CN112300306A - Biodegradable radiation-curable (methyl) acrylate and preparation method thereof - Google Patents
Biodegradable radiation-curable (methyl) acrylate and preparation method thereof Download PDFInfo
- Publication number
- CN112300306A CN112300306A CN202011240223.7A CN202011240223A CN112300306A CN 112300306 A CN112300306 A CN 112300306A CN 202011240223 A CN202011240223 A CN 202011240223A CN 112300306 A CN112300306 A CN 112300306A
- Authority
- CN
- China
- Prior art keywords
- xylitol
- reaction
- methyl
- acid
- polyester polyether
- 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.)
- Granted
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title description 9
- -1 xylitol acetal Chemical class 0.000 claims abstract description 89
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims abstract description 67
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000000811 xylitol Substances 0.000 claims abstract description 65
- 235000010447 xylitol Nutrition 0.000 claims abstract description 65
- 229960002675 xylitol Drugs 0.000 claims abstract description 65
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims abstract description 54
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 41
- 229920000570 polyether Polymers 0.000 claims abstract description 41
- 229920000728 polyester Polymers 0.000 claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 9
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims abstract description 8
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000004185 ester group Chemical group 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 72
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 58
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 22
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 20
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 18
- 229920005862 polyol Polymers 0.000 claims description 18
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 17
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 12
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- CWZPGMMKDANPKU-UHFFFAOYSA-L butyl-di(dodecanoyloxy)tin Chemical compound CCCC[Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O CWZPGMMKDANPKU-UHFFFAOYSA-L 0.000 claims description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 9
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 8
- 238000005886 esterification reaction Methods 0.000 claims description 8
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 8
- 150000005846 sugar alcohols Polymers 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- PRMVSMUXJRDBJF-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O.CCCCOC(C)=O PRMVSMUXJRDBJF-UHFFFAOYSA-N 0.000 claims description 6
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 6
- 230000032050 esterification Effects 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000006011 modification reaction Methods 0.000 claims description 6
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims description 6
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 6
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 4
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 4
- RJUIDDKTATZJFE-UHFFFAOYSA-N but-2-enoyl chloride Chemical compound CC=CC(Cl)=O RJUIDDKTATZJFE-UHFFFAOYSA-N 0.000 claims description 4
- 150000002118 epoxides Chemical group 0.000 claims description 4
- 150000002148 esters Chemical group 0.000 claims description 4
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical group C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 4
- 239000003377 acid catalyst Substances 0.000 claims description 3
- XKXHCNPAFAXVRZ-UHFFFAOYSA-N benzylazanium;chloride Chemical compound [Cl-].[NH3+]CC1=CC=CC=C1 XKXHCNPAFAXVRZ-UHFFFAOYSA-N 0.000 claims description 3
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- QJFMCHRSDOLMHA-UHFFFAOYSA-N phenylmethanamine;hydrobromide Chemical compound Br.NCC1=CC=CC=C1 QJFMCHRSDOLMHA-UHFFFAOYSA-N 0.000 claims description 3
- 150000001263 acyl chlorides Chemical class 0.000 claims description 2
- 239000012024 dehydrating agents Substances 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 125000003700 epoxy group Chemical group 0.000 abstract 1
- 239000000047 product Substances 0.000 description 32
- 239000000463 material Substances 0.000 description 28
- 238000010992 reflux Methods 0.000 description 22
- 238000002474 experimental method Methods 0.000 description 20
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 238000001723 curing Methods 0.000 description 12
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 10
- 239000003973 paint Substances 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000005457 ice water Substances 0.000 description 8
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 6
- 230000002035 prolonged effect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 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 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 238000003847 radiation curing Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241000609240 Ambelania acida Species 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000010905 bagasse Substances 0.000 description 2
- WIMGUTMJIVMCMY-UHFFFAOYSA-N benzaldehyde;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.O=CC1=CC=CC=C1 WIMGUTMJIVMCMY-UHFFFAOYSA-N 0.000 description 2
- 229920013724 bio-based polymer Polymers 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- HEBKCHPVOIAQTA-NGQZWQHPSA-N d-xylitol Chemical compound OC[C@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-NGQZWQHPSA-N 0.000 description 2
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 238000002372 labelling Methods 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 2
- 239000002953 phosphate buffered saline Substances 0.000 description 2
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- 229920005989 resin Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 244000274847 Betula papyrifera Species 0.000 description 1
- 235000009113 Betula papyrifera Nutrition 0.000 description 1
- 235000009109 Betula pendula Nutrition 0.000 description 1
- 235000010928 Betula populifolia Nutrition 0.000 description 1
- 235000002992 Betula pubescens Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 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
- 229920000229 biodegradable polyester Polymers 0.000 description 1
- 239000004622 biodegradable polyester Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000003599 food sweetener Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- LJJFYAPFNPSEFD-UHFFFAOYSA-N hexane-1,6-diol;2-(2-hydroxypropoxy)propan-1-ol Chemical compound OCCCCCCO.CC(O)COC(C)CO LJJFYAPFNPSEFD-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000021096 natural sweeteners Nutrition 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000003765 sweetening agent Substances 0.000 description 1
- 210000003813 thumb Anatomy 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F22/10—Esters
- C08F22/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
Abstract
The invention discloses biodegradable radiation-curable (methyl) acrylate, which has a structural formula as follows:
Description
Technical Field
The invention relates to biodegradable radiation-curable (methyl) acrylate and a preparation method thereof, belonging to the field of bio-based modified biodegradable photocuring materials.
Background
The photocuring technology has the advantages of rapid curing, energy and time saving, low solvent release, low curing temperature, small equipment volume, low investment and the like, and the application field of the photocuring technology is developed from the initial wood coating to a plurality of industrial production fields such as plastic decoration, metal part coating, medical instruments, electronic components, information recording media, photosensitive printing, plastic materials, optical fibers and the like, and the photocuring technology mainly appears in the forms of UV coatings, UV printing inks, UV adhesives and the like.
The ultraviolet curing material consists of a photosensitive prepolymer (oligomer), an active dilution monomer, a photoinitiator and various addition additives (pigment, filler, defoaming agent and the like). The prepolymer is a base resin of an ultraviolet curing system and occupies a large proportion in the whole system. The reactive diluent is used to dilute the prepolymer to achieve the desired viscosity of the resin system. The prepolymer and reactive diluent monomer together generally account for more than 90% of the total curing system mass, with the reactive diluent monomer accounting for 40-60%. They play a decisive role in the properties of the overall system, such as hardness, adhesion, flexibility, durability, abrasion resistance, tensile strength, impact resistance, and aging resistance.
Due to the gradual decrease of petroleum resources, the renewable resources are used as raw materials to prepare the bio-based polymer material, so that the sustainable development of the polymer material is promoted, and the bio-based polymer material is widely concerned in academia and industry. The bio-based materials are one of the hot spots of new materials in the world at present, according to the Research report issued by Occams Research, the global yield of bio-based chemicals and high molecular materials is about 5000 ten thousand tons at present, and the yield value can reach 100-. In developed countries, in order to promote the development and use of the bio-based material industry in this country, a series of relevant laws and regulations are developed, such as the plan of preferential procurement of bio-based products in the united states, the plan of the seventh development framework of the european union (FP7), the plan of the bio-based material 2020 in japan, and the plan of sustainable packaging in australia. In particular to a European bio-based product technology open platform which is composed of a seventh development framework plan (FP7) of the European Union leading from the Netherlands, England, Germany, France, Italy and the like and a united scientific and technological field of industrial bio-based product enterprises. The technology platform studies specific standards of any link of the whole bio-based product value chain, from production standards, industrial standards, commercial standards and regulatory standards to detection methods and product labeling. Especially, a whole set of European Union bio-based product labeling system is established to stimulate and expand market consumption. Biobased materials are one of the strategic emerging industries of China. China's biobased materials develop rapidly in recent years, keep about 20% of annual growth rate, the total yield has reached 600 ten thousand tons/year, the yield is expected to double in 2020.
Xylitol is originally produced in Finland, is a natural sweetener extracted from plant raw materials such as white birch, oak, corncob, bagasse and the like, has a wide distribution range in nature, is widely present in various fruits, vegetables and grains, but has a low content. The commercial xylitol is prepared by deep processing agricultural crops such as corncobs, bagasse and the like, and is a natural and healthy sweetener. Xylitol is used as a cheap and easily-obtained renewable material, can be absorbed by human metabolism, is approved by the Food and Drug Administration (FDA), has better biocompatibility, meets the requirements of sustainable development and can reduce the consumption of petrochemical resources if the xylitol can be applied to the preparation of a high polymer material for sustainable development.
Disclosure of Invention
The invention provides a biodegradable radiation-curable (meth) acrylate and a preparation method thereof, the biodegradable radiation-curable (meth) acrylate is prepared from a xylitol acetal component, a polyester polyether modified component and a (meth) acrylated compound, is remarkably improved in hardness, flexibility, oxidation resistance, adhesion and the like, has biocompatibility and biodegradability, and is environment-friendly; meanwhile, the utilization of the biological resource xylitol is widened, and the consumption of petrochemical resources is reduced.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a biodegradable radiation curable (meth) acrylate having the formula:
The compound is mainly suitable for radiation curing coatings, such as radiation curing printing ink, radiation curing adhesive and the like.
The adhesion of the above compounds to plastics (PVC, ABS, PE, PP, PC, etc.) is particularly outstanding.
Herein, (meth) acrylate refers to acrylate or methacrylate, and is similarly expressed elsewhere, with similar meaning, e.g. (poly) caprolactone refers to caprolactone or polycaprolactone.
The biodegradable radiation-curable (meth) acrylate is prepared from a xylitol acetal component, a polyester polyether modified component, and a (meth) acrylating compound.
The xylitol acetal component is xylitol formal and acetal derivatives thereof, and the hydroxyl functionality is 2.5-3.5; preferably, xylitol formal, xylitol benzaldehyde, and most preferably xylitol formal. Therefore, the hardness, flexibility and adhesive force of the product can be better improved.
The polyester-polyether modifying component comprises at least one of (poly) caprolactone, (poly) lactide, (poly) glycolide, a compound providing an epoxide group, or a unit providing an alkylene oxide residue having 2 to 3 carbon atoms.
The (meth) acrylating compound is: at least one of an unsaturated acid, an unsaturated acid halide, an epoxy compound having a terminal (meth) acryloyl group, an unsaturated acid having a (meth) acryloyl group, or an alkyl ester of an unsaturated acid. Such as: (meth) acrylic acid, acyl chloride/bromine/iodine (meth) acrylate, methyl/ethyl/(n/i) propyl methacrylate, glycidyl (meth) acrylate. More preferably: a (meth) acrylic acid chloride, (meth) acrylic acid, methyl (meth) acrylate, or a terminal (meth) acryloyl epoxy compound.
The preparation of the biodegradable radiation curable (meth) acrylate comprises the following steps connected in sequence:
a. reacting xylitol with aldehyde compounds with reactive carbonyl under the action of an acid catalyst, azeotropically removing water generated by the reaction by using a solvent with water, and preparing a xylitol acetal component containing polyhydroxy and substituent groups; the aldehyde compound with the reactive carbonyl group is formaldehyde, or linear or branched alkyl aldehyde containing C1-C10, or phenyl aldehyde containing C1-C4 branches, preferably formaldehyde, benzaldehyde or phenylacetaldehyde, and most preferably formaldehyde;
b. carrying out modification reaction on the xylitol acetal component and the polyester polyether modified component under the action of a catalyst to obtain polyester polyether modified xylitol acetal polyol;
c. the method is carried out according to any one of the following modes c1-c 4:
c1. polyester polyether modified xylitol acetal polyalcohol reacts with (methyl) acrylic acid acyl chloride to prepare biodegradable radiation-curable (methyl) acrylate, and other solvents are not required to be added in the reaction process;
c2. the polyester polyether modified xylitol acetal polyol and (methyl) acrylic acid are subjected to esterification reaction under the action of an esterification catalyst, a polymerization inhibitor and a dehydrating agent to generate the polyester polyether modified xylitol acetal polyol.
c3. And carrying out ester exchange reaction on the polyester polyether modified xylitol acetal polyol and methyl (meth) acrylate under the action of an esterification catalyst and a polymerization inhibitor to generate the polyester polyether modified xylitol acetal polyol.
c4. And (3) carrying out ester exchange reaction on the polyester polyether modified xylitol acetal polyol and an epoxy compound with a terminal (methyl) acryloyl group under the action of a catalyst to generate the polyester polyether modified xylitol acetal polyol.
The preparation method is simple and easy to control, and the obtained product has high purity and good comprehensive performance.
The applicant finds that the xylitol acetal with the specific structure is combined with the polyester polyether with the specific structure to modify (methyl) acrylate, so that the oxidation resistance, hardness, flexibility and adhesive force of the material are improved remarkably; because xylitol can be absorbed by human metabolism and is approved by the Food and Drug Administration (FDA), the xylitol has better biocompatibility, can be applied to food packaging coatings and coatings or adhesives of medical device materials, and greatly expands the application field of the obtained materials; and the xylitol acetal and the biodegradable polyester polyether are combined for modification, so that the mechanical property and the oxidation resistance of the material are remarkably improved, the adhesion force of the material on a used base material is improved through the hydrophilicity of the polyester polyether, and the material has the biodegradability, so that the applicant provides the application.
In order to promote the complete reaction of the materials and ensure the performance of the modified product, in the step a, the reaction temperature is 40-100 ℃, and the reaction time is 6-16 h; the molar ratio of the xylitol, the aldehyde and the acid catalyst is (100-;
in order to improve the reaction rate and reduce side reactions, in step a, the acidic catalyst is one or a mixture of more than two of sulfuric acid, sulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid in any proportion, preferably methanesulfonic acid, and the molar amount of the acidic catalyst is 1-6% of the molar amount of xylitol.
The above-mentioned selection of solvent with water not only can disperse material, but also can azeotropically remove water produced by reaction. In order to improve the reaction efficiency, in the step a, the water-carrying solvent is one or a mixture of more than two of methanol, ethanol, benzene, toluene, C5 alkane or C6 alkane in any proportion, and the mass amount of the water-carrying solvent is 10-40% of the mass sum of the xylitol and the aldehyde compound with carbonyl.
To facilitate the reaction, step b is reacted in cyclohexane, heptane or toluene;
in order to improve the reaction rate and reduce side reactions, in the step b, the catalyst is one or a mixture of more than two of butyltin dilaurate, tetrabutyl titanate, tetraisopropyl titanate, stannous octoate, dibutyl diacetate, zinc naphthenate, cobalt naphthenate and bismuth naphthenate in any proportion.
In the step b, the reaction temperature is 70-120 ℃, and the reaction time is 2-6 hours, so that the full reaction of the reaction can be ensured, and the comprehensive performance of the obtained material can be ensured.
In order to ensure the smooth and smooth reaction and the yield and performance of the product, step c1 is: slowly (30-60 drops/min) dripping (methyl) acryloyl chloride into the polyester polyether modified xylitol acetal polyalcohol, reacting for 1-3 hours at room temperature after finishing dripping, and separating to obtain biodegradable radiation-curable (methyl) acrylate; wherein the molar consumption of the (methyl) acryloyl chloride is 1 to 1.3 times of the molar number of the polyester polyether modified xylitol acetal polyalcohol.
In order to improve the reaction efficiency, in the reaction of step c1, a low-boiling-point amine alkaline substance is added to neutralize hydrochloric acid generated after the acid chloride reacts, so as to help to accelerate the reaction, wherein the low-boiling-point amine alkaline substance is one or a mixture of more than two of methylamine, ethylamine, diethylamine or triethylamine in any proportion, and the molar amount of the low-boiling-point amine alkaline substance is 1-1.3 times of the molar amount of the polyester polyether modified xylitol acetal polyol.
In order to improve the reaction efficiency and the purity of the product, in the steps c2 and c3, the esterification catalyst is one or a mixture of more than two of sulfuric acid, sulfonic acid, methanesulfonic acid, ethylsulfonic acid, benzenesulfonic acid or p-toluenesulfonic acid in any ratio.
In order to ensure the sufficiency of the reaction and the excellence of the comprehensive performance of the product, in the steps c2 and c3, the reaction temperature is 70-110 ℃, the reaction time is 6-14h, and after the reaction is finished, the polyester polyether modified xylitol acetal polyol is generated through water washing, neutralization and desolventizing; wherein the molar amount of the (methyl) acrylic acid or the methyl (meth) acrylate is 2.4 to 4 times of the molar number of the polyester polyether modified xylitol acetal polyalcohol.
In order to further improve the adhesion of the product, in step c4, the epoxy compound with terminal (meth) acryloyl groups is a mixture of glycidyl acrylate and glycidyl methacrylate in any ratio; the catalyst is one or a mixture of more than two of triethylamine, benzyl ammonium chloride, benzyl ammonium bromide or triphenylphosphine in any proportion.
The prior art is referred to in the art for techniques not mentioned in the present invention.
The biodegradable radiation-curable (meth) acrylate is prepared from a xylitol acetal component, a polyester polyether modified component and a (meth) acrylated compound, is remarkably improved in hardness, flexibility, oxygen resistance, adhesion and the like, is biodegradable, and is environment-friendly; meanwhile, the utilization of the biological resource xylitol is widened, and the consumption of petrochemical resources is reduced.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
In the examples, "room temperature" and "ambient temperature" are 25 ℃; the yield is as follows: the percentage of the mass of the product actually produced to the mass produced according to the xylitol theory.
Example 1
(1) Preparing xylitol formal:
to a 500mL four-necked flask equipped with a mechanical stirrer and thermometer was added D-xylitol (152g,1mol), 35% formaldehyde (103g,1.2mol), 70% methanesulfonic acid (18.2g, 1.9mmol), methanol (76.5g) at room temperature; the reaction reflux temperature is 60-70 ℃, methanol and calcium chloride are added into a reflux pipe to react for 8 hours, after the reaction is basically finished, redundant formaldehyde and methanol are removed through reduced pressure distillation, 40g of n-heptane is added, the mixture is stirred for 2 hours and then is subjected to suction filtration, a filter cake is washed for 2 times by 20ml of hot cyclohexane to obtain a xylitol acetal component M1, 134.6g of xylitol acetal is obtained through drying, and the yield is 82%. About 2500g of the crude product was prepared according to the above methodThe right xylitol acetal component M1 was used for the experiment. Separating the obtained product with silica gel chromatographic column, and separating the final product1H-NMR nuclear magnetic analysis is carried out,1H-NMR is measured by a Bruker AV400 NMR nuclear magnetic resonance instrument, TMS is used as an internal standard reference,1H NMR (400MHz,CDCl3) δ 4.75(d,1H),4.65(d,1H),3.96(m,2H),3.79(m,2H),3.54(m,2H),3.39 (m,1H),2.0(s, 3H); hydrogen nuclear magnetic resonance (1H NMR) spectroscopy gave the product of formula I:
example 2
(2) Preparing xylitol benzaldehyde:
to a 500mL four-necked flask equipped with a mechanical stirrer and thermometer was added D-xylitol (152g,1mol), benzaldehyde (117g,1.1mol), 70% methanesulfonic acid (19.2g, 2mmol), and methanol (80.7g) at room temperature; the reaction reflux temperature is 60-70 ℃, and methanol and calcium chloride are added into a reflux pipe. And (3) reacting for 8h, after the reaction is basically finished, distilling under reduced pressure to remove redundant methanol, adding 40g of water, stirring for 2h, carrying out suction filtration, washing a filter cake for 2 times by using 20ml of hot cyclohexane to obtain a xylitol acetal component M2, and drying to obtain 171.1g, wherein the yield is 71%. About 2500g of xylitol acetal component M2 was prepared according to the above method and used for experiments. Separating the obtained product with silica gel chromatographic column, and separating the final product1H-NMR nuclear magnetic analysis is carried out,1H-NMR is measured by a Bruker AV400 NMR nuclear magnetic resonance instrument, TMS is used as an internal standard reference,1H NMR(400MHz, CDCl3) δ 7.18-7.20(m,5H),5.98(s,1H),3.96(m,2H),3.79(m,2H),3.54(m,2H),3.39(m, 1H),2.0(s, 3H); hydrogen nuclear magnetic resonance (1H NMR) spectroscopy gave the product of formula ii:
experiments prove that the reaction can be catalyzed by adopting hydrochloric acid, phosphoric acid, sulfuric acid and p-toluenesulfonic acid to replace methanesulfonic acid in the embodiment.
Example 3
Caprolactone modified xylitol formal:
xylitol formal M1(82g, 0.5mol), 6-caprolactone (171g, 1.5mol), toluene (50g), butyltin dilaurate (2g) were added to a 500mL four-necked flask (reflux condenser) equipped with a mechanical stirrer and thermometer at room temperature, heated to 105 deg.C, and kept under micro reflux for 5 hours, and the reaction was substantially completed to obtain a caprolactone-modified xylitol acetal backbone (R2 n-A-R2' n (R2 "n) abbreviated as intermediate M1A2), and the toluene solvent was removed under reduced pressure and used in the next reaction.
Experiments prove that tetrabutyl titanate, tetraisopropyl titanate, stannous octoate, dibutyl diacetate, zinc naphthenate, cobalt naphthenate or bismuth naphthenate are adopted to replace butyltin dilaurate in the embodiment, and the reaction can also be catalyzed; the solvent can also be cyclohexane or heptane instead of toluene in the embodiment, and when cyclohexane is adopted as the solvent, the reflux temperature is changed to 88 ℃, and the time is prolonged to 6 hours.
Example 4
Caprolactone modified xylitol benzaldehyde:
xylitol benzaldehydes M2(120g, 0.5mol), 6-caprolactone (171g, 1.5mol), toluene (54g), butyltin dilaurate (2.16g) were added to a 500mL four-necked flask (reflux condenser) equipped with a mechanical stirrer and thermometer at room temperature, the reaction was substantially complete by heating to 105 ℃ and maintaining under micro-reflux for 5 hours, to thereby obtain caprolactone-modified xylitol benzaldehydes backbone (R2 n-A-R2' n (R2 "n) abbreviated as intermediate M2A2), and the toluene solvent was removed under reduced pressure and used in the next reaction.
Experiments prove that tetrabutyl titanate, tetraisopropyl titanate, stannous octoate, dibutyl diacetate, zinc naphthenate, cobalt naphthenate or bismuth naphthenate are adopted to replace butyltin dilaurate in the embodiment, and the reaction can also be catalyzed; cyclohexane or heptane can be used as the solvent instead of toluene in the embodiment, and when cyclohexane is used as the solvent, the reflux temperature is changed to 88 ℃, and the time is prolonged to 6 hours.
Example 5
Glycolide-modified xylitol formal:
xylitol formal M1(82g, 0.5mol), glycolide (174g, 1.5mol), toluene (51g), butyltin dilaurate (2.04 g) were added to a 500mL four-necked flask (reflux condenser) equipped with a mechanical stirrer, thermometer at room temperature, heated to 105 deg.C and maintained under micro reflux for 5 hours, and the reaction was substantially complete to prepare a caprolactone-modified xylitol acetal backbone (R2 n-A-R2' n (R2 "n) abbreviated as intermediate M1A3), and the toluene solvent was removed under reduced pressure and used for the next reaction.
Experiments prove that tetrabutyl titanate, tetraisopropyl titanate, stannous octoate, dibutyl diacetate, zinc naphthenate, cobalt naphthenate or bismuth naphthenate are adopted to replace butyltin dilaurate in the embodiment, and the reaction can also be catalyzed; cyclohexane or heptane can be used as the solvent instead of toluene in the embodiment, and when cyclohexane is used as the solvent, the reflux temperature is changed to 88 ℃, and the time is prolonged to 6 hours.
Experiments further prove that the xylitol formal M1 can be replaced by xylitol formal to carry out the glycolide modification reaction.
Example 6
Lactide modified xylitol formal:
a500 mL four-necked flask (reflux condenser) equipped with a mechanical stirrer and thermometer was charged at room temperature with xylitol formal M1(82g, 0.5mol), lactide (216g, 1.5mol), toluene (59.6g), butyltin dilaurate (2.38g), warmed to 105 ℃ and maintained under micro reflux for 4-6 hours, and the reaction was substantially complete, thereby preparing caprolactone-modified xylitol acetal backbone (R2 n-A-R2' n (R2 "n) abbreviated as intermediate M1A4), and used for the next reaction after removal of the toluene solvent under reduced pressure.
Experiments prove that tetrabutyl titanate, tetraisopropyl titanate, stannous octoate, dibutyl diacetate, zinc naphthenate, cobalt naphthenate or bismuth naphthenate are adopted to replace butyltin dilaurate in the embodiment, and the reaction can also be catalyzed; cyclohexane or heptane can be used as the solvent instead of toluene in the embodiment, and when cyclohexane is used as the solvent, the reflux temperature is changed to 88 ℃, and the time is prolonged to 6 hours.
Experiments further prove that the xylitol formal M1 can be replaced by xylitol formal to carry out the lactide modification reaction.
Example 7
Ethylene oxide modified xylitol formal:
at room temperature, adding xylitol formal M1(164g, 1mol), potassium hydroxide (57.1g, 1.02mol) and toluene (40g) into a 500mL four-mouth bottle (connected with a reflux condenser tube) provided with a mechanical stirring thermometer, heating to 110 ℃, keeping for 2-3 hours under reflux, and removing water to obtain potassium xylitol; pumping (formal) potassium xylitol (222g, 1mol) into a high-pressure reaction kettle (controllable temperature is 0-200 ℃) with mechanical stirring and an independent air inlet and exhaust valve, firstly replacing with nitrogen, the replacement pressure is not more than 0.2MPa, closing the reaction kettle after emptying, starting stirring, and gradually increasing the material temperature to 110 ℃. Then, the pressure material tank (3 mol of ethylene oxide, 132g) with an independent air inlet and exhaust valve is pressurized to 0.5 to 0.6MPa by nitrogen, so that the ethylene oxide is continuously and slowly pressed into a polymerization kettle according to the requirements of the polymerization process, the pressure in the kettle is kept to be not more than 0.3MPa, the temperature is not more than 120 ℃, and the polymerization is carried out at low pressure. After the feeding of the ethylene oxide is finished, the kettle temperature is maintained at 120 ℃ under stirring, and the heat preservation is stopped after 0.5 hour. When the pressure in the kettle is reduced to be below 0.05MPa and the temperature of the materials is reduced to be below 70 ℃, the reaction is finished; the mixture was transferred to a flask and neutralized with acetic acid (63g, 1.05mol), washed twice with 50ml of water, the lower layer was separated and removed by water separation, and the upper layer was desolventized under reduced pressure to remove excess toluene, thereby preparing an ethylene oxide-modified xylitol acetal main chain (R2 n-A-R2' n (R2 "n) abbreviated as intermediate M1A 5).
Experiments prove that the reaction can be catalyzed by replacing potassium hydroxide in the embodiment with sodium hydroxide, sodium methoxide, sodium ethoxide, potassium methoxide or potassium ethoxide; cyclohexane or heptane can be used as the solvent instead of toluene in the embodiment, and when cyclohexane is used as the solvent, the reflux temperature is changed to 88 ℃, and the time is prolonged to 4 hours.
Experiments further prove that the xylitol formal M1 can be replaced by xylitol formal to carry out the above-mentioned ethylene oxide modification reaction.
Example 8
Propylene oxide modified xylitol formal:
at room temperature, a 500mL four-mouth bottle (connected with a reflux condenser tube) provided with a mechanical stirring thermometer is added with xylitol formal M1(164g, 1mol), potassium hydroxide (57.1g, 1.02mol) and toluene (40g), the temperature is raised to 110 ℃, and the mixture is kept under reflux for 2-3 hours to remove water; pumping (formal) potassium xylitol (222g, 1mol) into a high-pressure reaction kettle (controllable temperature is 0-200 ℃) with mechanical stirring and an independent air inlet and exhaust valve, firstly replacing with nitrogen, the replacement pressure is not more than 0.2MPa, closing the reaction kettle after emptying, starting stirring, and gradually increasing the material temperature to 110 ℃. And then pressurizing a pressure material tank (3 mol of propylene oxide, 174g) with an independent air inlet and exhaust valve with nitrogen at the pressure of 0.5-0.6 MPa, so that the propylene oxide is continuously and slowly pressed into a polymerization kettle according to the requirements of the polymerization process, the pressure in the kettle is kept to be not more than 0.3MPa, the temperature is not more than 120 ℃, and low-pressure polymerization is carried out. After the feeding of the propylene oxide is finished, the kettle temperature is maintained at 120 ℃ under stirring, and the heat preservation is stopped after 0.5 hour. When the pressure in the kettle is reduced to be below 0.05MPa and the temperature of the materials is reduced to be below 70 ℃, the reaction is finished; the mixture was transferred to a flask and neutralized with acetic acid (63g, 1.05mol), washed twice with 50ml of water, the lower layer was separated and removed by water separation, and the upper layer was desolventized under reduced pressure to remove excess toluene, thereby preparing a propylene oxide-modified xylitol acetal main chain (R2 n-A-R2' n (R2 "n) abbreviated as intermediate M1A 6).
Experiments prove that the reaction can be catalyzed by replacing potassium hydroxide in the embodiment with sodium hydroxide, sodium methoxide, sodium ethoxide, potassium methoxide or potassium ethoxide; cyclohexane or heptane can be used as the solvent instead of toluene in the embodiment, and when cyclohexane is used as the solvent, the reflux temperature is changed to 88 ℃, and the time is prolonged to 4 hours.
Experiments further prove that the xylitol formal M1 can be replaced by xylitol formal to carry out the propylene oxide modification reaction.
Example 9:
preparing caprolactone modified xylitol formal acrylate from caprolactone modified xylitol formal:
after cooling the remaining M1A2 solution obtained in example 3 to room temperature, adding (182g, 1.8mol) triethylamine, removing the heating mantle, cooling the temperature to 0 ℃ with an ice-water bath to smooth the reaction to be generated, slowly dropping (136g, 1.5mol, 30 drops/min) acryloyl chloride into an ice-bath cooled flask with electric stirrer by using a dropping funnel with a constant pressure for loading, after the dropwise addition of acryloyl chloride, removing the ice water bath, gradually heating the flask to room temperature, maintaining the reaction mixture at room temperature for 2 hours, after the reaction is finished, carrying out acid cleaning on the product by using 300ml of hydrochloric acid with the concentration of 1M, after the acid cleaning is finished, washing by using 100ml of distilled water, after the washing is finished, adding 0.15g of p-hydroxyanisole into the product solution, and (3) distilling under reduced pressure to remove a small amount of water and redundant cyclohexane solution to obtain the caprolactone modified xylitol formal acrylate.
Experiments prove that the acryloyl chloride can replace methacryloyl chloride to prepare propiolactone modified methacrylate with similar properties; methylamine, ethylamine or diethylamine may also be used instead of triethylamine to carry out the above reaction.
Example 10:
preparing glycolide modified xylitol formal methacrylate from glycolide modified xylitol formal:
after cooling the remaining M1A3 solution obtained in example 5 to room temperature, adding (182g, 1.8mol) triethylamine, removing the heating mantle, cooling the temperature to 0 ℃ with an ice-water bath to smooth the reaction to be reacted, slowly dropping (157g, 1.5mol) methacryloyl chloride into an ice-cooled flask with electric stirrer by using a dropping funnel with a constant pressure for sample addition, after the dropwise addition of the methacryloyl chloride, removing the ice-water bath, gradually heating the flask to room temperature, maintaining the reaction mixture at the room temperature for 2 hours, after the reaction is finished, carrying out acid washing on the product by using 300ml of hydrochloric acid with the concentration of 1M, after the acid washing is finished, washing by using 100ml of distilled water, after the washing is finished, adding 0.16g of p-hydroxyanisole into the product solution, and distilling under reduced pressure to remove a small amount of water and redundant cyclohexane solution to obtain the glycolide modified xylitol formal methacrylate.
Experiments prove that the methacrylic chloride can replace acryloyl chloride to prepare glycolide modified acrylate with similar properties; methylamine, ethylamine or diethylamine may also be used instead of triethylamine to carry out the above reaction.
Example 11:
preparing lactide modified xylitol benzaldehydemethacrylate from lactide modified xylitol benzaldehydes:
the xylitol formal in the example 6 adopts xylitol benzaldehyde to replace the reaction, the residual solution of M2A4 obtained in the experiment is cooled to room temperature, (182g, 1.8mol) triethylamine is added, an electric heating jacket for heating is removed, the temperature is cooled to 0 ℃ by using an ice-water bath to ensure that the reaction to be generated is relatively smooth, then (157g, 1.5mol) methacrylic acid chloride is slowly dripped into an electric stirring flask cooled by an ice bath by using a loading constant pressure dropping funnel, the ice-water bath is removed after the methacrylic acid chloride is dripped, the temperature of the flask is gradually increased to the room temperature, the reaction mixture is maintained for 2 hours at the room temperature, the product is acid-washed by 300ml of hydrochloric acid with the concentration of 1M, after the acid-washing is finished, 100ml of distilled water is used for washing, 0.17g of p-hydroxyanisole is added into the product solution after the washing is finished, a small amount of water and redundant cyclohexane solution are removed, obtaining the lactide modified xylitol benzal formaldehyde methacrylate.
Experiments prove that the methacryloyl chloride can be used for replacing the acryloyl chloride to prepare lactide modified acrylate with similar properties; lactide modified xylitol formal (M2a4) may be used instead of lactide modified (meth) acrylate prepared from lactide modified xylitol formal (M1a 4); methylamine, ethylamine or diethylamine may also be used instead of triethylamine to carry out the above reaction.
Example 12:
preparing epoxypropane modified xylitol benzaldehyde methacrylate by using epoxypropane modified xylitol benzaldehyde:
the xylitol formal in the example 8 adopts xylitol benzaldehyde to replace the reaction, the residual solution of M2A6 obtained in the experiment is cooled to room temperature, 364g (3.6 mol) triethylamine is added, an electric heating jacket for heating is removed, the temperature is cooled to 0 ℃ by using an ice-water bath, the reaction to be generated is relatively smooth, then (314g, 3mol) methacrylic acid chloride is slowly dripped into an electric stirring flask cooled by an ice bath by using a loading constant pressure dropping funnel, the ice-water bath is removed after the methacrylic acid chloride is dripped, the temperature of the flask is gradually raised to the room temperature, the reaction mixture is maintained at the room temperature for 2 hours, the product is pickled by 600ml of hydrochloric acid with the concentration of 1M, 200ml of distilled water is used for washing after the pickling is finished, 0.34g of p-hydroxyanisole is added into the product solution after the washing is finished, a small amount of water and redundant cyclohexane solution are removed by reduced pressure distillation, to obtain the epoxypropane modified xylitol benzaldehyde methacrylate.
Experiments prove that the methacryloyl chloride can be used for replacing acryloyl chloride to prepare propylene oxide modified acrylate with similar properties; wherein the propylene oxide modified xylitol formal (M2A6) can be replaced by propylene oxide modified xylitol formal (M1A6) to prepare similar propylene oxide modified (methyl) acrylate; methylamine, ethylamine or diethylamine may also be used instead of triethylamine to carry out the above reaction.
Example 13:
preparation of caprolactone-modified xylitol formal (epoxy ether) acrylate from caprolactone-modified xylitol formal:
after the remaining solution of M1A2 obtained in example 3 was cooled to room temperature, it was charged into a flask with electric stirring, and (192g, 1.5mol) of glycidyl acrylate, 2.67g of triphenylphosphine, and 1.78g of p-hydroxyanisole were added, slowly heated to 95 deg.C, and kept at the temperature for 2 hours, and further heated to 105 deg.C, and kept at 103 deg.C and 107 deg.C for 2-4 hours until the reaction was substantially completed, to thereby prepare caprolactone-modified xylitol formal (epoxy ether) acrylate.
Experiments prove that the acrylic acid glycidyl ether can be used for replacing methacrylic acid glycidyl ether to prepare caprolactone modified methacrylate with similar properties; triethylamine, benzyl ammonium chloride or benzyl ammonium bromide can also be used to replace triphenylphosphine for the above reaction.
The following table 1 shows the product performance test results, and the following table 2 shows the product degradation test data; table 3 shows the results of evaluation of the drawdown application properties after the product formulation.
In Table 1, the acid values were determined with reference to HB/FG 02-2009; the chromaticity is measured according to GB 9282; the polymerization inhibitors were determined in accordance with GB/T17530.5-1998; the viscosity is determined according to GB/T5561-1994; the curing rate is expressed in terms of the critical curing rate, which is defined as the maximum allowable speed of the conveyor belt at which the surface of the paint film is fully cured, i.e. the paint film is not fully cured when the conveyor belt speed is above the critical curing rate value; when the speed of the conveyor belt is lower than the critical curing speed value, the paint film is completely cured, the judgment basis for the complete curing of the paint film surface is that no scratch is generated by thumb twisting and pressing and dust-free paper wiping, the thickness of the paint film is 12 mu m, and the specific method for the curing speed refers to the following steps: aged and cool, Schopper, characteristics of alkoxylated bisphenol A di (meth) acrylate monomers, proceedings of the Chinese radiation curing annual meeting 2003, 16-26.
TABLE 1 evaluation tables for the properties of the products obtained in examples 9 to 13
Note that: the curing speed was measured after mixing in the following proportions: 220330 parts of Kaifolia Reyang RY of aliphatic polyurethane acrylate, 40 parts of example, 18 parts of TMPTA (trimethylolpropane triacrylate), 1843 parts of photoinitiator, 4 parts of BP benzophenone, 5 parts of initiator active amine (P115), 0.2 part of leveling agent Eterslip and BYK-0520.1 parts of defoaming agent;
and (3) sample degradation test:
degradation in water (accelerated degradation):
the sample was formed into a film of 1X 1cm2Drying the sample with the size in a vacuum oven at 80 ℃ for 24h, taking out the sample and weighing the sample with the mass W0Then placing the sample in 100 deg.C water, changing water at same time interval, taking out a piece of sample, drying surface water with absorbent paper, drying in 80 deg.C vacuum oven for 24 hr, and weighing the residual mass Wg。
According to V ═ W0-Wg)/W0The weight loss rate was calculated at 100%.
Degradation in PBS (phosphate buffered saline) (PH 7.4):
at normal temperature, the degradation of the polymer material is slow, and the degradation in a phosphoric acid buffer solution of 310K is often used to evaluate the degradation of biodegradable materials such as polylactic acid under natural conditions, especially in animal bodies.
The sample is prepared in the same way, dried in a vacuum oven at 80 ℃ for 24h, taken out and weighed to obtain the mass W0Then the sample was placed in a 10ml test tube containing phosphate buffer solution at pH 7.4, the tube was placed in a 37 ℃ thermostatic water bath, the water was changed every 96h, and a piece of the sample was taken out, dried in a vacuum oven at 80 ℃ for 24h, and weighed W was taken outgThe weight loss rate was calculated in the same manner.
TABLE 2 evaluation tables of degradation properties of products obtained in examples 9 to 13
Application example 1
30 parts of products obtained in examples 9-13, 12 parts of Kaifolia PEA (bisphenol A epoxy acrylate (20% TMPTA) RY1101A80), 18 parts of urethane acrylate (Kaifolia RY2204), 20 parts of 1, 6 hexanediol dipropylene glycol (Kaifolia R206), 14 parts of trimethylolpropane triacrylate (Kaifolia TMPTA R302), 1844 parts of an initiator, 0.8 part of a flatting agent Eterslip and BYK-0520.2 parts are respectively subjected to paint preparation according to the prior art, wherein the parts are mass parts, and the performance test of the obtained paint is carried out, and the impact resistance of a paint film is determined according to GB 1732-1979; the determination of the adhesion of paint films (plastic substrates such as ABS, PP, PE, PVC, PC and the like) is carried out according to GB 1720-; the hardness of the paint film is determined according to GB 6739-1986; the application properties of the resulting coating are shown in Table 3.
TABLE 3 application Properties of the examples
Claims (10)
1. A biodegradable radiation curable (meth) acrylate characterized by: the structural formula is as follows:
wherein R1 is hydrogen, or C1-C10 straight chain or branched chain alkyl, or C1-C4 branched chain phenyl; r2, R2 'and R2' are each a polyester polyether modifying group comprising at least one of (poly) caprolactone, (poly) lactide, (poly) glycolide, a compound providing epoxide groups or units providing alkylene oxide residues containing 2 to 3 carbon atoms; n, n 'and n' are each integers from 0 to 4, and the sum of n, n 'and n' is greater than 0; r3, R3' and R3 "are all residues of (meth) acrylated compounds linked to the molecular backbone through ester groups.
2. A method for preparing a biodegradable radiation curable (meth) acrylate, characterized in that: is prepared from xylitol acetal component, polyester polyether modified component and (methyl) acrylic ester compound.
3. The method of claim 2, wherein: the xylitol acetal component is xylitol acetal prepared by the reaction of xylitol and aldehydes with reactive carbonyl; the polyester polyether modification component comprises at least one of (poly) caprolactone, (poly) lactide, (poly) glycolide, a compound providing epoxide groups, or a unit providing an alkylene oxide residue containing 2 to 3 carbon atoms; the (meth) acrylating compound is: a (meth) acrylate residue linked to the main chain by reaction with one of (meth) acrylic acid chloride, (meth) acrylic acid, methyl (meth) acrylate, or a terminal (meth) acryloyl epoxy compound.
4. The production method as set forth in claim 2 or 3, characterized in that: comprises the following steps that:
a. reacting xylitol with aldehyde compounds with reactive carbonyl under the action of an acid catalyst, azeotropically removing water generated by the reaction by using a solvent with water, and preparing a xylitol acetal component containing polyhydroxy and substituent groups; the aldehyde compound with the reactive carbonyl group is formaldehyde, or linear or branched alkyl aldehyde containing C1-C10, or phenyl aldehyde containing C1-C4 branches;
b. carrying out modification reaction on the xylitol acetal component and the polyester polyether modified component under the action of a catalyst to obtain polyester polyether modified xylitol acetal polyol;
c. the method is carried out according to any one of the following modes c1-c 4:
c1. polyester polyether modified xylitol acetal polyalcohol reacts with (methyl) acrylic acid acyl chloride to prepare biodegradable radiation-curable (methyl) acrylate, and other solvents are not required to be added in the reaction process;
c2. the polyester polyether modified xylitol acetal polyol and (methyl) acrylic acid are subjected to esterification reaction under the action of an esterification catalyst, a polymerization inhibitor and a dehydrating agent to generate the polyester polyether modified xylitol acetal polyol.
c3. And carrying out ester exchange reaction on the polyester polyether modified xylitol acetal polyol and methyl (meth) acrylate under the action of an esterification catalyst and a polymerization inhibitor to generate the polyester polyether modified xylitol acetal polyol.
c4. And (3) carrying out ester exchange reaction on the polyester polyether modified xylitol acetal polyol and an epoxy compound with a terminal (methyl) acryloyl group under the action of a catalyst to generate the polyester polyether modified xylitol acetal polyol.
5. The method of claim 4, wherein: in the step a, the reaction temperature is 40-100 ℃, and the reaction time is 6-16 h; the molar ratio of the xylitol to the aldehyde compound with the reactive carbonyl group is (100-;
in the step a, the acidic catalyst is one or a mixture of more than two of sulfuric acid, sulfonic acid, methanesulfonic acid, ethylsulfonic acid, benzenesulfonic acid or p-toluenesulfonic acid in any proportion, and the molar amount of the acidic catalyst is 1-6% of the molar amount of the xylitol.
In the step a, the water-carrying solvent is one or a mixture of more than two of methanol, ethanol, benzene, toluene, C5 alkane or C6 alkane in any proportion, and the mass amount of the water-carrying solvent is 10-40% of the mass sum of the xylitol and the aldehyde compound with carbonyl.
6. The method of claim 4, wherein: b, reacting in cyclohexane, heptane or toluene at 70-120 ℃ for 2-6 hours; in the step b, the catalyst is one or a mixture of more than two of butyltin dilaurate, tetrabutyl titanate, tetraisopropyl titanate, stannous octoate, dibutyl diacetate, zinc naphthenate, cobalt naphthenate and bismuth naphthenate in any proportion.
7. The method of claim 4, wherein: step c1 is: slowly dripping (methyl) acryloyl chloride into polyester polyether modified xylitol acetal polyalcohol, reacting for 1-3 hours at room temperature after dripping is finished, and separating to obtain biodegradable radiation-curable (methyl) acrylate; wherein the molar consumption of the (methyl) acryloyl chloride is 1 to 1.3 times of the molar number of the polyester polyether modified xylitol acetal polyalcohol.
8. The method of claim 7, wherein: and c, adding a low-boiling-point amine alkaline substance to the reaction of the step c1 to neutralize hydrochloric acid generated after the reaction of acyl chloride, wherein the low-boiling-point amine alkaline substance is one or a mixture of more than two of methylamine, ethylamine, diethylamine or triethylamine in any proportion, and the molar amount of the low-boiling-point amine alkaline substance is 1-1.3 times of the molar number of the polyester polyether modified xylitol acetal polyol.
9. The method of claim 4, wherein: in the steps c2 and c3, the esterification catalyst is one or a mixture of more than two of sulfuric acid, sulfonic acid, methanesulfonic acid, ethylsulfonic acid, benzenesulfonic acid or p-toluenesulfonic acid in any proportion;
in the steps c2 and c3, the reaction temperature is 70-110 ℃, the reaction time is 6-14 hours, and after the reaction is finished, polyester polyether modified xylitol acetal polyol is generated through water washing, neutralization and desolventizing; wherein the molar amount of the (methyl) acrylic acid or the methyl (meth) acrylate is 2.4 to 4 times of the molar number of the polyester polyether modified xylitol acetal polyalcohol.
10. The method of claim 4, wherein: in the step c4, the epoxy compound with the terminal (methyl) acryloyl group is a mixture of acrylic acid glycidyl ether and methacrylic acid glycidyl ether in any proportion; the catalyst is one or a mixture of more than two of triethylamine, benzyl ammonium chloride, benzyl ammonium bromide or triphenylphosphine in any proportion.
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