CN107501463B - 一种紫外光自交联聚丙烯酸酯及其制备方法 - Google Patents
一种紫外光自交联聚丙烯酸酯及其制备方法 Download PDFInfo
- Publication number
- CN107501463B CN107501463B CN201710580434.7A CN201710580434A CN107501463B CN 107501463 B CN107501463 B CN 107501463B CN 201710580434 A CN201710580434 A CN 201710580434A CN 107501463 B CN107501463 B CN 107501463B
- Authority
- CN
- China
- Prior art keywords
- acrylate
- methacrylate
- crosslinking
- acrylate monomer
- polyacrylate
- 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.)
- Active
Links
- 238000004132 cross linking Methods 0.000 title claims abstract description 56
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 66
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 15
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 9
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 6
- 239000000853 adhesive Substances 0.000 claims abstract description 5
- 230000001070 adhesive effect Effects 0.000 claims abstract description 5
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 5
- 230000000977 initiatory effect Effects 0.000 claims abstract description 4
- 150000003254 radicals Chemical class 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 claims description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 2
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 claims description 2
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 claims description 2
- TVWTZAGVNBPXHU-FOCLMDBBSA-N dioctyl (e)-but-2-enedioate Chemical compound CCCCCCCCOC(=O)\C=C\C(=O)OCCCCCCCC TVWTZAGVNBPXHU-FOCLMDBBSA-N 0.000 claims description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-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
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 2
- 238000012650 click reaction Methods 0.000 abstract description 10
- 238000000016 photochemical curing Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 abstract description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003973 paint Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 8
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000005859 coupling reaction Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- -1 mercapto compounds Chemical class 0.000 description 6
- 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 6
- 238000001228 spectrum Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007142 ring opening reaction Methods 0.000 description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000006136 alcoholysis reaction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 150000003568 thioethers Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 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 description 2
- HXBMIQJOSHZCFX-UHFFFAOYSA-N 1-(bromomethyl)-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1CBr HXBMIQJOSHZCFX-UHFFFAOYSA-N 0.000 description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000000944 Soxhlet extraction Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000006276 transfer reaction Methods 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 1
- NNAHKQUHXJHBIV-UHFFFAOYSA-N 2-methyl-1-(4-methylthiophen-2-yl)-2-morpholin-4-ylpropan-1-one Chemical compound CC1=CSC(C(=O)C(C)(C)N2CCOCC2)=C1 NNAHKQUHXJHBIV-UHFFFAOYSA-N 0.000 description 1
- YJIHPMSQOPZABY-UHFFFAOYSA-N 2-nitrosobenzaldehyde Chemical compound O=CC1=CC=CC=C1N=O YJIHPMSQOPZABY-UHFFFAOYSA-N 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical group C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 238000000119 electrospray ionisation mass spectrum Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical class [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002576 ketones Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Images
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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/243—Two or more independent types of crosslinking for one or more polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
- C09J133/12—Homopolymers or copolymers of methyl methacrylate
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明公开了一种紫外光自交联聚丙烯酸酯及其制备方法。本发明首先合成一种含有潜在巯基基团的丙烯酸酯单体A和含有降冰片烯双键基团的丙烯酸酯单体B,然后将合成的丙烯酸酯单体A和B与可聚合光引发剂,甲基丙烯酸甲酯和丙烯酸丁酯按一定投料比通过热引发自由基共聚反应,得到紫外光自交联聚丙烯酸酯;本发明通过将潜在巯基结构以及双键接入聚丙烯酸酯侧链中,当紫外光照射下才产生巯基,并同时发生巯烯光点击反应实现交联,这样可以解决巯基和烯烃双键共同存在的体系在存放过程中不稳定的问题,制备得到的紫外光自交联聚丙烯酸酯在光固化涂料、光固化粘合剂、光致抗蚀剂、印刷板材、电子工业等方面具有较大的应用前景。
Description
技术领域
本发明属于高分子材料技术领域。更具体地,涉及一种紫外光自交联聚丙烯酸酯及其制备方法。
背景技术
紫外光交联丙烯酸酯在光固化涂料、光固化粘合剂、光致抗蚀剂、印刷板材、电子工业等方面的应用越来越广泛。聚丙烯酸酯成膜后经过光交联处理形成聚合物网络结构,可以提高成膜性能,例如:强度、硬度、耐磨性、耐溶剂性以及抗老化性等。
聚合物光交联的途径有多种,例如分子链上可聚合基团的光聚合反应、光致双自由基耦合反应、光环合加成反应、叠氮基团的光耦合反应、光致巯烯点击反应等等。目前大部分的紫外光交联型丙烯酸酯一般在侧链或主链上引入双键(如POLYMERIC MATERIALSSCIENCE AND ENGINEERING,第3期,第43-48页,1993年5月),这种通过自由基聚合或耦合反应交联的途径存在氧阻聚和收缩率高等问题。
而巯烯点击反应具有对氧和水均不敏感,体积收缩小,反应效率高的优点,而且基于巯烯点击交联的聚合物涂膜,由于巯基基团的引入,反应后生成硫醚的结构,硫醚在交联网状结构中旋转位垒较低,使得涂层具有很好的韧性和粘接性,高的折光系数,耐热性、抗氧性和低的吸水性。但是,巯基化合物小分子味道难闻,虽然已有报道将巯基基团引入聚合物分子链上有利于减轻难闻味道,但是巯烯体系的保存期较短(巯基在放置过程中有可能与双键加成反应,或两个巯基之间形成双硫键,从而交联和凝胶化),这阻碍了它在相应工业化中的应用。
发明内容
本发明所要解决的技术问题是克服上述现有技术的缺陷和不足,提供一种紫外光自交联聚丙烯酸酯的制备,通过将潜在巯基结构以及双键接入聚丙烯酸酯侧链中,当紫外光照射下才产生巯基,并同时发生巯烯光点击反应实现交联,这样可以解决巯基和烯烃双键共同存在的体系在存放过程中不稳定的问题。本发明还同时将二苯甲酮结构接入聚合物侧链中,作为光引发基团在光照下引发巯基点击反应,这样在使用时无需外加光引发剂。而且,二苯甲酮在光照下发生氢转移反应而产生的双自由基也具有偶合交联作用,进一步提高交联度。
本发明的目的是提供一种紫外光自交联聚丙烯酸酯。
本发明的另一目的是提供所述紫外光自交联聚丙烯酸酯的制备方法。
本发明的上述目的是通过以下技术方案给予实现的:
一种含有潜在巯基基团的丙烯酸酯单体A,结构式如下式(I)所示:
其中,R1选自甲基或氢;R2选自1~4个亚甲基;R3、R4、R5、R6选自氢或烷基。
优选地,R1为甲基;R2为2个亚甲基;R3、R4、R5、R6均为氢。
优选地,所述含有潜在巯基基团的丙烯酸酯单体A的制备方法如下:
(1)将邻硝基苄溴与3-巯基丙酸在一定缚酸剂,温度条件下反应形成硫醚(如反应式III所示);
(2)将步骤(1)的反应产物与甲基丙烯酸缩水甘油酯的环氧基在催化剂的作用下发生开环反应,得到丙烯酸酯单体A(如反应式IV所示)。
优选地,所述缚酸剂为氢氧化钠,氢氧化钾,碳酸钠,碳酸钾,三乙胺或吡啶(优选氢氧化钠)。
优选地,步骤(1)中反应温度为30~70℃(优选45℃)。
优选地,步骤(2)中的开环催化剂为三乙胺,四甲基氯化铵,四丁基溴化铵或三苯基膦(优选三苯基膦)。
优选地,所述开环催化剂用量为0.5~3wt%(优选1wt%)。
优选地,步骤(2)中开环反应温度为80~120℃(优选110℃)。
一种含有降冰片烯双键基团的丙烯酸酯单体B,结构式如下式(II)所示:
其中,R1选自甲基或氢;R2选自1~4个亚甲基;R3选自氢或羧基。
优选地,R1为甲基;R2为2个亚甲基;R3为羧基。
优选地,所述含有降冰片烯双键基团的丙烯酸酯单体B的制备方法为:将降冰片烯二酸酐与甲基丙烯酸羟乙酯在一定温度下发生醇解反应,得到丙烯酸酯单体B(如反应式V所示)。
优选地,降冰片烯二酸酐与甲基丙烯酸羟乙酯的投料摩尔比为1:1~1.5(优选1:1.1)。
优选地,醇解反应的温度为100~140℃(优选130℃)。
优选地,醇解反应时间为3~8h(优选5h)。
一种紫外光自交联聚丙烯酸酯的制备方法,将上述含有潜在巯基基团的丙烯酸酯单体A和含有降冰片烯双键基团的丙烯酸酯单体B通过热引发自由基共聚反应,得到紫外光自交联聚丙烯酸酯。
优选地,所述丙烯酸酯单体A投入量为1~50wt%(优选5~10wt%)。
优选地,所述丙烯酸酯单体B投入量为1~50wt%(优选5~10wt%)。
本发明发现,在实际制备聚合物时,丙烯酸酯单体A和丙烯酸酯单体B的添加量并不是越多越好,当丙烯酸酯的单体B的添加量过高时,聚合反应中容易产生凝胶从而影响聚合反应的进行,当丙烯酸酯单体A的添加量多高时,会引起体系变黄;此时,可加入常规的聚合单体来作为共聚和稀释单体来解决丙烯酸酯单体A和B添加量过高时带来的影响,通过试验证明,确定丙烯酸酯单体A和丙烯酸酯单体B的投入量均为10%时效果最理想,聚合时不会有凝胶产生。
优选地,所述常规聚合单体投入量为0~98wt%(优选50~80wt%)。
优选地,所述聚合反应温度为40~120℃(优选60~90℃,最优75℃)。
优选地,所述聚合反应时间为2~10h(优选3~6h,最优4h)。
优选地,所述常规聚合单体为乙酸乙烯酯、苯乙烯、丙烯酸、甲基丙烯酸、衣康酸、顺丁烯二酸二丁酯、顺丁烯二酸二辛酯、丙烯酰胺、甲基丙烯酰胺或丙烯腈、为丙烯酸甲酯、丙烯酸乙酯、丙烯酸异冰片酯、丙烯酸丁酯、丙烯酸月桂酯、丙烯酸-2-羟乙酯、丙烯酸缩水甘油酯、丙烯酸异丁酯、丙烯酸异癸酯、丙烯酸异辛酯或丙烯酸-2-羟丙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸异冰片酯、甲基丙烯酸丁酯、甲基丙烯酸月桂酯、甲基丙烯酸-2-羟乙酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸异丁酯、甲基丙烯酸异癸酯、甲基丙烯酸异辛酯、甲基丙烯酸二甲基氨基乙酯或甲基丙烯酸-2-羟丙酯中的一种或几种。
优选地,所述热引发使用的热引发剂为过氧化二苯甲酰,过氧化二月桂酰,过氧化二碳酸二异丙酯,过氧化苯甲酸叔丁酯,偶氮二异丁腈或偶氮二异庚腈。
优选地,所述热引发剂用量为0.5~3wt%(优选1%)。
优选地,聚合反应在有机溶剂中进行,有机溶剂为乙酸乙酯,乙酸丁酯、乙二醇乙酸酯、四氢呋喃、二氧六环、苯、甲苯、二甲苯、丙酮、丁酮、甲乙酮、环己酮、乙醇、丙醇、丁醇等常规有机溶剂(优选乙酸丁酯)。
优选地,聚合反应中可加入可聚合光引发剂,其作用不仅可以作为光引发巯烯点击反应,而且还可以通过夺氢使分子链间发生双基耦合,进一步提高交联度;其投入量为0~10wt%(优选0~5wt%)。
更优选地,所述可聚合光引发剂为MHPBP,其结构式如下式(VI)所示,其具体合成方法如ACS Appl.Mater.Interfaces,2015,7(31)pp 17489–17498)。
另外,上述方法制备得到的紫外光自交联聚丙烯酸酯及其在光固化涂料、光固化粘合剂、光致抗蚀剂、印刷板材或电子工业中的应用亦在发明保护范围内。
所述紫外光自交联聚丙烯酸酯的树脂溶液的固含量为5~80%;优选地,固含量为20~50%;更优选地,固含量为35%。
本发通过将潜在巯基结构以及双键接入聚丙烯酸酯侧链中,当紫外光照射下才产生巯基,并同时发生巯烯光点击反应实现交联,这样可以解决巯基和烯烃双键共同存在的体系在存放过程中不稳定的问题。同时将二苯甲酮结构接入聚合物侧链中,作为光引发基团在光照下引发巯基点击反应,这样在使用时无需外加光引发剂。而且,二苯甲酮在光照下发生氢转移反应而产生的双自由基也具有偶合交联作用,进一步提高交联度。
本发明中的紫外光自交联聚丙烯酸酯,在应用时给予光照即可自交联,其光交联机理如下:聚合物侧链上的邻硝基苄基吸收光能后,苄基上α键发生断裂脱去邻亚硝基苯甲醛并且生成巯基;在光引发剂的作用下,巯基与降冰片烯双键发生高活性的巯烯点击反应从而形成交联网络结构(如反应式VII所示)。
在交联过程中所需要的光引发剂,包括但不限于二苯甲酮、异丙基硫杂蒽酮、米氏酮、香豆素、取代二茂铁、2-羟基-2-甲基-1-苯基-1-丙酮、1-羟基环己基苯基甲酮、2-甲基-1-(4-甲硫基苯基)-2-吗啉基-1-丙酮、安息香双甲醚、2,4,6-三甲基苯甲酰基-二苯基氧化磷等。
与现有技术相比,本发明具有以下有益效果:
本发明制备得到了一种紫外光自交联聚丙烯酸酯,通过将潜在巯基结构以及双键接入聚丙烯酸酯侧链中,当紫外光照射下才产生巯基,并同时发生巯烯光点击反应实现交联,解决了巯基和烯烃双键共同存在的体系在存放过程中不稳定的问题;同时在聚合反应中加入可聚合光引发剂,不仅可以作为光引发巯烯点击反应,而且还可以通过夺氢使分子链间发生双基耦合,进一步提高交联度;制备得到的紫外光自交联聚丙烯酸酯在光固化涂料、光固化粘合剂、光致抗蚀剂、印刷板材、电子工业等方面具有较大的应用前景。
附图说明
图1为含有潜在巯基基团的丙烯酸酯单体A的1H NMR图。
图2为含有潜在巯基基团的丙烯酸酯单体A的ESI-MS正谱图。
图3为含有降冰片烯双键基团的丙烯酸酯单体B的1H NMR图。
图4为含有降冰片烯双键基团的丙烯酸酯单体B的ESI-MS负谱图。
具体实施方式
以下结合说明书附图和具体实施例来进一步说明本发明,但实施例并不对本发明做任何形式的限定。除非特别说明,本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
除非特别说明,以下实施例所用试剂和材料均为市购。
实施例1
1、制备紫外光自交联聚丙烯酸酯
(1)丙烯酸酯单体A的制备:
2.46g 3-巯基丙酸溶于20mL的丙酮,加入NaOH水溶液(2.04gNaOH、14mLH2O);降温至0℃,5g邻硝基苄基溴溶于20mL丙酮,并慢慢滴加;加热至45℃,继续反应4h;溶剂通过减压蒸馏除去,残留物重新溶解于20mL二氯甲烷和20mL水混合液中。水相用二氯甲烷清洗,随后用10%HCl溶液酸化,用30mL二氯甲烷萃取2遍,合并有机相,用无水硫酸钠干燥,减压旋蒸,得到浅黄色固体。
取5g上述浅黄色固体和三苯基膦溶于甲苯中,加热至110℃,将3.5g甲基丙烯酸缩水甘油酯慢慢滴加,反应5h;减压蒸馏除去甲苯,得到棕色粘稠状液体,然后用硅胶层析柱进一步提纯,流动相为乙酸乙酯和石油醚(v/v=2:3),得到淡黄色粘稠状液体。图1为产物的核磁氢谱1H NMR(400MHz,CDCl3,δ,ppm):8.00(a,1H),7.65~7.40(b,c,d,3H),6.17(m,1H),5.65(n,1H),4.35~4.00(h,i,j,k,6H),4.12(e,2H),2.76(f,2H),2.65(g,2H),1.99(l,3H);图2为ESI-MS正谱:特征峰401.1=[M+NH4 +]。
(2)丙烯酸酯单体B的制备:
在150mL三颈烧瓶中加入14.3g甲基丙烯酸羟乙酯、16.4g降冰片烯二酸酐、0.015g对羟基苯甲醚,通入氮气保护,加热至130℃,反应5h,测定酸值达到理论值后,冷却,得到白色固体。图3为产物的核磁氢谱1H NMR(400MHz,CDCl3,δ,ppm):6.30(a,1H),6.25(b,1H),6.15(j,1H),5.61(k,1H),4.42~4.22(g,h,4H),3.33(c,2H),3.22(d,2H),1.97(i,3H),1.50(e,1H),1.37(f,1H);图4为ESI-MS负谱:特征峰292.9=[M-H+]。
(3)紫外光自交联聚丙烯酸酯的制备:
将上述合成的1.0g丙烯酸酯单体A、1.0g丙烯酸酯单体B、9.0g甲基丙烯酸甲酯和9.0g丙烯酸丁酯单体,以及0.2g偶氮二异丁氰,加入30g乙酸丁酯为溶剂配成单体溶液。在装有冷凝管、机械搅拌、氮气导管以及滴液漏斗的四口烧瓶,滴入配好的1/3单体溶液,通入氮气,75℃下反应0.5h后,2h内滴加完剩余单体溶液以及引发剂,恒温反应1h,升温至95℃继续反应0.5h,把未反应的单体反应完全。在FT-IR光谱上1652cm-1处为降冰片烯C=C双键吸收峰,710cm-1处为C-S键吸收峰。
2、涂膜及光交联效果测试
上述所合成的聚丙烯酸酯树脂中加入基于树脂固体分的1wt%光引发剂2-羟基-2-甲基-1-苯基-1-丙酮,混合均匀后,用25μm的线棒涂布在聚四氟乙烯板上,将涂覆好的板材置于鼓风烘箱85℃下干燥30min后,在抽屉式的UV固化机上进行UV辐照固化3min,使涂覆好的板材在距光源约20cm处,光强为25.0至28.5mW/cm2。将薄膜揭下后,采用索氏抽提法测其交联度,结果如表1所示。
表1索氏抽提法测交联度结果
实施例2
将0.5g丙烯酸酯单体A、1.0g丙烯酸酯单体B、9.25g甲基丙烯酸甲酯和9.25g丙烯酸丁酯单体以及0.2g偶氮二异丁氰,加入30g乙酸丁酯为溶剂配成单体溶液。其余步骤均匀实施例1中相同,得到紫外光自交联聚丙烯酸酯。
涂膜步骤与实施例1相同,当丙烯酸酯A的含量从5%降为2.5%,交联点减少,交联度为35.76%。
实施例3
将2.0g丙烯酸酯单体A、1.0g丙烯酸酯单体B、8.5g甲基丙烯酸甲酯和8.5g丙烯酸丁酯单体以及0.2g偶氮二异丁氰,加入30g乙酸丁酯为溶剂配成单体溶液。其余步骤均匀实施例1中相同,得到紫外光自交联聚丙烯酸酯。
涂膜步骤与实施例1相同,由于丙烯酸酯A的含量从5%增致10%,交联点增加,交联度为54.91%。
实施例4
将2.0g丙烯酸酯单体A、2.0g丙烯酸酯单体B、8.0g甲基丙烯酸甲酯和8.0g丙烯酸丁酯单体以及0.2g偶氮二异丁氰,加入30g乙酸丁酯为溶剂配成单体溶液。其余步骤均匀实施例1中相同,得到紫外光自交联聚丙烯酸酯。
涂膜步骤与实施例1相同,同时将丙烯酸酯A和B的含量从5%增致10%,交联点增加,交联度为73.92%。
实施例5
将0.2g可聚合光引发剂,2.0g丙烯酸酯单体A、2.0g丙烯酸酯单体B、7.9g甲基丙烯酸甲酯和7.9g丙烯酸丁酯单体以及0.2g偶氮二异丁氰,加入30g乙酸丁酯为溶剂配成单体溶液。其余步骤均匀实施例1中相同,得到紫外光自交联聚丙烯酸酯。
将上述所合成的聚丙烯酸酯直接涂布在聚四氟乙烯板上,将涂覆好的板材置于鼓风烘箱85℃下干燥30min后,在抽屉式的UV固化机上进行UV辐照固化3min。由于聚合物侧链含有二苯甲酮单元,无需外加光引发剂,而且实现双机理交联,与实施例4相比,交联度增致88.48%。
对比例1
将1.0g丙烯酸酯单体B、9.5g甲基丙烯酸甲酯和9.5g丙烯酸丁酯单体以及0.2g偶氮二异丁氰,加入30g乙酸丁酯为溶剂配成单体溶液。其余步骤均匀实施例1中相同,得到侧链只含降冰片烯双键的聚丙烯酸酯。
涂膜步骤与实施例1相同。由于体系中不含丙烯酸酯单体A,不能产生巯基进行点击交联,仅靠降冰片烯双键固化,活性很低,交联度仅为4.70%。
Claims (9)
3.根据权利要求2所述的制备方法,其特征在于,所述丙烯酸酯单体A投入量为1~50wt%,丙烯酸酯单体B投入量为1~50wt%。
4.根据权利要求2所述的制备方法,其特征在于,共聚反应体系中加入常规聚合单体,其投加量为0~98%。
5.根据权利要求2所述的制备方法,其特征在于,所述聚合反应温度为40~120℃,聚合反应时间为2~10h。
6.根据权利要求4所述的制备方法,其特征在于,所述常规聚合单体为乙酸乙烯酯、苯乙烯、丙烯酸、甲基丙烯酸、衣康酸、顺丁烯二酸二丁酯、顺丁烯二酸二辛酯、丙烯酰胺、甲基丙烯酰胺或丙烯腈、为丙烯酸甲酯、丙烯酸乙酯、丙烯酸异冰片酯、丙烯酸丁酯、丙烯酸月桂酯、丙烯酸-2-羟乙酯、丙烯酸缩水甘油酯、丙烯酸异丁酯、丙烯酸异癸酯、丙烯酸异辛酯或丙烯酸-2-羟丙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸异冰片酯、甲基丙烯酸丁酯、甲基丙烯酸月桂酯、甲基丙烯酸-2-羟乙酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸异丁酯、甲基丙烯酸异癸酯、甲基丙烯酸异辛酯、甲基丙烯酸二甲基氨基乙酯或甲基丙烯酸-2-羟丙酯中的一种或几种。
7.根据权利要求2所述的制备方法,其特征在于,共聚反应中加入可聚合光引发剂,其投入量为0~10wt%。
8.权利要求2~7任一项所述制备方法制备得到的紫外光自交联聚丙烯酸酯。
9.权利要求8所述紫外光自交联聚丙烯酸酯在光固化涂料、光固化粘合剂、光致抗蚀剂、印刷板材或电子工业中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710580434.7A CN107501463B (zh) | 2017-07-17 | 2017-07-17 | 一种紫外光自交联聚丙烯酸酯及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710580434.7A CN107501463B (zh) | 2017-07-17 | 2017-07-17 | 一种紫外光自交联聚丙烯酸酯及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107501463A CN107501463A (zh) | 2017-12-22 |
CN107501463B true CN107501463B (zh) | 2020-03-20 |
Family
ID=60679863
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710580434.7A Active CN107501463B (zh) | 2017-07-17 | 2017-07-17 | 一种紫外光自交联聚丙烯酸酯及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107501463B (zh) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020104302A1 (en) * | 2018-11-20 | 2020-05-28 | Agfa-Gevaert Nv | Radiation curable inkjet ink for manufacturing printed circuit boards |
CN110128655B (zh) * | 2019-04-19 | 2021-08-27 | 岭南师范学院 | 一种基于硫醇-烯自修复光敏树脂组合物及应用 |
CN110314673B (zh) * | 2019-08-08 | 2021-06-01 | 福州大学 | 一种基于光引发混杂聚合的核酸适配体功能化亲和整体柱及其制备方法 |
CN111100309B (zh) * | 2019-11-14 | 2021-08-24 | 电子科技大学 | 一种光热图案化自增强聚合物材料及其制备方法 |
CN113061409A (zh) * | 2021-04-19 | 2021-07-02 | 昆山石梅新材料科技有限公司 | 一种丙烯酸胶黏剂树脂及其制备方法和应用 |
CN113214420B (zh) * | 2021-06-07 | 2022-09-09 | 东莞长联新材料科技股份有限公司 | 一种植物油基聚丙烯酸酯阴离子乳液及其制备方法和应用 |
CN114752324B (zh) * | 2022-04-18 | 2023-11-24 | 中国乐凯集团有限公司 | 柔性印刷版材用粘合剂组合物及柔性印刷版材 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1173885A (zh) * | 1995-02-09 | 1998-02-18 | 希巴特殊化学控股公司 | 可聚合组合物,交联聚合物的制备方法和可交联聚合物 |
CN101870793A (zh) * | 2010-05-28 | 2010-10-27 | 中山大学 | 一种自交联聚丙烯酸酯胶乳及其制备方法与水基纸张油墨 |
CN101891619A (zh) * | 2009-05-20 | 2010-11-24 | 日立化成工业株式会社 | 含羧基(甲基)丙烯酸酯及其制造方法 |
CN103153277A (zh) * | 2010-09-02 | 2013-06-12 | 路博润高级材料公司 | 聚合物和组合物 |
WO2016132224A1 (en) * | 2015-02-20 | 2016-08-25 | Natrix Separations Inc. | Chromatography membranes formed by thiol-ene or thiol-yne click polymerization reactions |
-
2017
- 2017-07-17 CN CN201710580434.7A patent/CN107501463B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1173885A (zh) * | 1995-02-09 | 1998-02-18 | 希巴特殊化学控股公司 | 可聚合组合物,交联聚合物的制备方法和可交联聚合物 |
CN101891619A (zh) * | 2009-05-20 | 2010-11-24 | 日立化成工业株式会社 | 含羧基(甲基)丙烯酸酯及其制造方法 |
CN101870793A (zh) * | 2010-05-28 | 2010-10-27 | 中山大学 | 一种自交联聚丙烯酸酯胶乳及其制备方法与水基纸张油墨 |
CN103153277A (zh) * | 2010-09-02 | 2013-06-12 | 路博润高级材料公司 | 聚合物和组合物 |
WO2016132224A1 (en) * | 2015-02-20 | 2016-08-25 | Natrix Separations Inc. | Chromatography membranes formed by thiol-ene or thiol-yne click polymerization reactions |
Also Published As
Publication number | Publication date |
---|---|
CN107501463A (zh) | 2017-12-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107501463B (zh) | 一种紫外光自交联聚丙烯酸酯及其制备方法 | |
KR100778755B1 (ko) | 가교성 수지 조성물 | |
CN110423304B (zh) | 乙烯基聚合物的光热自由基聚合制备方法及应用 | |
CN113248636B (zh) | 一种硫杂蒽酮可见光引发剂及制备方法和应用 | |
WO1995000573A1 (en) | Reactive polymers having pendant flexible side chains prepared from ethylenically unsaturated isocyanates | |
JP2003002919A (ja) | 新規ジ(メタ)アクリレート及びこれを含有してなる硬化性組成物 | |
CN115710457A (zh) | 一种紫外光固化组合物及其制备方法和应用 | |
TWI838455B (zh) | 含環碳酸酯基的(甲基)丙烯酸酯單體及聚合物 | |
JP2002284829A (ja) | 水性架橋型樹脂組成物 | |
CN107602759A (zh) | 一种含氟的水性光固化丙烯酸酯化聚丙烯酸酯树脂的制备方法 | |
JP3680705B2 (ja) | 架橋性樹脂組成物 | |
JP2004143344A (ja) | 紫外線吸収能を有する架橋性樹脂組成物 | |
JP2004277660A (ja) | 熱硬化型組成物 | |
US5242955A (en) | Composition comprising polyether compounds, a process for the preparation thereof and a curable resin composition | |
JPH08259623A (ja) | 反応性樹脂の製造方法 | |
JP2019156802A (ja) | 新規化合物、該化合物を含んでなる活性エネルギー線重合開始剤及び該重合開始剤を含有する活性エネルギー線硬化性組成物 | |
JP2004285113A (ja) | 側鎖に二重結合を有する(共)重合体からなる活性エネルギー線硬化型組成物および熱硬化型組成物 | |
JP2001310916A (ja) | 重合性樹脂組成物、その製造方法及びその硬化物 | |
JPS6118563B2 (zh) | ||
JP2001081111A (ja) | カチオン重合性樹脂組成物の製造方法 | |
JP3333303B2 (ja) | 樹脂組成物およびその製造方法 | |
JPH11140127A (ja) | 両末端に官能基を有するアクリル系重合体の製造方法 | |
CN114085165A (zh) | 一种含α-H的氰基改性丙烯酸酯树脂及其制备方法和应用 | |
JP4374171B2 (ja) | 新規連鎖移動剤及びこれを使用する重合体の製造方法 | |
JP6872918B2 (ja) | 重合体及びその用途 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |