CN105037297B - It is a kind of containing carboxy-modified polycyclic amines and preparation method thereof and its application in polyfunctional acrylic ester - Google Patents
It is a kind of containing carboxy-modified polycyclic amines and preparation method thereof and its application in polyfunctional acrylic ester Download PDFInfo
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- CN105037297B CN105037297B CN201510348618.1A CN201510348618A CN105037297B CN 105037297 B CN105037297 B CN 105037297B CN 201510348618 A CN201510348618 A CN 201510348618A CN 105037297 B CN105037297 B CN 105037297B
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- modified
- ester
- polyfunctional acrylic
- polycyclic amines
- acrylic ester
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- -1 carboxy-modified polycyclic amines Chemical class 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 150000002148 esters Chemical class 0.000 claims abstract description 37
- 238000007711 solidification Methods 0.000 claims abstract description 35
- 230000008023 solidification Effects 0.000 claims abstract description 35
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005915 ammonolysis reaction Methods 0.000 claims abstract description 4
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 claims abstract 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 53
- 229920000570 polyether Polymers 0.000 claims description 52
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- 239000000178 monomer Substances 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 108090000790 Enzymes Proteins 0.000 claims description 14
- 102000004190 Enzymes Human genes 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000003112 inhibitor Substances 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 238000005292 vacuum distillation Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000006845 Michael addition reaction Methods 0.000 claims description 4
- 230000036961 partial effect Effects 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- 108090001060 Lipase Proteins 0.000 claims description 3
- 239000004367 Lipase Substances 0.000 claims description 3
- 102000004882 Lipase Human genes 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical group 0.000 claims description 3
- 235000019421 lipase Nutrition 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- JRHPOFJADXHYBR-UHFFFAOYSA-N 1-n,2-n-dimethylcyclohexane-1,2-diamine Chemical compound CNC1CCCCC1NC JRHPOFJADXHYBR-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- 108090000371 Esterases Proteins 0.000 claims description 2
- 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 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 125000004386 diacrylate group Chemical group 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- 230000002459 sustained effect Effects 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims 2
- SEPPVOUBHWNCAW-FNORWQNLSA-N (E)-4-oxonon-2-enal Chemical compound CCCCCC(=O)\C=C\C=O SEPPVOUBHWNCAW-FNORWQNLSA-N 0.000 claims 1
- NNNLYDWXTKOQQX-UHFFFAOYSA-N 1,1-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OC(CC)(OC(=O)C=C)OC(=O)C=C NNNLYDWXTKOQQX-UHFFFAOYSA-N 0.000 claims 1
- LJRSZGKUUZPHEB-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxypropoxy)propoxy]propyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COC(C)COC(=O)C=C LJRSZGKUUZPHEB-UHFFFAOYSA-N 0.000 claims 1
- LLBZPESJRQGYMB-UHFFFAOYSA-N 4-one Natural products O1C(C(=O)CC)CC(C)C11C2(C)CCC(C3(C)C(C(C)(CO)C(OC4C(C(O)C(O)C(COC5C(C(O)C(O)CO5)OC5C(C(OC6C(C(O)C(O)C(CO)O6)O)C(O)C(CO)O5)OC5C(C(O)C(O)C(C)O5)O)O4)O)CC3)CC3)=C3C2(C)CC1 LLBZPESJRQGYMB-UHFFFAOYSA-N 0.000 claims 1
- 102100023336 Chymotrypsin-like elastase family member 3B Human genes 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 claims 1
- 229940051250 hexylene glycol Drugs 0.000 claims 1
- 108010043524 protease E Proteins 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 150000001412 amines Chemical class 0.000 abstract description 35
- 230000005012 migration Effects 0.000 abstract description 11
- 238000013508 migration Methods 0.000 abstract description 11
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 abstract 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 19
- 230000000977 initiatory effect Effects 0.000 description 14
- 229920000768 polyamine Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 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 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 230000007812 deficiency Effects 0.000 description 10
- 229920001451 polypropylene glycol Polymers 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- ZXAJZEODAIBNIB-UHFFFAOYSA-K lanthanum(3+) methanesulfonate Chemical compound [La+3].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O ZXAJZEODAIBNIB-UHFFFAOYSA-K 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 108010084311 Novozyme 435 Proteins 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 150000005682 diethyl carbonates Chemical class 0.000 description 2
- 230000002255 enzymatic effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- QTKDDPSHNLZGRO-UHFFFAOYSA-N 4-methylcyclohexane-1,3-diamine Chemical compound CC1CCC(N)CC1N QTKDDPSHNLZGRO-UHFFFAOYSA-N 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- RZYKUPXRYIOEME-UHFFFAOYSA-N CCCCCCCCCCCC[S] Chemical compound CCCCCCCCCCCC[S] RZYKUPXRYIOEME-UHFFFAOYSA-N 0.000 description 1
- VVNCNSJFMMFHPL-VKHMYHEASA-N D-penicillamine Chemical compound CC(C)(S)[C@@H](N)C(O)=O VVNCNSJFMMFHPL-VKHMYHEASA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- 108091005804 Peptidases Proteins 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-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
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- 150000005686 dimethyl carbonates Chemical class 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- NAPHXISIYHAKAH-UHFFFAOYSA-N lanthanum;trifluoromethanesulfonic acid Chemical compound [La].OS(=O)(=O)C(F)(F)F NAPHXISIYHAKAH-UHFFFAOYSA-N 0.000 description 1
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
- C07D295/215—Radicals derived from nitrogen analogues of carbonic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
- C07C273/1809—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
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Abstract
The present invention relates to a kind of containing carboxy-modified polycyclic amines and preparation method thereof and its application in polyfunctional acrylic ester, described is the polycyclic amines with least two ring structures formed with carbonic ester and alicyclic diamine through ammonolysis reaction containing carboxy-modified polycyclic amines;Wherein, the alicyclic diamine refers to the one or more in piperazine, IPD, Isosorbide-5-Nitrae hexamethylene diamine, the cyclohexanediamine of 1 methyl 2,4 and the cyclohexanediamine of N, N' dimethyl 1,2.By it is described be applied to containing carboxy-modified polycyclic amines in polyfunctional acrylic ester when, the solidification rate of polyfunctional acrylic ester can be significantly improved, reduces cure shrinkage and the hardness and resistance to elevated temperatures of polyfunctional acrylic ester can be significantly improved, while the characteristics of there is small smell, small amine migration and small xanthochromia containing carboxy-modified polycyclic amines polyfunctional acrylic ester of generation.
Description
Technical field
The present invention relates to the synthesis containing carboxy-modified polycyclic amines, and in particular to one kind contains carboxy-modified polycyclic amines and its preparation
Method and its application in polyfunctional acrylic ester, more particularly to containing carboxy-modified polycyclic amines in polyfunctional acrylate monomer
And(It is branched)Application in polyether acrylate.
Background technology
It is well known that aliphatic tertiary amine can be as a kind of aided initiating, with hydrogen-capture-type light initiator benzophenone(BP)Or
Heterocycle arone constitutes composite initiator, and collaboration under ultraviolet light promotes the generation of living radical and effectively reduction oxygen inhibition to make
With so as to improve UV solidification rates, contributing to being fully cured for deep layer and top layer;But existing reactive amines are mostly with small molecule amine
Class, such as diethylamine, di-n-propylamine, di-n-butylamine, by Michael addition reaction, make the partial double bond of many official's monomers is tertiary-aminated to obtain
Arrive, the reactive amines that such as TMPTA or TPGDA are modified, but such reactive amines are still suffered from that smell is big, easily occur amine migration and xanthochromia is tight
Disadvantage, should not largely use in UV systems, be only capable of as a kind of aided initiating of outer addition again etc.;Therefore, still need to seek one
Plant smell small, be not susceptible to amine migration and the small reactive amines aided initiating of xanthochromia;Or seeking one kind, there is tertiary amine to help initiation
The low viscosity resin of active group to overcome that reactive amines aided initiating of the prior art consumption in UV systems is small, smell big,
The problem of easily occurring amine migration and serious xanthochromia.
The content of the invention
Contain carboxy-modified polycyclic amines it is an object of the invention to overcome the deficiencies of the prior art and provide one kind, it is described to contain carbonyl
Base is modified the polycyclic amines with least two ring structures that polycyclic amines are formed by carbonic ester and alicyclic diamine through ammonolysis reaction, will
It is described when being applied to containing carboxy-modified polycyclic amines in polyfunctional acrylic ester, the solidification speed of polyfunctional acrylic ester can be significantly improved
Rate, reduction cure shrinkage can simultaneously significantly improve the hardness and resistance to elevated temperatures of polyfunctional acrylic ester, while what is generated contains carbonyl
Base is modified the characteristics of polycyclic amines polyfunctional acrylic ester has small smell, small amine migration and small xanthochromia.
Another object of the present invention is to provide the above-mentioned preparation method containing carboxy-modified polycyclic amines.
It is above-mentioned many in the preparation modification of polycyclic amines containing carbonyl containing carboxy-modified polycyclic amines another object of the present invention is to provide
Application in functional acrylate.
The preparation method of polyfunctional acrylic ester is modified another object of the present invention is to provide above-mentioned polycyclic amines containing carbonyl.
Another object of the present invention is to provide a kind of polycyclic amines containing carbonyl to be modified polyfunctional acrylic ester.
To achieve the above object, the present invention is adopted the following technical scheme that:
One kind contains carboxy-modified polycyclic amines, and described is through ammonolysis with carbonic ester and alicyclic diamine containing carboxy-modified polycyclic amines
React the polycyclic amines with least two ring structures formed;Wherein, the alicyclic diamine refers to piperazine, isophorone two
One or more in amine, 1,4- hexamethylene diamines, 1- methyl -2,4- cyclohexanediamine and N, N'- dimethyl -1,2- cyclohexanediamine.
What the present invention was provided has at least two ring structures containing carboxy-modified polycyclic amines, changes what the present invention was provided containing carbonyl
Property polycyclic amines when applying in polyfunctional acrylic ester, the solidification rate of polyfunctional acrylic ester can be significantly improved, reduce solidification
Shrinkage factor and the hardness and resistance to elevated temperatures that polyfunctional acrylic ester can be significantly improved, while containing for generation is carboxy-modified polycyclic
The characteristics of amine polyfunctional acrylic ester has small smell, small amine migration and small xanthochromia.
Preferably, the carbonic ester is dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate, carbonic acid two
One or more in butyl ester, ethylene carbonate and propene carbonate.
The above-mentioned preparation method containing carboxy-modified polycyclic amines, specifically includes following steps:Carbonic ester and alicyclic diamine are pressed
Mol ratio is 1:1~2 ratio reacts 3~12h under the conditions of 60~120 DEG C, and vacuum distillation removes the anti-of accessory substance and excess
Thing is answered to produce.
A kind of polycyclic amines containing carbonyl are modified polyfunctional acrylic ester, and the polycyclic amines containing carbonyl are modified polyfunctional acrylic ester
Contain carboxy-modified polycyclic amines with polyfunctional acrylic ester through Michael addition reaction by above-mentioned, in the part of polyfunctional acrylic ester
Polycyclic tertiary amine structure is introduced in double bond.
In the present invention, above-mentioned polyfunctional acrylic ester include polyfunctional acrylate monomer and(It is branched)Polyoxyalkylene acrylate
Ester, the polyfunctional acrylate monomer is diacrylate -1,6 hexylene glycol ester, trimethylolpropane trimethacrylate, two contractings threePropane diolsTwoAcrylate, one or more in pentaerythritol triacrylate;It is described(It is branched)Polyether acrylate is by gathering
Ethoxylated polyhydric alcohol or branch polyether polyatomic alcohol with(Methyl)Acrylate carries out ester exchange reaction and obtained;The PPG or branch
The degree of functionality for changing PPG is 3~12, and relative molecular mass is 400~5000;
Wherein, the branch polyether polyatomic alcohol is obtained by trihydroxylic alcohol and/or tetrahydroxylic alcohol through catalyzing and condensing, or passes through epoxy again
Propane and/or oxirane are obtained after carrying out chain extension.
In the present invention, the degree of functionality of the PPG or branch polyether polyatomic alcohol refers to PPG or branched poly-
The number of the hydroxyl contained in ethoxylated polyhydric alcohol.
In the present invention, the branch polyether polyatomic alcohol is obtained by trihydroxylic alcohol and/or tetrahydroxylic alcohol through catalyzing and condensing, more specifically
Ground, can be condensed to yield by more than two trihydroxylic alcohols and/or tetrahydroxylic alcohol.
It is highly preferred that the branch polyether polyatomic alcohol is condensed to yield by the trihydroxylic alcohol and/or tetrahydroxylic alcohol of more than three.Invention
People has been surprisingly found that the PPG with this branched structure when being prepared into branch polyether acrylate of the present invention, is removed
Have outside low viscosity, have also obtained higher curing rate.
In the present invention, when the polyfunctional acrylic ester is polyfunctional acrylate monomer, above-mentioned reaction is generated
A kind of polyfunctional acrylate monomer containing carboxy-modified polycyclic amine structure, i.e., a kind of reactive amines aided initiating, reactive amines are helped
The characteristics of initiator has small smell, small amine migration and small xanthochromia, which overcomes the deficiency of regular activated amine aided initiating,
The polyfunctional acrylate monomer containing carboxy-modified polycyclic amine structure has higher solidification rate, less solidification simultaneously
Shrinkage factor and more excellent hardness and resistance to elevated temperatures;
When the polyfunctional acrylic ester is(It is branched)During polyether acrylate, above-mentioned reaction generates one kind and changed containing carbonyl
The polycyclic amine structure of property(It is branched)Polyether acrylate, it is described containing carboxy-modified polycyclic amine structure(It is branched)Polyether acrylate
It is a kind of low viscosity resin for having and helping and triggering group, it has higher solidification rate, less cure shrinkage, more excellent
Hardness and resistance to elevated temperatures, the gas that brings after reactive amines aided initiating is added into resin of the prior art while overcoming
Taste is big, easily occur amine migration and the serious deficiency of xanthochromia;In addition, described containing carboxy-modified polycyclic amine structure(It is branched)Polyethers third
Olefin(e) acid ester can largely be used in the formula of light-cured resin because viscosity is relatively low as a kind of resin, without the need for extra
Reactive amines are added, this avoids the deficiency of reactive amines of the prior art.
Preferably, the degree of functionality of the PPG is 3~6, and relative molecular mass is 700~2000;It is described branched
The degree of functionality of PPG is 5~9, and relative molecular weight is 400~3000.
Preferably, the acrylate is methyl acrylate, ethyl acrylate, methyl methacrylate or methacrylic acid
One or more in ethyl ester.
In the present invention, the PPG or branch polyether polyatomic alcohol with(Methyl)The ester exchange reaction of acrylate
Carried out under conditions of solidification enzyme and efficient accelerator, the solidification enzyme is esterase(E.C.3.1.1.1), lipase
(E.C.3.1.1.3)Or protease(E.C.3.4.-.-)In one or more;The efficient accelerator is lanthanide rare sulfonic acid
Salt.
The present invention is first using lanthanide rare sulfonate as the efficient accelerator of enzymatic ester exchange reaction, applied to preparation
(It is branched)The catalysis that polyether acrylate, solidification enzyme and efficient accelerator synergy greatly improve solidification enzyme catalyst is lived
Property, improve the esterification yield of product;In addition, compared with prior art, the present invention is carried out under low temperature condition of no solvent, low temperature is anti-
Degraded and the double-bond polymerization of ehter bond should be advantageously reduced, product purity is high;Solvent-free system is conducive to improving reaction substrate and production
The concentration of thing, purifying products processing is simple, step is few, without catalyst residual.
Preferably, the solidification enzyme is lipase(E.C.3.1.1.3), it is further preferred that the commodity board of the solidification enzyme
Number be Novozyme 435 or LVK-F100.
Preferably, the efficient accelerator is in lanthanum methanesulfonate, trifluoromethane sulfonic acid lanthanum or dodecyl sodium sulfonate lanthanum
It is one or more of;The efficient accelerator that the present invention is used can be bought or be made by oneself by market, lanthanum methanesulfonate and dodecyl sulphur
Sour lanthanum can be prepared via a method which to obtain:Lanthana is soluble in water with water-soluble sulfonate, pH is adjusted at a certain temperature,
Make water-insoluble sulfonic acid lanthanum Precipitation, dry.
Preferably, the consumption of the solidification enzyme catalyst is the 0.5%~2.0% of gross mass, the consumption of the accelerator
To solidify the 1%~2% of enzyme quality.
Trihydroxylic alcohol of the present invention, tetrahydroxylic alcohol can be ternary well known in the art or quaternary small molecule polyol, preferably
Ground, the trihydroxylic alcohol can be glycerine or trimethylolpropane;The tetrahydroxylic alcohol can be pentaerythrite.
It is above-mentioned(It is branched)The preparation method of polyether acrylate includes ester exchange reaction and the big step of purification process two, specifically
It is as follows:
S1:Ester exchange reaction:By PPG or branch polyether polyatomic alcohol, excessive(Methyl)Acrylate, antioxygen
Agent and polymerization inhibitor carry out ester exchange reaction under the conditions of 30~80 DEG C after being uniformly dispersed, 3~48h of sustained response obtains product standby
With;
S2:Purification process:Step S1 products therefroms are filtered, methanol or ethanol that reaction is generated is distilled off in filtrate decompression
And excessive(Methyl)Acrylate, produces final product.
Preferably,(It is branched)The preparation method of polyether acrylate is as follows:
S1:Ester exchange reaction:By PPG or branch polyether polyatomic alcohol, excessive(Methyl)Acrylate, antioxygen
After agent and polymerization inhibitor are uniformly dispersed, solidification enzyme catalyst and efficient accelerator is added, reaction 3 under being stirred at 30~80 DEG C~
48h, obtains that product is standby, and the consumption of the solidification enzyme catalyst is the 0.5%~2.0% of gross mass, the consumption of the accelerator
To solidify the 1%~2% of enzyme quality;
S2:Purification process:Step S1 products therefroms are filtered, methanol or ethanol that reaction is generated is distilled off in filtrate decompression
And excessive(Methyl)Acrylate, produces final product.
In the present invention, the addition of polymerization inhibitor can be prevented(Methyl)Acrylic double bond polymerize, it is ensured that handed in ester
Change the stability in the stages such as course of reaction, purification process, Product transport and storage;The present invention preferentially from it is of light color, inhibition when
Between the long and good polymerization inhibitor of stability, it is further preferred that the polymerization inhibitor be cupric oxide, copper sulphate, ferrous sulfate, to benzene two
One or more in phenol, MEHQ, 2,6 di tert butyl 4 methyl phenol and phenthazine;In order to avoid polymerization inhibitor
Content is excessive, influences the light-cured performance of final products, and the consumption of the polymerization inhibitor has certain restriction, is usually no more than total matter
The 1.0% of amount.
The addition of antioxidant can be effectively improved low viscosity(It is branched)The outward appearance of polyether acrylate product, to keeping producing
The permanent performance of product also has certain effect, the antioxidant be mainly Hinered phenols or/andPhosphorous acidEsters auxiliary is anti-
Oxygen agent, specifically can from TBHQ, four [β-(3,5- di-tert-butyl-hydroxy phenyls)Propionic acid] pentaerythrite
Ester, β-(3,5- di-tert-butyl-hydroxy phenyls)The positive octadecanol ester of propionic acid, Wytox 312 or diphosphites
One or more in the different certain herbaceous plants with big flowers ester of pentaerythrite two.
The preparation method of the above-mentioned polyfunctional acrylic ester containing carboxy-modified polycyclic amine structure, specifically includes following steps:
Catalyst is added into the polyfunctional acrylic ester, is added dropwise under the conditions of 20~80 DEG C described containing carboxy-modified polycyclic amines, perseverance
Temperature 3~12h of reaction, produces product.
Preferably, the mol ratio containing carboxy-modified polycyclic amines and the polyfunctional acrylic ester is 1:1~1:2.
Compared with prior art, the present invention has the advantages that:
(1)The present invention by adjust carbonic ester and alicyclic diamine with when synthesis condition, products therefrom has a variety of
Structure, now can be modified intermediate containing carboxy-modified polycyclic amines as a kind of wider reactive amines of applicability, by its with it is multifunctional
Acrylate monomer is after Michael addition reaction, and the resulting polyfunctional acrylate monomer of polycyclic amines containing carbonyl is used as one
Plant reactive amines and overcome big regular activated amine smell, easy xanthochromia, the deficiency for easily occurring amine migration;
(2)The present invention will contain carboxy-modified polycyclic amines and apply(It is branched)When in polyether acrylate, one kind one has been synthesized
Plant with the low viscosity resin for helping initiation group, there should be the low viscosity resin for helping initiation group that there is higher solidification rate,
Less cure shrinkage, more excellent hardness and resistance to elevated temperatures, are added while overcoming into resin of the prior art
Amine migration and the serious deficiency of xanthochromia greatly, easily occur for the smell brought after reactive amines;
(3)The present invention contains carboxy-modified polycyclic amines, technique letter using alicyclic diamine as raw material through carbonate-modified formed
Single, raw material is cheap and easy to get.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Unless stated otherwise, material involved in embodiment, method are material commonly used in the art and method.
A kind of ring polyamines 1 containing carbonyl two of synthesis example 1
177.2g diethyl carbonates and 258.4g are added in the three-necked flask equipped with rectifier unit, thermometer and agitator
Piperazine anhydrous;After stirring, 80 DEG C are gradually heating to, isothermal reaction 6h, rectifying mouthful temperature control is treated at 60~70 DEG C or so
Substantially after being separated without rectifying liquid, 90~100 DEG C of vacuum distillations is warming up to and remove low-boiling by-products and impurity, obtain clear, colorless production
Thing 350.2g(Actual recovery 95.5%).
A kind of polycyclic oligomeric polyamines 2 containing carbonyl of synthesis example 2
162.0g dimethyl carbonates and 194.6g are added in the three-necked flask equipped with rectifier unit, thermometer and agitator
Piperazine anhydrous;After stirring, be gradually heating to 80 DEG C, isothermal reaction 12h, rectifying mouthful temperature control at 60~70 DEG C or so,
After being separated substantially without rectifying liquid, it is warming up to 90~100 DEG C of vacuum distillations and removes low-boiling by-products and impurity, obtain clear, colorless
Product 290.2g(Actual recovery 95.9%).
A kind of ring polyamines 3 containing carbonyl two of synthesis example 3
97.0g ethylene carbonates and 374.7g are added in the three-necked flask equipped with rectifier unit, thermometer and agitator
IPD;After stirring, 80 DEG C of reaction 6h are gradually heating to, rectifying mouthful temperature control is treated at 60~70 DEG C or so
Substantially after being separated without rectifying liquid, 90~100 DEG C of vacuum distillations is warming up to and remove low-boiling by-products and impurity, obtain clear, colorless production
Thing 385.2g(Actual recovery 95.5%).
The polyether acrylate 1 of synthesis example 4(Mn ≈ 1162, degree of functionality is 3)
A kind of polyethers triacrylate and preparation method thereof, including following two steps:
A. ester exchange reaction:Take 400g polyether-tribasic alcohols (Mn ≈ 1000, VOANOL CP-1055), 384.4g acrylic acid first
Ester, 3.2g Wytox 312s, 0.4g MEHQs, after being uniformly dispersed, add 6g solidification enzyme LVK-F100 and
0.1g lanthanum methanesulfonates, the stirring reaction 24h at 40 DEG C;
A. purification process:After mixture filtering obtained by upper step, filtrate carries out vacuum rotary steam, eliminates the methanol of reaction generation
With excessive methyl acrylate, clear, colorless carboxylate 463.0g is obtained(Solid content 99.5%, 105mPas/25 DEG C of viscosity, ester
Rate is 97.1%).
The branch polyether acrylate 2 of synthesis example 5(Mn ≈ 1022, degree of functionality is 9)
A kind of branch polyether acrylate and preparation method thereof, is comprised the following steps that:
(1)The synthesis of branch polyether polyatomic alcohol
Using glycerine as raw material, in acid condition, it is condensed to form branch polyether polyatomic alcohol through a step(Mn ≈ 536, degree of functionality
For 9, the degree of branching is 0.72);
(2)Enzymatic ester exchange reaction, including following two steps:
A. ester exchange reaction:Take above-mentioned branch polyether polyatomic alcohol 300g, 550.0g methyl acrylate, the nonyl of 1.8g phosphorous acid three
Base phenylester, 0.25g MEHQs, after being uniformly dispersed, add 8g solidification enzymes Novozyme 435 and 0.1g dodecyls
Sulfonic acid lanthanum, the stirring reaction 24h at 50 DEG C;Chemical equation is as follows
B. purification process:After mixture filtering obtained by upper step, filtrate carries out vacuum rotary steam, eliminates the methanol of reaction generation
With excessive methyl acrylate, clear, colorless carboxylate 553.0g is obtained(Solid content 99.3%, 65mPas/25 DEG C of viscosity, ester
Rate is 96.7%).
A kind of ring modified polyamine TMPTA monomers 1 containing carbonyl two of embodiment 1
Take the commercially available TMPTA monomers of 59.3g (0.2mol) to be placed in there-necked flask, add 0.16g DBU catalyst, gradually heat up
To 60 DEG C;Start that the ring polyamines 1 containing carbonyl two that 19.8g (0.1mol) synthesis example 1 is prepared is added dropwise under stirring, dripped in 1h
Add entirely, continue isothermal reaction 6h, cooling discharging obtains colourless transparent liquid 75.6g(Solid content is 99.3%, and viscosity is
100mPa·s/25℃).
A kind of ring modified polyamine polyether acrylate 2 containing carbonyl two of embodiment 2
232.4g (0.2mol) synthesis example 4 is taken to synthesize obtained polyether acrylate 1(Mn ≈ 1162, degree of functionality is 3),
It is placed in there-necked flask, adds 0.4g DBU catalyst, be gradually heating to 60 DEG C;Start to be added dropwise 0.1mol under stirring by synthesis example 2
The ring polyamines 2 containing carbonyl two prepared, is added dropwise completely in 1h, continues isothermal reaction 6h, cooling discharging obtains water white transparency liquid
Body 235.1g(Solid content is 99.5%, and viscosity is 120 mPas/25 DEG C).
A kind of ring modified polyamine branch polyether acrylate 3 containing carbonyl two of embodiment 3
The branch polyether acrylate 2 for taking 102.2g (0.1mol) synthesis example 5 to prepare(Mn ≈ 1022, degree of functionality is
9)Add in there-necked flask, add 0.3g DBU catalyst, be gradually heating to 60 DEG C;Start to be added dropwise 0.1mol under stirring by synthesis example
The 3 ring polyamines 3 containing carbonyl two prepared, are added dropwise completely in 1h, continue isothermal reaction 6h, cooling discharging obtains water white transparency
Liquid 121.1g(Solid content is 99.4%, and viscosity is 80mPas/25 DEG C).
A kind of urethane-modified TMPTA monomers containing single ring architecture of comparative example 1
(1)A kind of synthesis of the carbamate containing single ring architecture
177.2g diethyl carbonates and 129.2g are added in the three-necked flask equipped with rectifier unit, thermometer and agitator
Piperazine anhydrous;After stirring, 80 DEG C are gradually heating to, isothermal reaction 3h, rectifying mouthful temperature control is treated at 60~70 DEG C or so
Substantially after being separated without rectifying liquid, 90~100 DEG C of vacuum distillations is warming up to and remove low-boiling by-products and impurity, obtain clear, colorless production
Thing 233.8g(Actual recovery 98.5%).
(2)The synthesis of urethane-modified TMPTA monomers containing single ring architecture
Take the commercially available TMPTA monomers of 59.3g (0.2mol) to be placed in there-necked flask, add 0.16g DBU catalyst, gradually heat up
To 60 DEG C;Start that 0.2mol steps are added dropwise under stirring(1)The carbamate containing single ring architecture prepared, drips in 1h
Add entirely, continue isothermal reaction 6h, cooling discharging obtains colourless transparent liquid 90.4g(Solid content is 99.5%, and viscosity is 95
mPa·s/25℃).
A kind of urethane-modified branch polyether acrylate containing single ring architecture of comparative example 2
(1)The synthesis of carbamate containing single ring architecture
Synthetic method is with comparative example 1(1);
(2)The synthesis of urethane-modified branch polyether acrylate containing single ring architecture
The branch polyether acrylate 2 for taking 102.2g (0.1mol) synthesis example 5 to prepare(Mn ≈ 1022, degree of functionality is
9)Add in there-necked flask, add 0.3g DBU catalyst, be gradually heating to 60 DEG C;Start that 0.1mol steps are added dropwise under stirring(1)
The carbamate containing single ring architecture prepared, is added dropwise completely in 1h, continues isothermal reaction 6h, cooling discharging obtains nothing
The g of color transparency liquid 116.6(Solid content is 98.8 %, and viscosity is 90 mPas/25 DEG C).
The synthesis of embodiment 1 is obtained respectively synthesizes what is obtained containing the ring modified polyamine TMPTA monomers of carbonyl two, comparative example 1
Urethane-modified TMPTA monomers containing single ring architecture are added in photocurable formulation as additive, then to photocuring
The performance such as the viscosity of formula and the xanthochromia of shaped article, cure shrinkage, solidification rate and hardness is tested, test knot
Fruit is as shown in table 1:
Table 1:Partial properties are contrasted
Note:Solidification rate test condition:1173,25 μm of wet films of addition 3%, 200mJ/ cm2;So that linear speed is fully cured
Degree(Unit:m/s)Solidification rate is represented, linear velocity is more big, illustrates that solidification rate is faster.
Embodiment 1 in table 1 is a kind of ring modified polyamine TMPTA monomers containing carbonyl two, and it can be used as a kind of reactive amines
Aided initiating, it is inhibited from yellowing when being used in photocurable formulation, be not susceptible to amine migration, it is tasteless, overcome conventional reactive amines
Deficiency, in addition, the shaped article prepared using it as the photocuring system of reactive amines aided initiating have higher solidification
Speed, less cure shrinkage and more excellent hardness, have broad application prospects;By contrast, comparative example 1 is through surveying
Examination, urethane-modified TMPTAs containing single ring architecture of the TMPTA through being obtained after urethane-modified containing single ring architecture
Although viscosity is smaller, its solidification rate is not high, and has that shrinkage factor is larger and deficiency of slight xanthochromia;As can be seen here,
Polycyclic amines containing carbonyl are much more desirable as the modification intermediate of active amine monomer.
It is 2-in-1 to embodiment into the obtained ring modified polyamine containing carbonyl two respectively(It is branched)Polyether acrylate and comparative example
2-in-1 viscosity and the xanthochromia of shaped article into the obtained urethane-modified branch polyether acrylate containing single ring architecture
The performance such as property, cure shrinkage, solidification rate and hardness is tested, and with branch polyether acrylate 2 and commercially available reactive amines
The scheme as a comparison case 3 that CN371 coordinates, test result is as shown in table 2:
Table 2:Partial properties are contrasted
Note:Solidification rate test condition:1173,25 μm of wet films of addition 3%, 200mJ/ cm2;So that linear speed is fully cured
Degree(Unit:m/s)Solidification rate is represented, linear velocity is more big, illustrates that solidification rate is faster.
Embodiment 2 and 3 is to form one kind after being reacted containing carboxy-modified polycyclic amines and branch polyether acrylate
With the resin for helping the low viscosity for triggering group, comparative example 2 is the urethane-modified branch polyether propylene containing single ring architecture
The product that acid esters is obtained, comparative example 3 is the scheme that branch polyether acrylate 2 and commercially available reactive amines CN371 coordinate, with existing skill
Reactive amines are added in resin in art is compared(I.e. compared with comparative example 3), contain carbonyl in embodiments of the invention 2 and 3
Modified polycyclic amines branch polyether acrylate itself, which possesses, helps initiation group, and described containing carboxy-modified polycyclic amines branch polyether
Acrylate is not susceptible to xanthochromia, overcomes the deficiency of the regular activated easy xanthochromia of amine aided initiating;In addition, described containing carboxy-modified
Polycyclic amines branch polyether acrylate possesses the low characteristic of viscosity, can as a kind of low viscosity resin in photocurable formulation it is a large amount of
Use;And the shaped article prepared using it as photocuring raw material also has higher solidification rate, less solidification is received
Shrinkage, and more excellent hardness have greatly widened its application;By contrast, comparative example 2 after tested, branch polyether propylene
Though the solidification rate of acid esters is higher, still suffer from that shrinkage factor is larger, the deficiency of slight xanthochromia.As can be seen here, polycyclic amines containing carbonyl
More suitably acrylate is modified.
Claims (6)
1. a kind of polycyclic amines containing carbonyl are modified polyfunctional acrylic ester, it is characterised in that the polycyclic amines containing carbonyl are modified many officials
Can acrylate by containing carboxy-modified polycyclic amines and polyfunctional acrylic ester through Michael addition reaction, in polyfunctional acrylic ester
Partial double bond in introduce polycyclic tertiary amine structure, the polyfunctional acrylic ester is polyfunctional acrylate monomer, polyethers propylene
Acid esters or branch polyether acrylate;The polyfunctional acrylate monomer is the hexylene glycol of diacrylate -1,6 ester, trihydroxy methyl
One or more in propane triacrylate, tri (propylene glycol) diacrylate, pentaerythritol triacrylate;It is described poly-
Ether acrylate carries out ester exchange reaction by PPG and methacrylate and obtained;The branch polyether acrylate by
Branch polyether polyatomic alcohol carries out ester exchange reaction with methacrylate and obtained;The PPG or branch polyether polyatomic alcohol
Degree of functionality be 3~12, relative molecular mass be 400~5000;
Described is to have at least two rings through what ammonolysis reaction was formed with carbonic ester and alicyclic diamine containing carboxy-modified polycyclic amines
The polycyclic amines of structure;Wherein, the alicyclic diamine refers to piperazine, IPD, Isosorbide-5-Nitrae-hexamethylene diamine, 1- methyl -2,4-
One or more in cyclohexanediamine and N, N'- dimethyl -1,2- cyclohexanediamine;The carbonic ester is dimethyl carbonate, carbonic acid
One or more in diethylester, methyl ethyl carbonate, dipropyl carbonate, dibutyl carbonate, ethylene carbonate and propene carbonate.
2. polycyclic amines containing carbonyl are modified polyfunctional acrylic ester according to claim 1, it is characterised in that described to change containing carbonyl
It by the carbonic ester and alicyclic diamine is 1 in molar ratio that the preparation method of property polycyclic amines, which is,:1~2 ratio is in 60~120 DEG C
Under the conditions of react 3~12h, vacuum distillation remove accessory substance and excess reactant produce.
3. polycyclic amines containing carbonyl are modified polyfunctional acrylic ester according to claim 1, it is characterised in that the ester exchange is anti-
It should be carried out under conditions of solidification enzyme and efficient accelerator, the solidification enzyme is esterase E.C.3.1.1.1, lipase
One or more in E.C.3.1.1.3 or protease E.C.3.4.-.-;The efficient accelerator is lanthanide rare sulfonate.
4. polycyclic amines containing carbonyl are modified polyfunctional acrylic ester according to claim 1, it is characterised in that the polyethers propylene
The preparation method of acid esters or branch polyether acrylate includes ester exchange reaction and the big step of purification process two, specific as follows:
S1:Ester exchange reaction:By PPG or branch polyether polyatomic alcohol, excessive methacrylate, antioxidant and
Polymerization inhibitor carries out ester exchange reaction under the conditions of 30~80 DEG C after being uniformly dispersed, 3~48h of sustained response obtains product standby;
S2:Purification process:Step S1 products therefroms are filtered, methanol or ethanol and the mistake that reaction is generated is distilled off in filtrate decompression
The polyfunctional acrylic ester of amount, produces final product.
5. polycyclic amines containing carbonyl described in Claims 1 to 4 any claim are modified the preparation method of polyfunctional acrylic ester, its
It is characterised by, DUB catalyst is added into the polyfunctional acrylic ester, changes under the conditions of 20~80 DEG C described in dropwise addition containing carbonyl
Property polycyclic amines, 3~12h of isothermal reaction produces product.
6. preparing the multifunctional acrylic acid of the modification of polycyclic amines containing carbonyl containing carboxy-modified polycyclic amines described in Claims 1 to 4 is any
Application in ester.
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