CN112521529B - 一种led敏感二苯乙烯基肟酯型光引发剂及其制备和应用 - Google Patents
一种led敏感二苯乙烯基肟酯型光引发剂及其制备和应用 Download PDFInfo
- Publication number
- CN112521529B CN112521529B CN202011327985.0A CN202011327985A CN112521529B CN 112521529 B CN112521529 B CN 112521529B CN 202011327985 A CN202011327985 A CN 202011327985A CN 112521529 B CN112521529 B CN 112521529B
- Authority
- CN
- China
- Prior art keywords
- product
- hours
- photoinitiator
- solvent
- oxime ester
- 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
- -1 distyryl oxime ester Chemical class 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims abstract description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005977 Ethylene Substances 0.000 claims abstract description 5
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims abstract description 5
- JFLKFZNIIQFQBS-FNCQTZNRSA-N trans,trans-1,4-Diphenyl-1,3-butadiene Chemical group C=1C=CC=CC=1\C=C\C=C\C1=CC=CC=C1 JFLKFZNIIQFQBS-FNCQTZNRSA-N 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N triethylamine Natural products CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 238000004440 column chromatography Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 claims description 3
- LSEFCHWGJNHZNT-UHFFFAOYSA-M methyl(triphenyl)phosphanium;bromide Chemical group [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 LSEFCHWGJNHZNT-UHFFFAOYSA-M 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 claims description 3
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 150000001263 acyl chlorides Chemical class 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 150000005840 aryl radicals Chemical class 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 claims description 2
- 229940077388 benzenesulfonate Drugs 0.000 claims description 2
- 150000004768 bromobenzenes Chemical class 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002923 oximes Chemical group 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N phenyl bromide Natural products BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 2
- 235000021286 stilbenes Nutrition 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
- 239000000017 hydrogel Substances 0.000 abstract description 14
- 238000001723 curing Methods 0.000 abstract description 12
- 239000003999 initiator Substances 0.000 abstract description 12
- 238000003847 radiation curing Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000010146 3D printing Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000003973 paint Substances 0.000 abstract 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 20
- 239000007787 solid Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000008034 disappearance Effects 0.000 description 6
- 238000000016 photochemical curing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- KEOLYBMGRQYQTN-UHFFFAOYSA-N (4-bromophenyl)-phenylmethanone Chemical compound C1=CC(Br)=CC=C1C(=O)C1=CC=CC=C1 KEOLYBMGRQYQTN-UHFFFAOYSA-N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007790 scraping Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001698 laser desorption ionisation Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- KUFSHIHMAHIGFS-UHFFFAOYSA-N 1-(4-bromophenyl)-2-(4-methylphenyl)ethanone Chemical compound C1=CC(C)=CC=C1CC(=O)C1=CC=C(Br)C=C1 KUFSHIHMAHIGFS-UHFFFAOYSA-N 0.000 description 1
- YPIVXJUHNLBQFJ-UHFFFAOYSA-N 1-(4-bromophenyl)-2-[4-(trifluoromethyl)phenyl]ethanone Chemical compound C1=CC(C(F)(F)F)=CC=C1CC(=O)C1=CC=C(Br)C=C1 YPIVXJUHNLBQFJ-UHFFFAOYSA-N 0.000 description 1
- MOSIKPSTRPODHQ-UHFFFAOYSA-N 1-(4-bromophenyl)-2-phenylethan-1-one Chemical compound C1=CC(Br)=CC=C1C(=O)CC1=CC=CC=C1 MOSIKPSTRPODHQ-UHFFFAOYSA-N 0.000 description 1
- FFRPJVVCCPSJBJ-UHFFFAOYSA-N 1-ethenyl-4-[2-(2-methoxyethoxy)ethoxy]benzene Chemical compound COCCOCCOC1=CC=C(C=C)C=C1 FFRPJVVCCPSJBJ-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical group COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- SLNYBUIEAMRFSZ-UHFFFAOYSA-N 2-(2-{2-[2-(2-methoxy-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethanol Chemical compound COCCOCCOCCOCCOCCO SLNYBUIEAMRFSZ-UHFFFAOYSA-N 0.000 description 1
- ROQKINZEVKZSGI-UHFFFAOYSA-N 2-[2-(2-methoxyethoxy)ethoxy]benzaldehyde Chemical compound COCCOCCOC1=CC=CC=C1C=O ROQKINZEVKZSGI-UHFFFAOYSA-N 0.000 description 1
- IUDNRKGPFWUYIC-UHFFFAOYSA-N 2-[2-(2-methoxyethoxy)ethoxy]ethyl 4-methylbenzenesulfonate Chemical compound COCCOCCOCCOS(=O)(=O)C1=CC=C(C)C=C1 IUDNRKGPFWUYIC-UHFFFAOYSA-N 0.000 description 1
- SZGNWRSFHADOMY-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound COCCOCCOCCOCCOCCOCCOCCOCCO SZGNWRSFHADOMY-UHFFFAOYSA-N 0.000 description 1
- OXZYBOLWRXENKT-UHFFFAOYSA-N 4-(trifluoromethyl)benzoyl chloride Chemical compound FC(F)(F)C1=CC=C(C(Cl)=O)C=C1 OXZYBOLWRXENKT-UHFFFAOYSA-N 0.000 description 1
- XLWQUESMILVIPR-UHFFFAOYSA-N 4-ethoxybenzoyl chloride Chemical compound CCOC1=CC=C(C(Cl)=O)C=C1 XLWQUESMILVIPR-UHFFFAOYSA-N 0.000 description 1
- NQUVCRCCRXRJCK-UHFFFAOYSA-N 4-methylbenzoyl chloride Chemical compound CC1=CC=C(C(Cl)=O)C=C1 NQUVCRCCRXRJCK-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- HPRZVRMPEUXGNG-SNAWJCMRSA-N CCC(C1=CC=C(/C=C/C(C=C2)=CC=C2OCCOCCOC)C=C1)=O Chemical compound CCC(C1=CC=C(/C=C/C(C=C2)=CC=C2OCCOCCOC)C=C1)=O HPRZVRMPEUXGNG-SNAWJCMRSA-N 0.000 description 1
- 102100026735 Coagulation factor VIII Human genes 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- TUEYHEWXYWCDHA-UHFFFAOYSA-N ethyl 5-methylthiadiazole-4-carboxylate Chemical compound CCOC(=O)C=1N=NSC=1C TUEYHEWXYWCDHA-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000013100 final test Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012949 free radical photoinitiator Substances 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- FHHGCKHKTAJLOM-UHFFFAOYSA-N hexaethylene glycol monomethyl ether Chemical compound COCCOCCOCCOCCOCCOCCO FHHGCKHKTAJLOM-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- XGISHOFUAFNYQF-UHFFFAOYSA-N pentanoyl chloride Chemical compound CCCCC(Cl)=O XGISHOFUAFNYQF-UHFFFAOYSA-N 0.000 description 1
- DUCKXCGALKOSJF-UHFFFAOYSA-N pentanoyl pentanoate Chemical compound CCCCC(=O)OC(=O)CCCC DUCKXCGALKOSJF-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- UFUASNAHBMBJIX-UHFFFAOYSA-N propan-1-one Chemical compound CC[C]=O UFUASNAHBMBJIX-UHFFFAOYSA-N 0.000 description 1
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
- C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
- C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/52—Amides or imides
- C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F120/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及新材料有机化学品技术领域,为一种LED敏感二苯乙烯基肟酯型光引发剂及其制备和应用。特别涉及一类LED敏感的水溶性光聚合引发剂,其为式I所示的缩乙二醇单甲醚连接二苯乙烯基的肟酯,其化学制备工艺技术,其作为辐射固化光引发剂的用途,以及其在辐射固化配方产品,特别是UV‑Vis‑LED可激发的光固化水性涂料或油墨、3D打印、水凝胶等诸多场合的应用用途。
Description
【技术领域】
本发明涉及新材料有机化学品技术领域,特别涉及一类LED敏感的水溶性光聚合引发剂,通过在二苯乙烯基肟酯型光引发剂中引入缩乙二醇单甲醚结构以赋予其水溶性,其化学制备工艺技术,其作为辐射固化光引发剂的用途,以及其在辐射固化配方产品,如涂料或油墨、3D打印,特别是水凝胶等诸多场合的应用用途。
【背景技术】
光引发剂化合物是一类重要的精细有机化学品材料。在以紫外光或可见(UV)光或LED(即Light-Emitting Diode)为光源的辐射固化技术领域,可在光辐照条件下生成自由基活性物种的光引发剂化合物是诱发含烯不饱和体系进行高效光聚合反应的关键物质因此是重要的辐射固化配方组分之一。光固化具有节能环保,高效快速和时间-空间可控等诸多优点,已广泛应用于涂料油墨、胶黏剂等传统领域以及3D打印等高新技术产品中。但是传统光固化仍存在一些不足之处,尤其是一般都要在体系中加入活性稀释剂和少量具有挥发性的有机溶剂,而这些通常会损害人体健康及污染环境。水溶性光引发剂则可以在使用过程中,用水代替活性稀释剂,更安全更环保,尤其是具有潜在的生物方面的应用,如水凝胶、药物载体等等。
目前市场上最为常用的水溶性是I2959,其结构式如下。但是I2959的水溶性较差,而且在LED光源波长内吸收较低。而与传统的紫外光固化相比,利用发光二极管作为光源的LED光固化具有能量利用率高、热效应小、不产生臭氧等显著优点。因此通过合理的分子设计开发出一系列LED可引发的水溶性光引发剂具有非常大的应用前景。
二苯乙烯基结构的肟酯在近紫外和可见光区都具有良好的光吸收性能,而且其热稳定性也比较优异,是一类非常具有潜在应用价值的自由基光引发剂。另外,缩乙二醇单甲醚的结构具有优良的水溶性,与二苯乙烯基的肟酯相结合可以制备出一种优异的水溶性光引发剂,且具有潜在的生物方面的应用,如水凝胶的合成等。
针对上述技术挑战,发明一类对LED光源敏感的、在光固化领域中具有高感光性、稳定性高、且易于制备,同时又有生物友好性的水溶性光引发剂是非常必要的,另外,这样的引发剂合成步骤应该具有简便、成本较低且合成过程环保、三废少等优点。随着人们对于环境保护、生产安全意识及劳保各类要求的不断提高、以及光聚合技术的不断发展,LED、LDI等低能耗、高安全性且环保的曝光灯源成为了本领域技术应用和发展的一种趋势。
【发明内容】
本项申请的目的是提供一类LED敏感的二苯乙烯基肟酯型水溶性光引发剂,其分子结构如下图(I)所示:
式Ⅰ中,R1,R2各自独立地选自含有1-20个碳原子(标记为C1-C20,下同)的直链或支链烷基、C3-C12环烷基、环烷基烷基、环杂烷基烷基、C6-C12芳基、烷基芳基,其中芳基可以被其他取代基,包括氢,卤素原子,R,OR,SR,SOR,SO2R,NRR’,CH2OH,CH2OR,CH2OCOR,CH2SR,CH2SCOR,或CH2NRR’,其中R是含有1-24个碳原子的直链或支链的烷基或-C6-C24芳基,R结构中可以用氟原子取代氢原子形成氟碳链结构,R结构中可以含有1-6个非连续的氧,氮,或硫元素,R和R’同时存在时也可以形成一个3-6元的环系结构等取代形成各种取代芳基。
n为3-20的整数。
本发明还提供了该类光引发的制备方法,其通用的合成工艺如下图所示:
在该引发剂的制备过程中:
步骤a中,含有不同链节数的缩乙二醇单甲醚与对甲基苯磺酰氯在碱催化下制备出苯磺酸盐的结构(I)-a,溶剂为二氯甲烷,反应温度为室温,反应时间8小时,产物用二氯甲烷萃取后蒸干即可;
步骤b中,将步骤a的产物(I)-a与对羟基苯甲醛在碱催化下制备出结构(I)-b,溶剂为N,N-二甲基甲酰胺,反应温度为110℃,反应时间12小时,产物通过柱层析提纯;
步骤c中,步骤b的产物(I)-b在催化剂作用下通过Witting反应制备出苯乙烯结构(I)-c,催化剂为甲基三苯基溴化膦和叔丁醇钾,溶剂为四氢呋喃,反应温度为0℃,反应时间8小时,该过程需要无水无氧操作,产物通过柱层析提纯;
步骤d中,带有不同取代基的羰基取代溴苯与(I)-c在催化剂下制备出二苯乙烯共轭结构(I)-d,催化剂为碳酸钾/双三苯基膦氯化钯,溶剂为N,N-二甲基甲酰胺,反应温度为110-120℃,反应时间3-5小时,该过程需要无水无氧操作,产物通过柱层析或者重结晶提纯;
步骤e中,将步骤d的产物(I)-d与亚硝酸异戊酯在浓盐酸的催化下制备出肟结构(I)-e,溶剂为四氢呋喃,反应温度为室温,反应时间1-2小时,产物沉淀出来后洗涤即可;
步骤f中,将步骤e的产物(I)-e与酰氯或者酸酐在碱催化下制备出肟酯结构(I)-f,溶剂为二氯甲烷,反应温度为0-5℃,反应时间3-5小时,该过程需要无水无氧操作。
在步骤a中,所用的碱优先选用三乙胺等有机碱。
在步骤d中也可以用醋酸钯/邻甲基三苯基膦为催化剂,用三乙胺吸收产生的酸,溶剂可为乙腈或四氢呋喃等,反应温度60-90℃,反应时间6-24小时,产物通过柱层析或者重结晶提纯。
上述通式中化合物的制备方法我们将结合实施例子做进一步的示例性说明。
本发明中,通式(I)所示二苯乙烯基肟酯型水溶性光引发剂在光固化配方体系中作为光引发剂或其它功能性添加剂成分的用途,及在化学合成中作为中间体或原料或试剂的用途。
本发明进一步披露一种含有上述通式(I)化合物可经由光(紫外或可见光或LED光或等价光源)辐射固化的混合物。
该类光辐射固化配方体系的特征是:
(1)含有至少一种通式(I)或(II)所描述的化合物作为光引发剂或光引发剂组分之一;
(2)含有至少一种含烯键(C=C)不饱和化合物。
以体系中含烯键不饱和组分总量每100份重量计算,含有的通式(I)化合物的合适的量是0.01-30重量份,优选0.5-10重量份。合适的辐射固化体系包含的可聚合的含烯键不饱和组分是可以通过该双键的自由基聚合反应被交联的化合物或混合物,这种含烯键不饱和组分可以是单体,低聚物或预聚物,或是它们的混合物或共聚物,或是上述组分的水性分散体。
具体步骤如下:(1)按单体:光引发剂:助剂的质量比100:0.5~1:0~4.5配比原料;(2)搅拌使其充分溶解;(3)以不同波长或者不同光强的光源照射聚合体系;(4)可以用在线红外的方法通过其特征峰的变化研究聚合转化率;其中:步骤(3)中的光源可为LED(高压,中压和低压),以及发射波长是365~425nm的LEDs,LDI光源。
上述所述的合适辐射固化体系均可以含有根据实际需要所添加的无机或有机填充剂和/或着色剂(例如颜料或染料等),以及其它添加剂(例如紫外线吸收剂,光稳定剂,阻燃剂,流平剂,或消泡剂等)和溶剂等任意成分。
合适的自由基聚合的单体是例如含烯键可聚合单体,包括但不限于(甲基)丙烯酸酯,丙烯醛,烯烃,共轭双烯烃,苯乙烯,马来酸酐,富马酸酐,乙酸乙烯酯,乙烯基吡咯烷酮,乙烯基咪唑,(甲基)丙烯酸,(甲基)丙烯酸衍生物例如(甲基)丙烯酰胺,乙烯基卤化物,亚乙烯基卤化物等。
合适的含烯键预聚物和低聚物包括但不限于(甲基)丙烯酰官能基的(甲基)丙烯酸共聚物,聚氨酯甲酸酯(甲基)丙烯酸酯,聚酯(甲基)丙烯酸酯,不饱和聚酯,聚醚(甲基)丙烯酸酯,硅氧烷(甲基)丙烯酸酯,环氧树脂(甲基)丙烯酸酯等,以及上述物质的水溶性或水分散性的类似物。
上述无论是含烯单体还是低聚物,预聚物,或共聚物,对本专业从业技术人员而言,都是熟知的,并无特别限定。
对于本发明的要旨,我们将结合下述系列实施例进一步说明。
符合通式(I)结构的示例性化合物列举如下:
【具体实施方式】
下面,通过实施例对本发明的实施方式进行具体的说明,但本发明的实施方式并不限定于这些实施例。
实施例1:示例化合物(I)-1的制备
(a)在单口烧瓶中加入三缩乙二醇单甲醚(50mmol)和三乙胺(55mmol)于100毫升二氯甲烷中,置于室温下搅拌,逐滴加入对甲基苯磺酰氯(55mmol)的二氯甲烷溶液。5小时后,TCL监测原料消失,体系中加入100毫升去离子水,用二氯甲烷萃取,有机层减压蒸干,产物为橙色液体,产率95.64%。
(b)在单口烧瓶中加入2-(2-(2-甲氧基乙氧基)乙氧基)乙基4-甲基苯磺酸盐(48mmol)、对羟基苯甲醛(48mmol)和碳酸钾(58mmol)于80毫升N,N-二甲基甲酰胺(DMF)中,置于110摄氏度油浴中搅拌反应。3小时后,TCL监测原料消失,减压浓缩DMF,体系中加入50毫升去离子水,用二氯甲烷萃取,有机层减压蒸干,产物为橙黄色液体,产率96.45%。
(c)在干燥的三颈烧瓶中,氮气保护下,依次加入4-(2-(2-(2-甲氧基乙氧基)乙氧基)乙氧基)苯甲醛(45mmol)和甲基三苯基溴化膦(45mmol)于20毫升四氢呋喃(THF)中,置于冰浴下冷却至0摄氏度,待体系变成亮黄色后,逐滴加入叔丁醇钾(45mmol),半小时后,将体系置于室温下反应。3小时后,TCL监测原料消失,体系中加入100毫升去离子水,用二氯甲烷萃取,有机层减压蒸干,产物为淡黄色液体,产率88.67%。
(d)在干燥的三颈烧瓶中,氮气保护下,依次加入2-(2-(2-甲氧基乙氧基)乙氧基)乙氧基-4-乙烯基苯(40mmol)、4-溴苯丙酮(44mmol)、双三苯基膦二氯化钯(1mmol)、碳酸钾(60mmol)于60毫升干燥的N,N-二甲基甲酰胺(DMF)中,置于120摄氏度油浴中搅拌反应,半小时后体系颜色变黑。6小时后,TCL监测原料消失,减压浓缩DMF,体系中加入100毫升去离子水,抽滤析出的沉淀,干燥后用柱层析提纯,产物为黄色固体,产率90.40%。
(e)在单口烧瓶中加入1-(4-(4-(2-(2-(2-甲氧基乙氧基)乙氧基)乙氧基)苯乙烯基)苯基)丙-1-酮(35mmol)和亚硝酸异戊酯(38mmol)于40毫升四氢呋喃中,置于室温下搅拌,逐滴加入3.5毫升浓盐酸。3小时后,TCL监测原料消失,减压浓缩THF,体系中加入50毫升去离子水,用二氯甲烷萃取,有机层减压蒸干,产物为黄色固体,产率90.06%。
(f)在干燥的三颈烧瓶中,氮气保护下,加入2-(羟基亚氨基)-1-(4-4-(2-(2-(2-甲氧基乙氧基)乙氧基)乙氧基)苯乙烯基)苯基)丙-1-酮(30mmol)和三乙胺(60mmol)于40毫升二氯甲烷(DCM)中,置于冰浴下冷却至0摄氏度,逐滴加入乙酸酐(60mmol),加完后保持在0摄氏度下搅拌反应。3小时后,TCL监测原料消失,体系中加入60毫升去离子水,分液出有机层,减压蒸馏,产物为黄色固体,产率85.82%。HR-MS(C26H31NO7):m/e:469.2101;实验结果:470.2163(M+H+)。
实施例2:引发剂2-16的制备
这些引发剂的制备方法与实施例1制备的引发剂(I)-1类似,不同之处在于在步骤d中使用不同取代基的4-溴苯酮和步骤f中使用不同的酰氯或酸酐。如在步骤d中,(I)-11和(I)-12使用与(I)-1相同的4-溴苯丙酮,而(I)-2,(I)-13,(I)-14使用4-溴苯丁酮,(I)-3使用1-(4-溴苯基)-2-苯基乙烷-1-酮,(I)-4使用1-(4-溴苯基)-2-(对甲苯基)乙烷-1-酮,(I)-5使用1-(4-溴苯基)-2-(4-(三氟甲基)苯基)乙烷-1-酮,(I)-6使用4-溴苯戊酮。在步骤f中,(I)-2,(I)-3,(I)-4和(I)-5使用与(I)-1相同的乙酸酐或乙酰氯,而(I)-6和(I)-13使用丙酸酐或丙酰氯,(I)-7使用丁酸酐或丁酰氯,(I)-8使用戊酸酐或戊酰氯,(I)-9和(I)-14使用苯甲酸酐或苯甲酰氯,(I)-10使用4-甲基苯甲酰氯,(I)-11使用4-乙氧基-苯甲酰氯,(I)-12使用4-三氟甲基-苯甲酰氯,从而制备出带有不同吸电子和推电子基团的二苯乙烯基肟酯型水溶性引发剂。
(I)-2,产率58%,淡黄色固体。HR-MS(C27H38NO7):m/e:483.2257;实验结果:484.2265(M+H+)。
(I)-3,产率61%,淡黄色固体。HR-MS(C31H33NO7):m/e:531.2257;实验结果:532.2265(M+H+)。
(I)-4,产率58%,黄色固体。HR-MS(C33H35NO7):m/e:545.2414;实验结果:546.2413(M+H+)。
(I)-5,产率59%,黄色固体。HR-MS(C32H32F3NO7):m/e:599.2131;实验结果:600.2163(M+H+)。
(I)-6,产率58%,黄色固体。HR-MS(C28H35NO7):m/e:497.2414;实验结果:498.2423(M+H+)。
(I)-7,产率61%,黄色固体。HR-MS(C27H33NO7):m/e:483.2257;实验结果:484.2265(M+H+)。
(I)-8,产率64%,黄色固体。HR-MS(C28H35NO7):m/e:497.2414;实验结果:498.2465(M+H+)。
(I)-9,产率68%,黄色固体。HR-MS(C31H33NO7):m/e:531.2257;实验结果:532.2235(M+H+)。
(I)-10,产率64%,黄色固体。HR-MS(C32H35NO7):m/e:545.2414;实验结果:546.2425(M+H+)。
(I)-11,产率59%,黄色固体。HR-MS(C33H37NO7):m/e:575.2519;实验结果:576.2528(M+H+)。
(I)-12,产率59%,黄色固体。HR-MS(C32H32F3NO7):m/e:599.2131;实验结果:600.2125(M+H+)。
(I)-13,产率56%,黄色固体。HR-MS(C28H35NO7):m/e:497.2414;实验结果:498.2428(M+H+)。
(I)-14,产率61%,黄色固体。HR-MS(C32H35NO7):m/e:454.2414;实验结果:455.2435(M+H+)。
实施例3:引发剂15-20的制备
这些引发剂的制备方法与引发剂1类似,不同之处在于用不同长度的缩乙二醇单甲醚制备出不同程度水溶性的肟酯型光引发剂。如(I)-15使用四缩乙二醇单甲醚,(I)-16使用五缩乙二醇单甲醚,(I)-17使用六缩乙二醇单甲醚,(I)-18,(I)-19和(I)-20使用八缩乙二醇单甲醚。
(I)-15,产率56%,黄色固体。HR-MS(C28H35NO8):m/e:513.2363;实验结果:514.2345(M+H+)。
(I)-16,产率55%,黄色固体。HR-MS(C30H39NO9):m/e:557.2625;实验结果:558.2635(M+H+)。
(I)-17,产率57%,黄色固体。HR-MS(C32H43NO10):m/e:601.2887;实验结果:602.2875(M+H+)。
(I)-18,产率60%,黄色固体。HR-MS(C36H51NO12):m/e:689.3411;实验结果:690.3423(M+H+)。
(I)-19,产率58%,黄色固体。HR-MS(C41H53NO12):m/e:751.3568;实验结果:752.3556(M+H+)。
(I)-20,产率59%,黄色固体。HR-MS(C42H55NO12):m/e:765.3724;实验结果:766.3715(M+H+)。
实施例4:薄膜聚合反应
依据下述的重量百分比配制光固化测试样品:环氧丙烯酸酯,28份;聚酯丙烯酸酯,32份;己二醇二丙烯酸酯,6份;季戊四醇三丙烯酸酯24份;二氧化钛染料,16份;选取的实施例(I)-1的光引发剂,4份。
取部分上述混合物充分研磨均匀后涂布在白色ABS基板上,在空气下形成约20微米的图层。以385nmLED固化试验机(和光同盛,广州)距离样品2厘米处辐照,传送带速度为20m/min。指压刮擦发判定涂层完全固化情况。上述实施例化合物中的光引发剂均引发膜层完全固化,显示了良好的光引发性能。
实施例5:厚膜聚合反应
配方同实施例4。
取部分上述混合物充分研磨厚徒步在白色ABS基板上,在空气下形成约200微米的图层。以385nmLED固化试验机(和光同盛,广州)距离样品2厘米处辐照,传送带速度为10m/min。压刮擦发判定涂层完全固化情况。上述实施例化合物中的光引发剂均引发膜层完全固化,显示了良好的光引发性能。
实施例6:水性聚合反应
依据下述的重量百分比配制光固化测试样品:丙烯酰胺,12份;去离子水,70份;二氧化钛染料,16份;选取的实施例(I)-1的光引发剂,2份。
取部分上述混合物充分研磨厚徒步在白色ABS基板上,在空气下形成约200微米的图层。以385nmLED固化试验机(和光同盛,广州)距离样品2厘米处辐照,传送带速度为10m/min。压刮擦发判定涂层完全固化情况。上述实施例化合物中的光引发剂均引发膜层完全固化,显示了良好的光引发性能。
实施例7:水性聚合反应
通过将甲基丙烯酸羟乙酯HEMA(0.5M),马来酰亚胺基聚乙二醇单甲醚mtthoxyPEGMA(0.2M,Mn≈300)和聚乙二醇二甲基丙烯酸酯PEGDMA(0.02M,Mn≈2000)在水中混合并通过实施例1中的引发剂来构建水凝胶(室温下1%w/w)。将该混合物搅拌并倒入模具中进行交联3小时。用新鲜PBS提取所得水凝胶以除去未反应的单体和残留的化学物质,然后将水凝胶置于PBS在黑暗中进一步稳定48小时后进行测试。
测试得到该水凝胶的聚合转化率为75.3%,动态平衡含水量为77.2%,其中,聚合转化率的计算公式为
其中,m0是所有单体及引发剂的质量,mdry是所得到的水凝胶的实际质量。
动态平衡水含量(EWC)的计算公式为
其中,mwet是水凝胶的实际质量,mdry是将水凝胶用滤纸吸干表面水分后所得到的质量。
将用PBS平衡至少48小时后的水凝胶样品切成直径为20mm的圆柱体。在25℃下使用一个20mm平行板在应力控制流变仪(HAAKE MARS III)上测量水凝胶的动态粘弹性。首先将上板移动到样品表面上方约2mm来设定上板和样品盘之间的间隙。上板非常缓慢地下降(5μms-1),同时监测法向力并且在100mN的极限法向力时停止。在水凝胶上进行动态应力和频率扫描流变学实验。首先进行应力扫描,以在1-100Pa的应力范围内以1Hz的恒定频率探索线性粘弹性区域(LVER)。以恒定应力(10pa)模式记录频率扫描振荡测试,并控制在0.1-50Hz的频率范围内以使测量值保持在线性范围内。G'和G”的值以1Hz确定。最终得到测试结果为G'=1356.2Pa,G”=135.3Pa。
需要强调的是,上述列举的实施例仅是一些示例性试验,不应被视为是限定性试验或条件。本发明申请所涵盖的创新范围应以权利要求书记载为准。
Claims (5)
1.一类LED敏感的缩乙二醇单甲醚连接二苯乙烯基的肟酯型光引发剂,其特征在于,这类光引发剂的分子结构如通式(I)所示:
式(Ⅰ)中,R1,R2各自独立地选自含有1-20个碳原子(标记为C1-C20,下同)的直链或支链烷基、C3-C12环烷基、环烷基、环杂烷基、C6-C12芳基、烷基芳基,
其中上述芳基被其他取代基取代,包括氢,卤素原子,R,OR,SR,SOR,SO2R,CH2OH,CH2OR,CH2OCOR,CH2SR,或CH2SCOR,
所述取代基中的R是含有1-24个碳原子的直链或支链的烷基或-C6-C24芳基,R结构中用氟原子取代氢原子形成氟碳链结构,R结构中含有1-6个非连续的氧,氮,或硫元素;
n为3-20的整数。
3.根据权利要求2所述制备方法,其特征在于,该光引发剂的制备过程包括以下步骤:
(1)步骤a中,含有不同重复单元数(n)的缩乙二醇单甲醚与对甲基苯磺酰氯在碱催化下制备出苯磺酸盐的结构(I)-a,溶剂为二氯甲烷,反应温度为室温,反应时间8小时,产物用二氯甲烷萃取后蒸干即可;
(2)步骤b中,将步骤a的产物(I)-a与对羟基苯甲醛在碱催化下制备出结构(I)-b,溶剂为N,N-二甲基甲酰胺,反应温度为110℃,反应时间12小时,产物通过柱层析提纯;
(3)步骤c中,步骤b的产物(I)-b在催化剂作用下通过Witting反应制备出苯乙烯结构(I)-c,催化剂为甲基三苯基溴化膦和叔丁醇钾,溶剂为四氢呋喃,反应温度为0-10℃,反应时间8小时,该过程需要无水无氧操作,产物通过柱层析提纯;
(4)步骤d中,带有不同取代基的羰基取代溴苯与(I)-c在催化剂下制备出二苯乙烯共轭结构(I)-d,催化剂为碳酸钾/双三苯基膦氯化钯,溶剂为N,N-二甲基甲酰胺,反应温度为110-120℃,反应时间3-5小时,该过程需要无水无氧操作,产物通过柱层析或者重结晶提纯;
(5)步骤e中,将步骤d的产物(I)-d与亚硝酸异戊酯在浓盐酸的催化下制备出肟结构(I)-e,溶剂为四氢呋喃,反应温度为室温,反应时间1-2小时,产物沉淀出来后洗涤即可;
(6)步骤f中,将步骤e的产物(I)-e与酰氯或者酸酐在碱催化下制备出肟酯结构(I)-f,溶剂为二氯甲烷,反应温度为0-5℃,反应时间3-5小时,该过程需要无水无氧操作。
4.根据权利要求3所述制备方法,其特征在于,步骤a中,所用的碱选用三乙胺有机碱。
5.根据权利要求3所述制备方法,其特征在于,步骤d中用醋酸钯/邻甲基三苯基膦为催化剂,用三乙胺吸收产生的酸,溶剂为乙腈或四氢呋喃,反应温度60-90℃,反应时间6-24小时,产物通过柱层析或者重结晶提纯。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011327985.0A CN112521529B (zh) | 2020-11-24 | 2020-11-24 | 一种led敏感二苯乙烯基肟酯型光引发剂及其制备和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011327985.0A CN112521529B (zh) | 2020-11-24 | 2020-11-24 | 一种led敏感二苯乙烯基肟酯型光引发剂及其制备和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112521529A CN112521529A (zh) | 2021-03-19 |
CN112521529B true CN112521529B (zh) | 2022-07-08 |
Family
ID=74992933
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011327985.0A Active CN112521529B (zh) | 2020-11-24 | 2020-11-24 | 一种led敏感二苯乙烯基肟酯型光引发剂及其制备和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112521529B (zh) |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5669386B2 (ja) * | 2009-01-15 | 2015-02-12 | 富士フイルム株式会社 | 新規化合物、重合性組成物、カラーフィルタ、及びその製造方法、固体撮像素子、並びに、平版印刷版原版 |
KR102369426B1 (ko) * | 2014-04-04 | 2022-03-03 | 가부시키가이샤 아데카 | 옥심에스테르 화합물 및 상기 화합물을 함유하는 광중합 개시제 |
CN104910053B (zh) * | 2014-06-09 | 2017-09-12 | 北京英力科技发展有限公司 | 不对称二肟酯化合物及其制造方法与应用 |
CN107344918B (zh) * | 2017-05-26 | 2020-06-16 | 同济大学 | 一类含二苯乙烯的肟酯类化合物及其制备方法和应用 |
EP3539924A1 (en) * | 2018-03-14 | 2019-09-18 | ETH Zurich | Novel vinyl phosphines and photo-initiators obtainable therefrom |
CN109991811A (zh) * | 2019-02-27 | 2019-07-09 | 江苏南大光电材料股份有限公司 | 一种酸扩散抑制剂及其制备方法与光刻胶组合物 |
CN110092851B (zh) * | 2019-04-30 | 2021-06-04 | 同济大学 | Led敏感的杂化型光引发剂及其制备方法和应用 |
-
2020
- 2020-11-24 CN CN202011327985.0A patent/CN112521529B/zh active Active
Also Published As
Publication number | Publication date |
---|---|
CN112521529A (zh) | 2021-03-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP2514804B2 (ja) | 共重合性光開始剤 | |
WO2018049976A1 (zh) | 芴类光引发剂、其制备方法、具有其的光固化组合物及其在光固化领域的应用 | |
Eren et al. | Thioxanthone-functionalized 1, 6-heptadiene as monomeric photoinitiator | |
US9353207B2 (en) | Alkylphenyl derivatives and application thereof as photoinitiator | |
CN114478436B (zh) | 一种含有可聚合的衣康酸基团改性的α-氨基酮类光引发剂及其制备方法和用途 | |
JP7387267B2 (ja) | 多環芳香族骨格を有するエンドペルオキシド化合物 | |
WO2019101142A1 (zh) | 二丁基芴基衍生物与其作为光引发剂的应用 | |
CN110117262B (zh) | 2-苯乙烯基苯并恶唑或苯并噻唑基酮肟酯类化合物及其制备方法和应用 | |
Chen et al. | Synthesis and preliminary photopolymerization envaluation of photopolymerizalbe type II photoinitiators BRA and TXRA | |
CN107400144B (zh) | 酰基膦(氧)化合物及其制备方法和应用 | |
Wu et al. | Synthesis and characterization of low-migration bisacylphenylphosphine oxide photoinitiators | |
CN112409550B (zh) | Led敏感二苯乙烯基肟酯型水溶性光引发剂制备及其应用 | |
CN114716315A (zh) | 一种芳乙烯基α-羰基酸酯类化合物在LED光聚合中作为光引发剂的用途及其制备方法 | |
CN112521529B (zh) | 一种led敏感二苯乙烯基肟酯型光引发剂及其制备和应用 | |
CN112961165B (zh) | 咔唑并吡喃化合物及其应用 | |
CN110156711B (zh) | 含有苯并恶唑或苯并噻唑基团的肟酯类化合物及其制备方法和应用 | |
CN114751861B (zh) | 一种含有吡唑啉和n,n-二烷基苯甲酸酯的分子内敏化大分子光引发剂及制备方法和用途 | |
CN114605572B (zh) | 一种含有可聚合基团乙烯基改性的α-氨基酮类光引发剂及其制备方法和用途 | |
WO2023174056A1 (zh) | 一种含有α-氨基酮多官能化大分子光引发剂及其制造方法和应用 | |
CN112441953A (zh) | 含二苯硫醚基酮甲酸酯水溶性光聚合引发剂及其制备方法 | |
CN112961099B (zh) | 一种双咔唑类肟酯型光引发剂及制备方法和应用 | |
CN110078693B (zh) | 含有香豆素的α-羟基酮类化合物及其制备方法和应用 | |
CN113683714B (zh) | 一种适用于uv-led有氧光固化的含供氢体硫醚型萘酰亚胺衍生物类光引发剂 | |
EP2858969B1 (en) | Copolymerizable photoinitiators | |
CN114591241B (zh) | 一种含有吡唑啉和α-氨基酮的分子内敏化大分子光引发剂及其制备方法和应用 |
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 |