CN101255229B - Self-sensitive polymeric hyper branched polyestermethylmethacrylate oligomer and preparation thereof - Google Patents
Self-sensitive polymeric hyper branched polyestermethylmethacrylate oligomer and preparation thereof Download PDFInfo
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- CN101255229B CN101255229B CN2008100270166A CN200810027016A CN101255229B CN 101255229 B CN101255229 B CN 101255229B CN 2008100270166 A CN2008100270166 A CN 2008100270166A CN 200810027016 A CN200810027016 A CN 200810027016A CN 101255229 B CN101255229 B CN 101255229B
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- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000000178 monomer Substances 0.000 claims abstract description 82
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920006150 hyperbranched polyester Polymers 0.000 claims abstract description 9
- 230000032050 esterification Effects 0.000 claims abstract description 8
- 238000005886 esterification reaction Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 92
- 239000002253 acid Substances 0.000 claims description 37
- -1 hydroxyalkyl acrylates Chemical class 0.000 claims description 26
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 23
- 150000002148 esters Chemical class 0.000 claims description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 20
- 150000008065 acid anhydrides Chemical class 0.000 claims description 17
- 238000006845 Michael addition reaction Methods 0.000 claims description 15
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 11
- 241000953555 Theama Species 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 claims description 5
- 238000006957 Michael reaction Methods 0.000 claims description 5
- 230000000903 blocking effect Effects 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 150000005690 diesters Chemical class 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims description 4
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- MUTGBJKUEZFXGO-UHFFFAOYSA-N hexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21 MUTGBJKUEZFXGO-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000007142 ring opening reaction Methods 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 claims description 2
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 claims description 2
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 claims description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims 2
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 claims 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- FLBJFXNAEMSXGL-UHFFFAOYSA-N het anhydride Chemical compound O=C1OC(=O)C2C1C1(Cl)C(Cl)=C(Cl)C2(Cl)C1(Cl)Cl FLBJFXNAEMSXGL-UHFFFAOYSA-N 0.000 claims 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 38
- 239000011347 resin Substances 0.000 abstract description 38
- 238000000034 method Methods 0.000 abstract description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 239000003973 paint Substances 0.000 abstract description 4
- 206010070834 Sensitisation Diseases 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 abstract description 2
- 230000008313 sensitization Effects 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 239000002966 varnish Substances 0.000 abstract description 2
- 125000005594 diketone group Chemical group 0.000 abstract 2
- 238000003756 stirring Methods 0.000 description 29
- 238000005070 sampling Methods 0.000 description 19
- 229920000728 polyester Polymers 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 238000000862 absorption spectrum Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 11
- 238000002329 infrared spectrum Methods 0.000 description 11
- 238000001816 cooling Methods 0.000 description 10
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 9
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 238000000016 photochemical curing Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 7
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 6
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 6
- 238000013461 design Methods 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 235000019589 hardness Nutrition 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 0 CCC(C)C(C(C)C1C(*[C@](*)C2(CCC(CCC(C(*3)C3(CC=C[*@@](C(C)(C*)C(C)C)O)N)O)(C(C)C3*C3)C(C(*)CC)=C)C=C2)C1)(C#C)O Chemical compound CCC(C)C(C(C)C1C(*[C@](*)C2(CCC(CCC(C(*3)C3(CC=C[*@@](C(C)(C*)C(C)C)O)N)O)(C(C)C3*C3)C(C(*)CC)=C)C=C2)C1)(C#C)O 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 125000004989 dicarbonyl group Chemical group 0.000 description 2
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000003512 tertiary amines Chemical group 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- NGZJECSTIJERAC-UHFFFAOYSA-N CC(C(OCC(COC(c1ccccc1C(OCCOC(C=C)=O)=O)=O)O)=C1CCCC1)=C Chemical compound CC(C(OCC(COC(c1ccccc1C(OCCOC(C=C)=O)=O)=O)O)=C1CCCC1)=C NGZJECSTIJERAC-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 241000233805 Phoenix Species 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
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- 238000005491 wire drawing Methods 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a synthetic method and technique for hyper branched polyester methacrylate oligomer. The feature of the oligomer is from the self-addition branching action of acroleic acid esterification beta-bi-carbonyl monomer (CH2=CH-CO-O-R-O-COCH2COCH3) to form hyper branched polyester with diketone structure, wherein the diketone structure is endued with resin sensitization activity. The methacrylate group in the resin gives ultraviolet light settability to the hyper branched polyester. The molecular weight of the obtained hyper branched polyester oligomer can be 2000-40000, with fine leveling performance, in application to light solidified ink, light solidified varnish, light solidified pigmented paint and light solidified adhesive.
Description
Technical field
The present invention relates to the synthetic of a class hyper-branched polyester methacrylate oligomers, belong to the synthetic field of macromolecular material.Specifically, be one to have polyester type oligopolymer (also claiming resin) synthetic of dissaving structure, the light-initiated activity of self-induction and polymerizable cross-linking properties roughly the same the time.This resin need not to add light trigger, under ultraviolet light irradiation polymerizing curable can take place directly, and many-sided performance contradictions such as its dissaving structure can the balance molecular weight, viscosity, cure shrinkage satisfy application printing construction and solidified coating performance demands.The product resin can be applicable to the prescription modulation of light-curable ink, photocuring varnish, photocuring colored paint and curable adhesive.
Background technology
Photo-curing material has the process characteristic of fireballing technical characterstic of cross-linking polymerization and solvent-free operation because of it, coating, printing ink, tackiness agent, plate making, electron device processing and other fields have been widely used in, have significant environmental friendliness, rapid processing and advantage such as energy-conservation, layer material is under ultraviolet light irradiation, several seconds, even can finish curing in the shorter time, realize coating, printing ink, tackiness agent by liquid state to insoluble solid-state transformation.
Photo-cured coating (printing ink and tackiness agent) generally is made up of the crosslinked light-cured resin of photopolymerization, the activity diluting monomer that is used to reduce working viscosity, light trigger and other kinds auxiliary agent etc., many application performances such as the shrinking percentage of light solidifying coating, sticking power, hardness, shock resistance, damage resistant and light-cured resin structural relation are close, and resin is one of key element of the final performance of decision coating.The light-cured resin of main flow can be divided into polyurethane-type, polyester type, epoxide resin type, polyether-type etc. at present, and comprises the acrylate active group, in order to photopolymerization crosslinking reaction point to be provided.For the consideration of coating decoration convenience and production of resins reliability, the viscosity of light-cured resin can not be too high, and the molecular weight of most light-cured resins only has hundreds to thousands of, and small part molecular resin amount can reach one to 20,000.Molecular weight is big more, and resin viscosity is high more, and is unfavorable more to links such as production, application, the controls of coating levelling.Yet the resin of macromolecule is very helpful to obtaining excellent coating machine mechanical property.Be this contradiction of balance, the hyperbranched light-cured resin of existing at present research institution's research and development is compared with the linear light-cured resin of tradition, and when its principal feature was to form larger molecular weight, viscosity was unlikely too high.In addition, in the light-curable ink field,, require matrix resin to have more satisfactory rheological, as the thixotropy of appropriateness, lower wire drawing characteristic etc. for the consideration of satisfying the printing ink printability.Hyperbranched resin has the performance of this respect mostly.Therefore, the research and development of hyperbranched light-cured resin receive the fervent concern in photocuring field.
The synthetic design of current hyperbranched light-cured resin generally adopts Michael reaction to obtain, promptly at first by diamine and acrylate reactions, formation remains with the acrylamide of primary amino structure, the amino continuation carries out Michael addition to the two keys of the C=C of acrylamide, because each amino can carry out twice addition, so realize AB
2Monomeric hyperbranched reaction, the ultrabranching polyamide resin of terminal more primary amino is dispersed in acquisition.But contain big quantity tertiary amine structure with this resin that designs acquisition, cause product colourity very dark, outward appearance product picture is not good, and stability in storage reduces, and also is difficult to by the general anti-xanthochromia of coating industry, anti-aging detection.How by simple and reliable synthetic route, develop the more excellent hyperbranched photosensitive resin of performance and be the current problem that solves of needing in this area.
Generally need in the photocurable formulation to add a spot of light trigger,, produce active free radical, cause resin, monomer crosslinked curing transformation fast in order to the efficient absorption UV-light.Although the kind of light trigger is more, yet can be phoenix feathers and unicorn horns by the light trigger of FDA authentication, the commercial light trigger of nearly all maturation self exists peculiar smell and certain toxicity, particularly in formulation for coating material, the by product that decomposes a series of aromatic ring structures that produce through ultraviolet light irradiation often causes more tangible peculiar smell and potential murder by poisoning easily.Thereby resolving the light trigger safety issue also is the further key in broadened application field of quick photo-cured coating of growing up.
Summary of the invention
The present invention is about class self-sensitive polymeric hyper branched polyestermethylmethaoligomer oligopolymer and preparation method thereof, and the synthetic design of this hyperbranched resin is with AB
2The monomeric head and the tail Michael addition/branching reaction of type is ultimate principle, wherein AB
2The type monomer is meant the compound that has acrylate group and beta-dicarbonyl structure simultaneously, and the acrylic double bond in the monomer is a functional group A, the active methylene radical-CH between the beta-dicarbapentaborane
2-have the addition reaction ability twice, be equivalent to the B of functional group.AB
2Michael addition takes place in the attack of the acceptant active methylene radical of acrylic double bond in the type monomer, and simultaneously, Michael addition can take place twice each active methylene radical, and two acrylic double bonds of attack addition promptly take place follow branching simultaneously.Its general structure is suc as formula 1.
Formula 1. indication AB of the present invention
2The general structure of type monomer
Wherein, the R group is expressed as follows:
This AB
2The type monomer can reacting by heating under sodium acetate, anhydrous catalysis be obtained by hydroxyalkyl acrylates and ketene dimer, and corresponding general reaction formula is seen formula 2.
Above-mentioned so-called hydroxyalkyl acrylates comprises vinylformic acid-beta-hydroxyl ethyl ester (HEA), Propylene glycol monoacrylate (two kinds of isomer mixtures), vinylformic acid-alpha-hydroxyl cyclohexyl, vinylformic acid-3-chloro-2-hydroxy propyl ester, and the open loop adduct of HEA and caprolactone.Other hydroxyalkyl acrylates also can adopt.
Formula 2.AB
2The type monomer synthesizes general reaction formula
Wherein R group counter structure is the same.
With above-mentioned AB
2Michael addition/branching reaction takes place in the type monomer under catalytic condition, obtain end and be the hyperbranched poly ester oligomer of active methylene radical, and this oligopolymer residual acrylic acid ester group content is lower, does not have further crosslinking polymerization activity substantially.The branching reaction process as shown in Equation 3.
Formula 3.AB
2Type monomer addition branching reaction
The practical structures of above-mentioned hyperbranched product is not necessarily equally regular as shown in FIG., may there be textural defect, the addition reaction of each active methylene radical may be not necessarily synchronous, and promptly addition branching growth length is not necessarily identical with algebraically on all directions, and branching algebraically has the low height that has on the different directions.In addition, the addition of active methylene radical also differs and establishes a capital very fully, may have the active methylene radical (CO-CH of minority
2-CO-) or active methyne (CO-CHR '-CO-) be wrapped in low algebraically shell, be difficult to further and the monomer addition.AB of the present invention
2In the type monomer active methylene radical through with acrylate generation Michael reaction after, formation according to existing bibliographical information, changes class formation to the UV-light sensitivity together with the quaternary carbon dicarbonyl structure, extinction decomposes the generation free radical, causes the radical polymerization of (methyl) acrylic double bond fast.By above-mentioned Michael addition branching reaction, obtained to have the photoactive hyperbranched poly ester oligomer of self-induction.
The algebraically control of reaction process and hyperbranched oligomer can realize by processing condition adjustment such as catalyzer, temperature of reaction, reaction times.Appropriate catalyst comprises organic bases (as triethylamine, N, N-dimethyl benzylamine, trolamine, DBU etc.), quaternary ammonium salt, triphenylphosphine of tertiary amines etc.
Be the stability in storage that improves this hyperbranched oligomer, the compound with regular structure and the oligomer molecules amount of branching resin, can use a small amount of methyl aceto acetate, methyl acetoacetate, methyl ethyl diketone or multifunctional acetoacetoxy groups compound as hyperbranched nucleator, remove the acrylate group of oligopolymer remnants, and significantly improve the degree of branching and oligomer molecules amount.This nucleator does not contain acrylate group, can add in the building-up reactions system before branching reaction.
Employed hyperbranched nucleator part can commercially availablely obtain, and multifunctional acetoacetoxy groups compound structure as shown in Equation 4.
The general structure of formula 4. multifunctional acetoacetoxy groups compounds
R in formula 4 structures
2Group derives from ethylene glycol, Diethylene Glycol, triethylene glycol, butyleneglycol, neopentyl glycol, 1,6-hexylene glycol etc., and reacting phase shown in its synthetic method and the formula 2 seemingly all is based on the ring-opening reaction of dibasic alcohol and ketene dimer.Hyperbranched reaction process under a small amount of nucleator coexistence can be represented with formula 5.
Hyperbranched reaction under formula 5. nucleators exist
Hyperbranched addition reaction under nucleator is regulated seems and is easy to control more, by changing the nucleator usage ratio, can conveniently control algebraically, molecular weight and the viscosity of hyper-branched polyester.
Based on active methylene radical in the beta-dicarbapentaborane to acrylate and the active difference of methacrylic ester addition reaction; when such active methylene radical and acrylate and methacrylic ester coexistence; Michael reaction only can betide acrylate usually; and methacrylic ester reacts hardly or it is very slow to react, and promptly Michael addition can show selectivity this moment.Above-mentioned end is rich in the hyper-branched polyester of active methylene radical and excessive vinylformic acid-methacrylic acid diester monomer (AMA) reaction, terminal active methylene radical of hyperbranched resin and the monomeric acrylate of AMA dibasic acid esters carry out Michael addition, active methylene radical transforms can be near complete, and methacrylate based group is kept, for the later stage application provides photopolymerization crosslinking reaction point.That is to say that AMA dibasic acid esters monomer carries out blocking modification in order to the hyper-branched polyester end to initial formation, sealing improves stable resin in conjunction with terminal active methylene radical, introduces polymerisable methacrylate based group simultaneously.AMA dibasic acid esters monomer generally is meant commercially available vinylformic acid-methacrylic acid diester monomer herein, or can be through simply knowing the similar dibasic acid esters monomer that building-up reactions obtains altogether.Its basic structure as shown in Equation 6.
Formula 6.AMA dibasic acid esters functional monomer basic structure
R in the above-mentioned AMA monomer structure
3Unit structure has diversity, and concrete structure is by following synthetic design decision.A kind of method is with glycidyl methacrylate (GMA) and vinylformic acid direct reaction, obtains methacrylic acid (3-acryloyl-oxy-2-hydroxyl) propyl ester (AHPMA).Another kind of preparation method is that the reaction under suitably catalyzer promotes with dibasic acid anhydride and Hydroxyethyl acrylate earlier makes acroleic acid esterification carboxylic acid intermediate, uses GMA and carboxyl reaction again, makes anhydride modified AMA dibasic acid esters monomer.Appropriate catalyst comprises tertiary amines organic bases, quaternary ammonium salt etc.Because acid anhydrides is selectivity more widely, can form a series of AMA dibasic acid esters monomers based on dibasic acid anhydride.For example following AMA monomer:
HEA-HHPA-GMA dibasic acid esters
HEA-maleic anhydride-GMA dibasic acid esters
The AMA monomer joins in the synthetic good aforementioned hyperbranched poly ester oligomer, continues reacting by heating, forms terminal the hyperbranched from photosensitive resin of metacrylic acid ester structure that be rich in.This end capping product basic structure as shown in Equation 7.
Formula 7.AMA monomer is to the end-blocking functionalization product basic structure of hyper-branched polyester
When the hyper-branched polyester that end is rich in active methylene radical carries out blocking modification, also the acrylate of AMA monomer and simple function can be mixed in proportion, the common Michael addition of accepting terminal active methylene radical, reduce two key functionality of final hyper-branched polyester methacrylate oligomers, cross-linking density and fragility during with the reduction photocuring.Suitable monofunctional acrylate monomer comprises ethyl propenoate, butyl acrylate, isopropyl acrylate, phenyl acrylate, vinylformic acid-beta-hydroxyl ethyl ester, Propylene glycol monoacrylate, vinylformic acid norborneol ester, Isooctyl acrylate monomer, lauryl acrylate, tridecyl acrylate, vinylformic acid stearyl etc.According to the application purpose and the performance requriements of final rosin products, the molar ratio of AMA monomer and monofunctional acrylate monomer can be adjusted between 3: 7～8: 2.
AB involved in the present invention
2Type acroleic acid esterification-general synthesis technique of beta-dicarbapentaborane monomer is as follows:
The sodium acetate, anhydrous that accounts for gross weight 0.1～2% is joined in a certain amount of hydroxyalkyl acrylates, add the p methoxy phenol that accounts for gross weight 0.2～1.0% and gather stablizer as resistance, be heated with stirring to 50～70 ℃, make the Glacial acetic acid sodium catalyst dissolve dispersion as far as possible.By the dicthenone of dropping funnel adding with respect to hydroxyalkyl acrylates excessive 10～30% (mol ratios), added in 1～3 hour, be warming up to 70～100 ℃ of reactions 1～6 hour afterwards.Take a sample in the reaction process, carry out infrared spectra and detect 3500cm in the infrared absorption spectrum
-1Near the absorption peak strength of corresponding hydroxyl reduces to very weak, and substantially changes with the reaction times, is considered as reaction near complete.Cooling finishes reaction, with the dilute hydrochloric acid solution washing reaction mixture of saturated brine preparation, divides water-yielding stratum, washs 2～3 times, is washed till water layer with deionized water at last and shows near neutral.Anhydrous sodium sulfate drying filters, and gets AB
2The type monomer.
As follows in order to hyper-branched polyester is carried out end capped AMA monomer typical case synthesis technique:
In a certain amount of GMA monomer, add the p methoxy phenol that accounts for gross weight 0.2～1.0% and gather stablizer as resistance, add again and account for gross weight 0.5～5% catalyzer, be heated with stirring to 50～80 ℃, add vinylformic acid with GMA equivalent by addition funnel stream, 0.5 adding ,～2 hours stream finishes, keep and original temperature, continued stirring reaction 1～6 hour.The infrared spectra detection is carried out in sampling in the reaction process, according to 910cm in the sample infrared absorption spectrum
-1Near the disappearance situation of epoxy group(ing) charateristic avsorption band judges whether reaction is complete.After cooling finishes reaction, titration measuring product acid number, acid number should be controlled at below the 5mgKOH/g.
As follows based on the synthetic general method of the AMA monomer of dibasic acid anhydride:
A certain amount of acid anhydrides is mixed with the HEA monomer, and excessive 1～8% (mol ratio) of HEA monomer adds poly-the stablizing of p methoxy phenol resistance that accounts for gross weight 0.2～1.0%, adds the catalyzer that accounts for gross weight 0.3～3% again, and heated and stirred is even.In 60～90 ℃ of reactions 2～8 hours.Acid number titration is carried out in sampling in the reaction process, react to acid number near theoretical value (this theoretical end point acid number is relevant with used acid anhydrides molecular weight), and almost no longer significantly increase, can tentatively be considered as reacting and reach terminal point.Examination of infrared spectrum is carried out in sampling simultaneously, as 1800～1900cm in infrared absorption spectrum
-1The charateristic avsorption band completely dissolve of the corresponding acid anhydrides of wave band can judge that acid anhydrides and HEA react completely, and obtains acid anhydrides monoesters product.Add GMA monomer with above-mentioned product acid number equivalent by dropping funnel stream, controlled temperature is in 60～90 ℃ of reactions 1～6 hour, measures acid number and reaches 5mgKOH/g when following, and cooling finishes reaction, acquisition AMA monomer.
General synthesis technique from sensitization hyper-branched polyester methacrylate oligomers involved in the present invention is summarized as follows:
With AB
2The type monomer mixed with the hyperbranched nucleator of diacetyl acetate ester in 6: 1 in molar ratio～100: 1, add the catalyzer that accounts for gross weight 0.1～3%, stir, be heated to 50～70 ℃ of reactions 1～5 hour, then add the stopper that accounts for gross weight 0.2～1%, adjust controlled temperature and continue reaction 0.5～2 hour in 70～90 ℃.Sampling is carried out infrared spectra and is detected 1630cm in the infrared absorption spectrum
-1And 811cm
-1Near the charateristic avsorption band completely dissolve of corresponding acrylic double bond promptly is considered as the Michael addition branching reaction and is tending towards complete.Temperature of reaction system is adjusted to 50～70 ℃, in molar ratio, stream adds with respect to the AMA monomer of 11～110 times of nucleators or the mixture of AMA monomer and monofunctional acrylate monomer, 0.5 added in～2 hours, continue stirring reaction 2～5 hours, be warming up to 70～90 ℃ of stirring reactions again 0.5～2 hour.Sampling is carried out
1Active methylene radical (the CO-CH of the corresponding beta dicarbapentaborane of chemical shift 3.45ppm and 3.50ppm place in the nuclear magnetic resonance spectrum is observed in H NMR test
2-CO-) and active methyne (CO-CHR '-whether CO-) signal disappear substantially, judges whether hyperbranched end capping carries out fully.It is complete substantially to treat that active methylene radical and active methyne transform, and cooling finishes reaction, obtains to have the light-initiated active hyper-branched polyester methacrylic ester of self-induction.
When selecting methyl aceto acetate or methyl ethyl diketone as hyperbranched nucleator, AB
2Type monomer and nucleator molar ratio can be regulated between 6: 1～100: 1 according to the design needs.End-blocking monomer and nucleator molar ratio are 9: 1～105: 1.
The final hyperbranched resin of institute's synthetic detects evaluation according to relevant national standard or industry universal method.According to the GB/T2794-1995 standard, adopt NDJ-7 rotary viscosity design determining viscosity.The molecular resin amount adopts gel chromatography.Resin is filmed on the general gold card paper in printing, and the photocuring paint film is by national standard test pencil hardness, and according to the ASTMD3359 standard, hundred lattice methods test sticking power is estimated whether surface drying of paint film photocuring with the finger mark method of enterprise practical.
The present invention is based on non-nitrogen Michael reaction, with a class AB
2The acroleic acid esterification beta dicarbapentaborane monomer of type carries out head and the tail addition/expansion reaction, form the only saturated hyper-branched polyester of carbon containing, hydrogen, Sauerstoffatom, with the active methylene radical in acrylate-terminal beta dicarbonyl structure of methacrylic ester dibasic acid esters monomer sealing hyper-branched polyester, introduce methacrylate based group simultaneously again.The quaternary carbon that forms in the oligomer structure that obtains gives hyperbranched resin certain photoreceptor activity together with dicarbonyl structure, need not light trigger, can cause photopolymerization voluntarily.Dissaving structure makes resin have higher molecular weight and relatively low viscosity simultaneously.The terminal labile methyl group acrylate group of introducing of resin branching is given resin photo-crosslinking curing performance.Assist so institute synthetic resins need not light trigger, have hyperbranchedly, can better tackle problems such as above-mentioned viscosity, rheological, light trigger harm from the initiated polymerization characteristics.
Embodiment
The invention will be further described by the following examples.
Embodiment one:
The 0.4g sodium acetate, anhydrous is joined in 85g (0.5mol) vinylformic acid-beta-hydroxyl cyclohexyl monomer, add the 0.5g p methoxy phenol.70 ℃ of stirring heating are dissolved fully substantially to sodium acetate, anhydrous, by dropping funnel Dropwise 5 0.4g (0.6mol) dicthenone, add in 2.5 hours, are warming up to 95 ℃, continue stirring reaction 2.5 hours, and examination of infrared spectrum, 3540cm are carried out in sampling
-1Place's hydroxyl absorption peak strength very a little less than, cooling finishes reaction.With the dilute hydrochloric acid solution washing reaction mixture of saturated brine preparation, divide water-yielding stratum, wash 2～3 times, be washed till water layer with deionized water at last and show near neutral.Anhydrous sodium sulfate drying spends the night, and filters, and gets the AB of following structure
2Type monomer 116.2g.
Embodiment two:
The 0.4g sodium acetate, anhydrous is joined in 59.0g (0.5mol) vinylformic acid-beta-hydroxyl ethyl ester monomer, add the 0.3g p methoxy phenol.60 ℃ of stirring heating are dissolved fully substantially to sodium acetate, anhydrous, by dropping funnel Dropwise 5 0.4g (0.6mol) dicthenone, add in 2.5 hours, are warming up to 75 ℃, continue stirring reaction 2 hours, and examination of infrared spectrum, 3546cm are carried out in sampling
-1Place's hydroxyl absorption peak strength very a little less than, cooling finishes reaction.With the dilute hydrochloric acid solution washing reaction mixture of saturated brine preparation, divide water-yielding stratum, wash 2～3 times, be washed till water layer with deionized water at last and show near neutral.Anhydrous sodium sulfate drying spends the night, and filters, and gets the AB of following structure
2Type monomer 97.4g.
Embodiment three:
In 71.0g (0.50mol) GMA monomer, add the 0.4g p methoxy phenol as the poly-stablizer of resistance, add 1.0g N again, the N-dimethyl benzylamine is as catalyzer, be heated with stirring to 65 ℃, add 35.3g (0.49mol) vinylformic acid by addition funnel stream, 1 hour stream adds and finishes, and keeps original temperature, continues stirring reaction after 2.5 hours.Sampling is carried out infrared spectra and is detected 910cm in the infrared absorption spectrum
-1Near the almost disappearance of epoxy group(ing) charateristic avsorption band is reacted complete substantially.Cooling finishes reaction, titration measuring product acid number 1.3mgKOH/g.Gained AMA monomer structure is as follows:
Embodiment four:
154g (1.0mol) HHPA is mixed with 121.8g (1.05mol) HEA monomer, add the 1.2g p methoxy phenol and hinder poly-stablizing, add the 3.0g Tetrabutyl amonium bromide again as catalyzer, heated and stirred is even.In 80 ℃ of reactions 2 hours.The sampling and measuring acid number reaches 196.4mgKOH/g (the theoretical acid number of complete reaction is 203mgKOH/g), 1857cm in the product infrared absorption spectrum
-1Locate the charateristic avsorption band completely dissolve of corresponding HHPA, judge that acid anhydrides and HEA react completely, obtain acid anhydrides monoesters product.Add 142g (1.0mol) GMA monomer by dropping funnel stream, controlled temperature is measured acid number and is reached 3.4mgKOH/g in 75 ℃ of reactions 3 hours, and cooling finishes reaction, obtains the AMA monomer of following structure.
Embodiment five:
148g (1.0mol) phthalic anhydride is mixed with 121.8g (1.05mol) HEA monomer, add the 1.2g p methoxy phenol and hinder poly-stablizing, add the 3.0g Tetrabutyl amonium bromide again as catalyzer, heated and stirred is even.In 80 ℃ of reactions 2 hours.The sampling and measuring acid number reaches 192.8mgKOH/g (the theoretical acid number of complete reaction is 208mgKOH/g), 1854cm in the product infrared absorption spectrum
-1The charateristic avsorption band of locating corresponding phthalic anhydride almost disappears, and judges that acid anhydrides and HEA react completely, and obtains acid anhydrides monoesters product.Add 142g (1.0mol) GMA monomer by dropping funnel stream, controlled temperature is measured acid number and is reached 2.7mgKOH/g in 70 ℃ of reactions 2.5 hours, and cooling finishes reaction, obtains the AMA monomer of following structure.
Embodiment six:
371.0g (1.0mol) phthalic anhydride is mixed with 121.8g (1.05mol) HEA monomer, and the resistance of adding 2.2g p methoxy phenol is poly-stable, adds the 5.0g Tetrabutyl amonium bromide again as catalyzer, preheats to stir.In 80 ℃ of reactions 4 hours.The sampling and measuring acid number reaches 94.8mgKOH/g (the theoretical acid number of complete reaction is 112mgKOH/g), 1869cm in the product infrared absorption spectrum
-1The charateristic avsorption band of locating corresponding phthalic anhydride almost disappears, and judges that acid anhydrides and HEA react completely, and obtains acid anhydrides monoesters product.Add 142g (1.0mol) GMA monomer by dropping funnel stream, controlled temperature is measured acid number and is reached 3.3mgKOH/g in 70 ℃ of reactions 2.5 hours, and cooling finishes reaction, obtains the AMA monomer of following structure.
Embodiment seven:
With the 101.6g among the embodiment one (0.4mol) AB
2The type monomer mixes with the hyperbranched nucleator of 4.6g (0.02mol) diacetyl acetate second diester, adds 0.2g DBU catalyzer, stirs, and is heated to 50 ℃ of reactions 2 hours, then adds the 0.4g stopper, adjusts controlled temperature and continues reaction 1.5 hours in 80 ℃.Sampling is carried out infrared spectra and is detected 1630cm in the infrared absorption spectrum
-1And 811cm
-1Near the charateristic avsorption band completely dissolve of corresponding acrylic double bond, it is complete that the Michael addition branching reaction is tending towards.Temperature of reaction system is adjusted to 50 ℃, adds the AMA monomer 107g (0.48mol) among the embodiment three, added in 1 hour, continued stirring reaction 2.5 hours, be warming up to 80 ℃ of stirring reactions again 0.5 hour.Sampling is carried out
1H NMR test, the active methylene radical (CO-CH of the corresponding beta dicarbapentaborane in chemical shift 3.45ppm and 3.50ppm place in the nuclear magnetic resonance spectrum
2-CO-) and active methyne (CO-CHR '-CO-) signal disappears substantially, hyperbranched end capping is complete substantially.Add 50ml dilute hydrochloric acid while hot, stir and remove the DBU catalyzer, with 50 ℃ of nearly saturated aqueous common salt extractions three times, anhydrous sodium sulfate drying spends the night, and removes solid sodium sulfate, gets light yellow viscosity hyper-branched polyester methacrylic ester again.Gel chromatography gained hyperbranched oligomer number-average molecular weight 8.72 * 10
3, molecular weight distribution width 2.13, viscosity 4650cps/30 ℃.
Embodiment eight:
With the 80.0g among the embodiment two (0.40mol) AB
2The type monomer mixes with the hyperbranched nucleator of 2.3g (0.01mol) diacetyl acetate second diester, adds 0.2g DBU catalyzer, stirs, and is heated to 50 ℃ of reactions 2 hours, then adds the 0.4g stopper, adjusts controlled temperature and continues reaction 1.5 hours in 80 ℃.Sampling is carried out infrared spectra and is detected 1630cm in the infrared absorption spectrum
-1And 811cm
-1Near the charateristic avsorption band completely dissolve of corresponding acrylic double bond, it is complete that the Michael addition branching reaction is tending towards.Temperature of reaction system is adjusted to 50 ℃, adds the AMA monomer 197.0g (0.48mol) among the embodiment four, added in 1 hour, continued stirring reaction 2.5 hours, be warming up to 80 ℃ of stirring reactions again 0.5 hour.Sampling is carried out
1H NMR test, the active methylene radical (CO-CH of the corresponding beta dicarbapentaborane in chemical shift 3.45ppm and 3.50ppm place in the nuclear magnetic resonance spectrum
2-CO-) and active methyne (CO-CHR '-CO-) signal disappears substantially, hyperbranched end capping is complete substantially.Add 50ml dilute hydrochloric acid while hot, stir and remove the DBU catalyzer, with 50 ℃ of nearly saturated aqueous common salt extractions three times, anhydrous sodium sulfate drying spends the night, and removes solid sodium sulfate, gets yellow viscosity hyper-branched polyester methacrylic ester again.Gel chromatography gained hyperbranched oligomer number-average molecular weight 2.48 * 10
4, molecular weight distribution width 2.85, viscosity 16800cps/30 ℃.
Embodiment nine:
With the 90.0g among the embodiment two (0.45mol) AB
2The type monomer mixes with the hyperbranched nucleator of 2.7g (0.01mol) neopentyl glycol diacetyl acetate ester, adds 0.2g DBU catalyzer, stirs, and is heated to 50 ℃ of reactions 2 hours, then adds the 0.4g stopper, adjusts controlled temperature and continues reaction 1.5 hours in 80 ℃.Sampling is carried out infrared spectra and is detected 1630cm in the infrared absorption spectrum
-1And 811cm
-1Near the charateristic avsorption band completely dissolve of corresponding acrylic double bond, it is complete that the Michael addition branching reaction is tending towards.Temperature of reaction system is adjusted to 50 ℃, adds the AMA monomer 203.0g (0.50mol) among the embodiment five, added in 1 hour, continued stirring reaction 2.5 hours, be warming up to 80 ℃ of stirring reactions again 0.5 hour.Sampling is carried out
1H NMR test, the active methylene radical (CO-CH of the corresponding beta dicarbapentaborane in chemical shift 3.45ppm and 3.50ppm place in the nuclear magnetic resonance spectrum
2-CO-) and active methyne (CO-CHR '-CO-) signal disappears substantially, hyperbranched end capping is complete substantially.Add 50ml dilute hydrochloric acid while hot, stir and remove the DBU catalyzer, with 70 ℃ of nearly saturated aqueous common salt extractions three times, anhydrous sodium sulfate drying two days is removed solid sodium sulfate, gets yellow viscosity hyper-branched polyester methacrylic ester again.Gel chromatography gained hyperbranched oligomer number-average molecular weight 3.11 * 10
4, molecular weight distribution width 3.19, viscosity 31460cps/30 ℃.
Embodiment ten:
With the 90.0g among the embodiment two (0.45mol) AB
2The type monomer mixes with the hyperbranched nucleator of 1.0g (0.01mol) methyl ethyl diketone, adds 0.2g DBU catalyzer, stirs, and is heated to 50 ℃ of reactions 2 hours, then adds the 0.4g stopper, adjusts controlled temperature and continues reaction 1.5 hours in 80 ℃.Sampling is carried out infrared spectra and is detected 1630cm in the infrared absorption spectrum
-1And 811cm
-1Near the charateristic avsorption band completely dissolve of corresponding acrylic double bond, it is complete that the Michael addition branching reaction is tending towards.Temperature of reaction system is adjusted to 50 ℃, add AMA monomer 41.2g (0.10mol) and 116.6g (0.36mol) vinylformic acid stearyl among AMA monomer 75.5g (0.10mol), the embodiment four among the embodiment six, added in 1 hour, continue stirring reaction 2.5 hours, be warming up to 80 ℃ of stirring reactions again 0.5 hour.Sampling is carried out
1H NMR test, the active methylene radical (CO-CH of the corresponding beta dicarbapentaborane in chemical shift 3.45ppm and 3.50ppm place in the nuclear magnetic resonance spectrum
2-CO-) and active methyne (CO-CHR '-CO-) signal disappears substantially, hyperbranched end capping is complete substantially.Add 50ml dilute hydrochloric acid while hot, stir and remove the DBU catalyzer, with 70 ℃ of nearly saturated aqueous common salt extractions three times, anhydrous sodium sulfate drying two days is removed solid sodium sulfate, gets tawny viscosity hyper-branched polyester methacrylic ester again.Gel chromatography gained hyperbranched oligomer number-average molecular weight 3.51 * 10
4, molecular weight distribution width 3.42, viscosity 21480cps/50 ℃.
Embodiment 11:
Embodiment seven, eight, nine, ten gained resins are directly filmed in the gold card paper surface, 25 microns of film thickness monitorings, through 800W medium pressure mercury lamp irradiation, each irradiation 15 seconds detects surperficial dryness, hundred lattice sticking power and pencil hardnesss, the results are shown in table 1.
Table 1 hyperbranched resin photocuring test result
Claims (10)
1. self-sensitive polymeric hyper branched polyestermethylmethaoligomer oligopolymer, it is by having the photoactive hyperbranched poly ester oligomer of self-induction through acrylate-methacrylic ester asymmetric dibasic acid esters AMA monomer or through the end capped blocking modification thing of the mixture of asymmetric dibasic acid esters of acrylate-methacrylic ester and monofunctional acrylate monomer, molecular weight is 2000～40000; Described hyperbranched poly ester oligomer then is AB
2The acroleic acid esterification beta-dicarbapentaborane monomer of type and the Michael addition branching reaction product of hyperbranched nucleator; Described hyperbranched nucleator is the compound that contains the active structure of beta-dicarbapentaborane.
2. self-sensitive polymeric hyper branched polyestermethylmethaoligomer oligopolymer according to claim 1 is characterized in that described AB
2The type monomer is that a class one end has acrylate structural, and the other end has the functional monomer of etheric acid ester structure, and acrylic double bond is equivalent to functional group A, and the active methylene radical between two carbonyls of the other end is equivalent to two functional group B; Its general structure is shown below:
Wherein, the R group is selected from following group:
-CH
2CH
2-
3. self-sensitive polymeric hyper branched polyestermethylmethaoligomer oligopolymer according to claim 2 is characterized in that described AB
2The type monomer is obtained by hydroxyalkyl acrylates and the reaction of dicthenone esterification by ring opening.
4. self-sensitive polymeric hyper branched polyestermethylmethaoligomer oligopolymer according to claim 3, the reaction conditions that it is characterized in that described esterification by ring opening reaction is: under catalytic condition, by molar weight, stream adds excessive 10～30% dicthenone in the hydroxyalkyl acrylates, temperature of reaction is 50～100 ℃, 1～9 hour reaction times.
5. according to claim 1 or 2 or 3 or 4 described self-sensitive polymeric hyper branched polyestermethylmethaoligomer oligopolymer, it is characterized in that described hyperbranched nucleator comprises methyl aceto acetate, methyl acetoacetate, methyl ethyl diketone and multifunctional acetoacetoxy groups compound.
6. self-sensitive polymeric hyper branched polyestermethylmethaoligomer oligopolymer according to claim 5, it is characterized in that described multifunctional acetoacetoxy groups compound comprises ethylene glycol bis acetylacetic ester, diethylene glycol bis-acetylacetic ester, triethylene glycol diacetyl acetate ester, 1,4-butyleneglycol diacetyl acetate ester, neopentyl glycol diacetyl acetate ester, 1,6-hexylene glycol diacetyl acetate ester.
7. according to claim 1 or 2 or 3 or 4 described self-sensitive polymeric hyper branched polyestermethylmethaoligomer oligopolymer, it is characterized in that described AMA monomer is meant that an end is an acrylate, the other end is two functional monomers of metacrylic acid ester structure, be specially: the asymmetric diester that methacrylic acid (2-acryloxy) ethyl ester or glycidyl methacrylate and vinylformic acid reaction form, and make acroleic acid esterification carboxylic acid intermediate by Hydroxyethyl acrylate and dibasic acid anhydride reaction earlier, use the prepared anhydride modified asymmetric diester of carboxyl reaction of glycidyl methacrylate and acroleic acid esterification carboxylic acid intermediate again.
8. self-sensitive polymeric hyper branched polyestermethylmethaoligomer oligopolymer according to claim 7 is characterized in that described dibasic acid anhydride mainly comprises maleic anhydride, Tetra hydro Phthalic anhydride, HHPA, tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, methyl tetrahydro phthalic anhydride, carbic anhydride, methyl carbic anhydride, chlorendic anhydride.
9. according to claim 1 or 2 or 3 or 4 described self-sensitive polymeric hyper branched polyestermethylmethaoligomer oligopolymer, it is characterized in that described monofunctional acrylate comprises ethyl propenoate, butyl acrylate, isopropyl acrylate, phenyl acrylate, vinylformic acid-beta-hydroxyl ethyl ester, Propylene glycol monoacrylate, vinylformic acid norborneol ester, Isooctyl acrylate monomer, lauryl acrylate, tridecyl acrylate, vinylformic acid stearyl.
10. the preparation method of a self-sensitive polymeric hyper branched polyestermethylmethaoligomer oligopolymer as claimed in claim 1 is characterized in that: with AB
2The type monomer mixed with hyperbranched nucleator in 6: 1 in molar ratio～100: 1, under catalyst action, in 50～90 ℃ of reactions 1～7 hour, temperature of reaction system is adjusted to 50～70 ℃ then, in molar ratio, the mixture that stream adds with respect to the AMA monomer of 9～110 times of nucleators or AMA monomer and monofunctional acrylate monomer carries out blocking modification, introduces the methylpropanoic acid ester group, and this blocking modification Michael reaction was carried out 2～7 hours in 50～90 ℃.
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| KR101459121B1 (en) * | 2011-11-10 | 2014-11-07 | 제일모직주식회사 | Hard coating film, composition for the hard coating film, polarizing plate comprising the same, and liquid crystal display comprising the same |
| US9340644B2 (en) | 2012-05-04 | 2016-05-17 | Eternal Materials Co., Ltd. | Self-sensitive polymerizable liquid resin and use thereof |
| CN109957083B (en) * | 2017-12-25 | 2021-06-29 | 江苏百赛飞生物科技有限公司 | Unsaturated polyol, photocurable polyurethane prepared from unsaturated polyol and preparation methods of unsaturated polyol and photocurable polyurethane |
| CN111117555A (en) * | 2019-12-30 | 2020-05-08 | 庄明磊 | Environment-friendly aqueous adhesive and preparation method thereof |
| CN112552483B (en) * | 2020-11-16 | 2023-06-30 | 新丰见微化工实业有限公司 | Self-photosensitive epoxy methacrylate resin and synthetic method thereof |
| CN115260857A (en) * | 2022-07-13 | 2022-11-01 | 广东希贵光固化材料有限公司 | UV skin-feel paint |
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