后加入13.794g甲基丙烯酸二甲氨基乙酯中和，得到紫外光固化水性聚氨酯改性环氧衣康酸树脂。
上述聚合物中异氰酸酯基含量的测定方法为：
准确称取约1g低聚物样品加入250ml碘瓶中，加入无水甲苯25ml，加塞并溶解，用移液管加入0.1mol/L的二正丁胺溶液25ml，加塞摇匀，15min后加入异丙醇100ml，溴甲酚绿指示剂4～6滴，用1mol/L盐酸溶液滴定至黄色终点，同时做空白试验。
异氰酸酯基(NCO)含量的计算公式为：NCO(％)＝(V0—V)×N×4.2/m；
式中V0——空白样所用盐酸的体积，mL；
V——滴定样品所用盐酸的体积，mL；
N——盐酸精确浓度，mol/L；
M——样品质量，g。
实施例2
1)向装有搅拌桨、冷凝管、温度计的四口烧瓶中加入12.6g衣康酸、20g环氧树脂E51、4g助溶剂三羟甲基丙烷三丙烯酸酯、0.0356阻聚剂对苯二酚和0.356催化剂N，N-二甲基苄胺，升温至110℃，恒温搅拌，每隔一段时间测量一次酸值(酸值的测量方法如实施例1所述)，直至酸值到达理论酸值，停止反应，制得产物A。
2)向装有搅拌桨、冷凝管、温度计的三口烧瓶中加入20g聚丙二醇(PPG2000)、5.33g异佛尔酮二异氰酸酯(IPDI)升温至65℃，搅拌10分钟后测量初始-NCO值(测量方法如实施例1所述)、后加入0.1g催化剂二醋酸二甲基锡，恒温反应并搅拌，每隔20分钟测量一次-NCO含量，直至-NCO含量变为原来的一半，停止反应，制得产物B。
3)将四口烧瓶中的产物A降温至60℃后，将产物B加入到产物A中，恒温反应，每隔一段时间测量-NCO含量(测量方法如实施例1所述)，当-NCO反应完全时，加14.55g三乙醇胺中和，得到紫外光固化水性聚氨酯改性环氧衣康酸树脂。
对上述制备的紫外光固化水性聚氨酯改性环氧衣康酸树脂进行红外光谱检测，检测结果如图1所示，图中，其中A曲线为环氧树脂E51的红外光谱图，B曲线为环氧衣康酸树脂的红外光谱图，C曲线为实施例制备的聚氨酯改性环氧衣康酸树脂的红外光谱图。由曲线A和曲线B对比可看出曲线B中3508cm-1环氧树脂的羟基吸收峰明显增强，914cm-1的环氧基的吸收峰基本消失，同时，在1637cm-1处出现C＝C吸收峰，在1715cm-1出现羰基、羧基的C＝O伸缩振动吸收峰，并在3413cm-1出现明显的-COOH缔合特征，这是因为环氧基与衣康酸反应之后，衣康酸中的羧基剩余，羧基产生强烈缔合作用，由此可证明产物B与理论的环氧衣康酸树脂的分子结构相符；由曲线B和曲线C对比可知在1715cm-1处都出现C＝O的伸缩振动吸收峰，曲线C在3318cm-1出现N-H键的伸缩振动吸收峰，在1537cm-1出现酰胺Ⅱ带振动吸收峰，由此可知和产物B相比产物C中出现了聚氨酯的特征基团氨基甲酸酯键。由此可以证明，反应产物C与理论的聚氨酯改性环氧衣康酸树脂的分子结构相符。
实施例3
1)向装有搅拌桨、冷凝管、温度计的四口烧瓶中加入10.616g衣康酸、23.181g环氧E51、3.5g助溶剂季戊四醇四丙烯酸酯、0.0347阻聚剂甲氧基苯酚和0.347催化剂三乙胺，升温至120℃，恒温搅拌，每隔一段时间测量一次酸值(测量方法如实施例1所述)，直至酸值到达理论酸值，停止反应，制得产物A。
2)向装有搅拌桨、冷凝管、温度计的三口烧瓶中加入10g聚丙二醇(PPG1000)、4.00g异佛尔酮二异氰酸酯(IPDI)升温至65℃，搅拌10分钟后测量初始-NCO值(测量方法如实施例1所述)，然后加入0.14g催化剂二氯化二甲基锡，恒温反应并搅拌，每隔20分钟测量一次-NCO浓度，直至-NCO含量变为原来的一半，停止反应，制得产物B。
3)将四口烧瓶中的产物A降温至55℃，后将产物B加入到产物A中，恒温反应，每隔一段时间测量-NCO含量(测量方法如实施例1所述)，当-NCO反应完全时，加9.57g三乙胺中和，得到紫外光固化水性聚氨酯改性环氧衣康酸树脂。
下面将上述实施例制备的紫外光固化水性聚氨酯改性环氧衣康酸树脂作进一步的性能检测。
检测方法：将上述实施例制备的紫外光固化水性聚氨酯改性环氧衣康酸树脂在加入光引发剂和其他助剂后配置成涂料，放入紫外光固化机后固化成膜，作进一步测试其成膜性能。检测结果如表1所示。紫外固化条件为：紫外灯功率为2kw，样品和光源距离为20cm。
表1 水性聚氨酯改性环氧衣康酸树脂的性能检测结果
从表1中可以看出，本发明方法制备紫外光固化水性聚氨酯改性环氧衣康酸树脂具有光固化速度快、绿色环保、耐水性良好、柔韧性优异，其他力学性能优良等特点。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (10)
1.一种水性聚氨酯改性环氧衣康酸树脂的制备方法，其特征在于：包括以下步骤：
1)环氧衣康酸树脂的合成：将衣康酸、环氧树脂、助溶剂、阻聚剂和催化剂a混匀，升温至80～120℃，直到酸值不再变化，停止反应，制得产物A；
2)-NCO封端聚氨酯半加成物的合成：按照基团-NCO和-OH的摩尔比为(1.9～2.5)：1的比例加入聚二元醇和多异氰酸酯，搅拌均匀，测量初始-NCO含量，然后加入催化剂b，升温至60～75℃并搅拌，直至-NCO含量变为初始的0.4～0.6倍时，停止反应，制得产物B；
3)将产物A降温至40～60℃后，将产物B加入到产物A中，混匀，当-NCO反应完全时，加碱中和，即得到紫外光固化的水性聚氨酯改性环氧衣康酸树脂。
2.根据权利要求1所述的方法，其特征在于：所述衣康酸和环氧树脂的用量为使衣康酸中羧基和环氧树脂中环氧基的摩尔比为(1.5～1.8):1。
3.根据权利要求1或2所述的方法，其特征在于：所述环氧树脂选自双酚A型环氧树脂E51、E44中的至少一种。
4.根据权利要求1所述的方法，其特征在于：所述助溶剂用量为环氧树脂和衣康酸总质量的5％～20％；所述助溶剂选自丙烯酸酯单体、甲基丙烯酸酯单体中的至少一种。
5.根据权利要求1所述的方法，其特征在于：所述阻聚剂用量为环氧树脂、助溶剂和衣康酸总质量的0.05％～0.2％；所述阻聚剂选自对羟基苯甲醚、对苯二酚、对苯醌、对叔丁基邻苯二酚、2，6-二叔丁基对乙基苯酚或2，6-二叔丁基对甲酚中的至少一种。
6.根据权利要求1所述的方法，其特征在于：所述催化剂a选自路易斯碱类、季胺盐类、季磷盐类中的至少一种。
7.根据权利要求1所述的方法，其特征在于：所述聚二元醇为分子量为400～2000的聚醚二元醇、聚酯二元醇中的至少一种。
8.根据权利要求1所述的方法，其特征在于：所述多异氰酸酯为二异氰酸酯。
9.根据权利要求1所述的方法，其特征在于：所述中和剂选自三乙胺、三乙醇胺、2-(二甲氨基)乙基丙烯酸酯、甲基丙烯酸二甲氨基乙酯中的至少一种。
10.根据权利要求1所述的方法，其特征在于：所述催化剂b为有机酸锡盐。
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