CN112409550A - Preparation and application of LED-sensitive distyryl oxime ester water-soluble photoinitiator - Google Patents
Preparation and application of LED-sensitive distyryl oxime ester water-soluble photoinitiator Download PDFInfo
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- CN112409550A CN112409550A CN202011316117.2A CN202011316117A CN112409550A CN 112409550 A CN112409550 A CN 112409550A CN 202011316117 A CN202011316117 A CN 202011316117A CN 112409550 A CN112409550 A CN 112409550A
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- product
- photoinitiator
- light
- hours
- led
- Prior art date
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- -1 distyryl oxime ester Chemical class 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract description 13
- 238000003847 radiation curing Methods 0.000 claims abstract description 9
- 238000009472 formulation Methods 0.000 claims abstract description 4
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 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 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 8
- 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
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical group ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 claims description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-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 3
- 150000001412 amines Chemical group 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 claims description 3
- 150000002923 oximes Chemical group 0.000 claims description 3
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 3
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 claims description 3
- 235000021286 stilbenes Nutrition 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 125000005265 dialkylamine group Chemical group 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 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
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims 3
- 125000003118 aryl group Chemical group 0.000 claims 2
- 239000002585 base Substances 0.000 claims 2
- 150000007529 inorganic bases Chemical class 0.000 claims 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims 1
- 229910052753 mercury Inorganic materials 0.000 claims 1
- 150000007530 organic bases Chemical class 0.000 claims 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 239000000017 hydrogel Substances 0.000 abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 238000001723 curing Methods 0.000 abstract description 12
- 238000000576 coating method Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000010146 3D printing Methods 0.000 abstract description 3
- 239000000976 ink Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000007787 solid Substances 0.000 description 26
- 239000000047 product Substances 0.000 description 22
- 238000004896 high resolution mass spectrometry Methods 0.000 description 20
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 239000011248 coating agent Substances 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
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 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
- 239000010408 film Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000007790 scraping Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- KEOLYBMGRQYQTN-UHFFFAOYSA-N (4-bromophenyl)-phenylmethanone Chemical compound C1=CC(Br)=CC=C1C(=O)C1=CC=CC=C1 KEOLYBMGRQYQTN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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
- 238000007341 Heck reaction Methods 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
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 2
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical group BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000011161 development Methods 0.000 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 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000001698 laser desorption ionisation Methods 0.000 description 2
- 230000031700 light absorption Effects 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000003544 oxime group Chemical group 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000003595 spectral effect Effects 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
- CFMMTXJMIJRUSH-UHFFFAOYSA-N 1-(4-bromophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C(Br)C=C1 CFMMTXJMIJRUSH-UHFFFAOYSA-N 0.000 description 1
- KLNLMCGEDKBXKH-UHFFFAOYSA-N 1-[4-[2-(4-methylphenyl)ethenyl]phenyl]propan-1-one Chemical compound CC1=CC=C(C=CC2=CC=C(C=C2)C(CC)=O)C=C1 KLNLMCGEDKBXKH-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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-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
- RKIDDEGICSMIJA-UHFFFAOYSA-N 4-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=C(Cl)C=C1 RKIDDEGICSMIJA-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
- 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
- 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
- 239000002253 acid Substances 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 150000001263 acyl chlorides Chemical class 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
- 125000003277 amino group Chemical group 0.000 description 1
- MXMOTZIXVICDSD-UHFFFAOYSA-N anisoyl chloride Chemical compound COC1=CC=C(C(Cl)=O)C=C1 MXMOTZIXVICDSD-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 150000004768 bromobenzenes Chemical class 0.000 description 1
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect 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
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000001993 dienes Chemical class 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
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000013100 final test Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012949 free radical photoinitiator Substances 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 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
- 150000002596 lactones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- QARVLSVVCXYDNA-UHFFFAOYSA-N phenyl bromide Natural products BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 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
- 238000001556 precipitation Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- MGNVWUDMMXZUDI-UHFFFAOYSA-N propane-1,3-disulfonic acid Chemical compound OS(=O)(=O)CCCS(O)(=O)=O MGNVWUDMMXZUDI-UHFFFAOYSA-N 0.000 description 1
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 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
- 239000002352 surface water Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 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
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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水溶性光引发剂制备及其应用.特别涉及一类LED敏感的水溶性光聚合引发剂，其为式I所示的肟酯连接二苯乙烯基的磺酸季胺盐，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。 The invention relates to the technical field of organic chemicals of new materials, and is the preparation and application of an LED-sensitive distyryl oxime ester-type water-soluble photoinitiator. In particular, it relates to a type of LED-sensitive water-soluble photopolymerization initiator, which is of formula Oxime ester shown in I connects the sulfonic acid quaternary ammonium salt of distyryl group, its chemical preparation technology, its purposes as radiation curing photoinitiator, and its use in radiation curing formulation products, especially UV-Vis-LED can be Excited light-curing water-based coatings or inks, 3D printing, hydrogels and many other applications. 
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of new material organic chemicals, in particular to a class of LED sensitive water-soluble photopolymerization initiators, which is endowed with water solubility by introducing a quaternary ammonium salt structure into a distyryl oxime ester type photoinitiator, a chemical preparation process technology thereof, application of the photoinitiator as a radiation curing photoinitiator, and application of the photoinitiator in radiation curing formula products, such as coating or printing ink, 3D printing, particularly hydrogel and other occasions.
[ background of the invention ]
Photoinitiator compounds are an important class of fine organic chemical materials. In the field of radiation curing technology using ultraviolet Light or visible (UV) Light or LED (Light-Emitting Diode) as a Light source, a photoinitiator compound capable of generating radical active species under a Light irradiation condition is a key species for inducing an ethylenically unsaturated system to perform efficient photopolymerization, and thus is one of important radiation curing formulation components. Photocuring has the advantages of energy conservation, environmental protection, high efficiency, rapidness, controllable time-space and the like, and is widely applied to the traditional fields of coating, printing ink, adhesive and the like and high and new technical products such as 3D printing and the like. However, the conventional photo-curing method still has some disadvantages, especially the reactive diluent and a small amount of volatile organic solvent are generally added into the system, and the reactive diluent and the small amount of volatile organic solvent generally cause harm to human health and environmental pollution. The water-soluble photoinitiator can replace a reactive diluent with water during the use process, is safer and more environment-friendly, and particularly has potential biological applications, such as hydrogel, drug carriers and the like.
The water-soluble compound most commonly used in the market at present is I2959, and the structural formula of the water-soluble compound is shown as the following formula. However, I2959 has poor water solubility and low absorption at the LED source wavelength. Compared with the traditional ultraviolet light curing, the LED light curing using the light emitting diode as the light source has the obvious advantages of high energy utilization rate, small heat effect, no ozone generation and the like. Therefore, a series of water-soluble photoinitiators which can be initiated by the LED are developed through reasonable molecular design, and the method has a very great application prospect.
The oxime ester with a distyryl structure has good light absorption performance in near ultraviolet and visible light regions, has excellent thermal stability, and is a free radical photoinitiator with potential application value. In addition, the sulfonic acid quaternary ammonium salt has little toxicity to cells and is very suitable for being applied to the biological aspect.
In order to solve the technical challenges, a water-soluble photoinitiator which is sensitive to an LED light source, has high photosensitivity and high stability in the field of photocuring, is easy to prepare and is biologically friendly is very necessary. With the increasing requirements of people on environmental protection, production safety awareness and labor protection and the continuous development of photopolymerization technology, low-energy-consumption, high-safety and environment-friendly exposure lamp sources such as LEDs and LDIs become a trend for technical application and development in the field.
[ summary of the invention ]
The application aims to provide a distyryl oxime ester type water-soluble photoinitiator sensitive to LED, and the molecular structure of the photoinitiator is shown as the following formula (I):
in the formula (I), R1，R2Each independently selected from the group consisting of 1-20 carbon atoms (labeled C)1-C20Straight or branched alkyl of the following, C)3-C12Cycloalkyl, cycloalkylalkyl, cycloheteroalkylalkyl, C6-C12Aryl, alkylaryl, wherein the aryl radical may be substituted by other substituents, including hydrogen, halogen atoms, R, OR, SR, SOR, SO2R，NRR’，CH2OH，CH2OR， CH2OCOR，CH2SR，CH2SCOR, or CH2NRR' wherein R is a linear or branched alkyl group containing 1 to 24 carbon atoms or-C6-C24The structure of R can be fluorine atom to replace hydrogen atom to form fluorocarbon chain structure, the structure of R can contain 1-6 discontinuous oxygen, nitrogen or sulfur elements, R and R' can form a 3-6-membered ring system structure when existing at the same time to form various substituted aryl groups;
R3selected from the group consisting of those containing 1-20 carbon atoms (labeled C)1-C20Straight or branched alkyl of the following, C)3-C12Cycloalkyl, cycloalkylalkyl, cycloheteroalkylalkyl.
The invention also provides a preparation method of the photo-initiation, and the general synthesis process is shown as the following formula:
during the preparation of the initiator:
in step (a), with different R1Preparing a stilbene conjugated structure (I) -a from carbonyl substituted bromobenzene of a substituent group and p-methylstyrene under a Pd catalyst, wherein the catalyst can be potassium carbonate/bis (triphenylphosphine) palladium chloride, palladium acetate/tri (o-methylphenyl) phosphine/triethylamine, palladium acetate/triethanolamine, a solvent is acetonitrile and N, N-dimethylformamide, the reaction temperature is 90-140 ℃, the reaction time is 3-24 hours, the process needs anhydrous and oxygen-free operation, and a product is purified by column chromatography or recrystallization;
in the step (b), the product (I) -a obtained in the step (a) and isoamyl nitrite are catalyzed by concentrated hydrochloric acid to prepare an oxime structure (I) -b, tetrahydrofuran is used as a solvent, the reaction temperature is room temperature, the reaction time is 1-2 hours, and the product is precipitated and then washed;
step (ii) of
In the method, the product (I) -b in the step (b) is reacted with acyl chloride or acid anhydride under the anhydrous and oxygen-free conditions to prepare the oxime ester structure (I) -c under the base catalysis, and the solvent is dichloromethane orTetrahydrofuran, the reaction temperature is 0-5 ℃, the reaction time is 1-12 hours, and the alkali can be organic alkali or inorganic alkali such as triethylamine, NaOH, KOH, NaH and the like;
in the step (d), the product (I) -c in the step (c) reacts with NBS to prepare a benzyl bromide structure (I) -d, a small amount of azobisisobutyronitrile or dibenzoyl peroxide is used for catalytic initiation, the solvent is carbon tetrachloride, the reaction temperature is reflux temperature, the reaction time is 6-12 hours, and the product is purified by column chromatography;
in the step (e), the product (I) -d in the step (d) and dialkyl amine are catalyzed by alkali to prepare an amine structure (I) -e, the alkali can be inorganic alkali such as potassium carbonate, NaOH, KOH, NaH and the like, the solvent is ethanol, the reaction temperature is 30-60 ℃, the reaction time is 6-24 hours, and the product is purified by column chromatography;
in the step (f), the product (I) -e in the step (e) reacts with 1, 3-propane sultone to obtain the general formula (I), the solvent is acetone, the heating reflux is carried out, the reaction time is 6-24 hours, the process needs anhydrous and oxygen-free operation, the product can be directly filtered, and the product is obtained without further purification.
The preparation of the compounds of the above formula is further illustrated by reference to the examples.
In the invention, the distyryl oxime ester type water-soluble photoinitiator shown in the general formula (I) is used as a photoinitiator or other functional additive components in a photocuring formula system, and is used as an intermediate or a raw material or a reagent in chemical synthesis.
The invention further discloses a mixture containing the compound of the general formula (I) which can be cured by irradiation with light (ultraviolet or visible light or LED light or equivalent light sources).
The light radiation curing formula system is characterized in that:
(1) containing at least one compound described by the general formula (I) or (II) as a photoinitiator or one of the components of a photoinitiator;
(2) contains at least one ethylenically (C ═ C) unsaturated compound.
The compound of the formula (I) is suitably contained in an amount of 0.01 to 30 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the total amount of the ethylenically unsaturated components in the system. Suitable radiation-curable systems comprise polymerizable ethylenically unsaturated components which are compounds or mixtures which can be crosslinked by free-radical polymerization of the double bonds, which ethylenically unsaturated components can be monomers, oligomers or prepolymers, or mixtures or copolymers thereof, or aqueous dispersions of the above-mentioned components.
The method comprises the following specific steps: (1) according to the monomer: photoinitiator (2): the mass ratio of the auxiliary agent is 100: 0.5-1: 0-4.5 parts of raw materials; (2) stirring to fully dissolve; (3) irradiating the polymerization system by light sources with different wavelengths or different light intensities; (4) the polymerization conversion rate can be researched by the change of the characteristic peak of the polymer by an online infrared method; wherein: the light source in step (3) can be LEDs (high voltage, medium voltage and low voltage), LEDs with the emission wavelength of 365-425 nm, and LDI light source.
The above-mentioned suitable radiation-curing systems may contain any of inorganic or organic fillers and/or colorants (e.g., pigments or dyes, etc.), and other additives (e.g., ultraviolet absorbers, light stabilizers, flame retardants, leveling agents, defoaming agents, etc.) and solvents, which may be added as needed.
Suitable free radically polymerizable monomers are, for example, ethylenically-containing polymerizable monomers including, but not limited to, (meth) acrylates, acrolein, olefins, conjugated dienes, styrene, maleic anhydride, fumaric anhydride, vinyl acetate, vinyl pyrrolidone, vinyl imidazole, (meth) acrylic acid derivatives such as (meth) acrylamide, vinyl halides, vinylidene halides, and the like.
Suitable ethylenic-containing prepolymers and oligomers include, but are not limited to, (meth) acryloyl-functional (meth) acrylic copolymers, urethane (meth) acrylates, polyester (meth) acrylates, unsaturated polyesters, polyether (meth) acrylates, silicone (meth) acrylates, epoxy (meth) acrylates, and the like, as well as water-soluble or water-dispersible analogs of the foregoing.
The above-mentioned monomers, oligomers, prepolymers, or copolymers, whether containing olefins, are well known to those skilled in the art and are not particularly limited.
For the gist of the present invention, we will further describe it in connection with the following series of examples.
Exemplary compounds conforming to the structure of formula (I) are listed below:
compared with a commercial water-soluble 2959 photoinitiator, the photoinitiator has better light absorption performance in the ultraviolet light range of 365-; in addition, the inner salt type water-soluble photoinitiator has low toxicity, so the inner salt type water-soluble photoinitiator has wide application prospect.
[ detailed description ] embodiments
Hereinafter, embodiments of the present invention will be specifically described with reference to examples, but the embodiments of the present invention are not limited to these examples.
Example 1: preparation of exemplary Compound 1
(a) In a dry three-neck flask, under the protection of nitrogen, 4-methylstyrene (50mmol), 4-bromophenylacetone (50mmol), bis (triphenylphosphine) palladium dichloride (1mmol) and potassium carbonate (60mmol) are sequentially added into 60 ml of dry N, N-Dimethylformamide (DMF), the mixture is placed in a 120 ℃ oil bath and stirred for reaction, and the system becomes black after half an hour. After 6 hours, TCL monitors the disappearance of the raw material, DMF is concentrated under reduced pressure, 100 ml of deionized water is added into the system, the precipitated precipitate is filtered by suction, and the product is purified by column chromatography after being dried, so that the product is yellow solid, and the yield is 90.40%.
(b) 1- (4- (4-Methylstyryl) phenyl) propan-1-one (45mmol) and isoamyl nitrite (54mmol) were added to 50 ml of tetrahydrofuran in a single-neck flask, and stirred at room temperature, and 4.5 ml of concentrated hydrochloric acid was added dropwise. After 3 hours, TCL monitored the disappearance of the starting material, THF was concentrated under reduced pressure, 50 ml of deionized water was added to the system, extraction was performed with dichloromethane, the organic layer was evaporated to dryness under reduced pressure, the product was a yellow solid with a yield of 90.06%.
(c) In a dry three-neck flask, under the protection of nitrogen, 2- (oximido) -1- (4- (-4-methylstyrene group) phenyl) acetone (40mmol) and triethylamine (80mmol) were added to 80 ml of Dichloromethane (DCM), the mixture was cooled to 0 ℃ in an ice bath, acetyl chloride (80mmol) was added dropwise, and the reaction was stirred at 0 ℃ after the addition. After 3 hours, the TCL monitored the disappearance of the starting material, 80 ml of deionized water was added to the system, the organic layer was separated, and the product was distilled under reduced pressure to give a yellow solid in 85.82% yield.
(d) In a dry one-neck flask were added 2- (acetoxyimino) -1- (4- (4-methylstyryl) phenyl) acetone (35mmol), N-bromosuccinimide (NBS) (40mmol) and Azobisisobutyronitrile (AIBN) (0.8mmol) in 50 ml of carbon tetrachloride, and the reaction was stirred at 78 ℃. After 8 hours, the TCL monitored the disappearance of the starting material, filtered while hot, the filtrate was distilled under reduced pressure to remove the solvent, and the solid was dried and purified by column chromatography to give the product as a yellow solid in 78.80% yield.
(e) In a dry one-neck flask were added 2- (acetoxyimino) -1- (4- (-4- (bromomethyl) styryl) phenyl) propanone (20mmol), potassium carbonate (40mmol) and diethylamine (24mmol) in 50 ml ethanol, and the reaction was stirred at 40 ℃. After 8 hours, the TCL monitored the disappearance of the starting material, the ethanol was concentrated under reduced pressure, 50 ml of deionized water were added to the system and the precipitate was filtered off with suction, the product being a yellow solid with a yield of 91.20%.
(f) In a dry three-neck flask, under nitrogen protection, 2- (acetoxyimino) -1- (4- (4- ((diethylamino) methyl) styryl) phenyl) propanone (15mmol) and 1, 3-propanesulfonic acid were addedThe lactone (20mmol) was dissolved in 60 ml of acetone and stirred at 70 ℃. After 12 hours, the TCL monitored the disappearance of the starting material, cooling to room temperature and precipitation in the system, which was filtered off with suction and the product was a yellow solid in 85.86% yield. HR-MS (C)27H34N2O6S): 514.2138 for m/e; the experimental results are as follows: 515.2166 (M + H)+)。
Example 2: preparation of initiators 2, 3, 4, 6, 8, 9, 10, 11, 13, 14, 15, 16, 17, 20
The preparation of these initiators was similar to the preparation of initiator 1 in example 1. In step (a), a Heck reaction is carried out using 4-bromophenyl alkyl ketones which may be the same as or different from (1) to produce distyrylalkyl ketones, for example, in accordance with (1), (2), (3), (4), (6), (8), (9), (13), (15) using 4-bromobenzophenone, (10), (16) using 4-bromobenzophenone, (11), (14), (17), (20) using 4-bromophenyl benzyl ketone. The next step (b) is identical to the preparation of (1), and isoamyl nitrite is utilized to carry out reaction to prepare the corresponding oxime group. In step (c), the same or different acid chloride as (1) is used to react with an oxime to produce each of the different target products, for example (9), (10), (11) in accordance with (1), (2) propionyl chloride, (3), (13), (14) butyryl chloride, (4), (15), (16), (17) benzoyl chloride, (6) 4-methoxybenzoyl chloride, (8), (20) 4-trifluoromethylbenzoyl chloride. The steps (d), (e) and (f) are the same as (1). Finally, the distyryl oxime ester type water-soluble photoinitiator with different electron withdrawing and electron donating groups is prepared. Specific yields and mass spectral characterization results are as follows:
2, 58% yield, light yellow solid. HR-MS (C)28H36N2O6S): 528.2294 for m/e; the experimental results are as follows: 529.2286(M+H+)。
3, 61% yield, light yellow solid. HR-MS (C)29H38N2O6S): 542.2451 for m/e; the experimental results are as follows: 543.2467(M + H)+)。
4, 58% yield, yellow solid. HR-MS (C)32H36N2O6S): 576.2294 for m/e; the experimental results are as follows: 577.2306(M + H)+)。
6, 58% yield, yellow solid. HR-MS (C)34H40N2O7S): 620.2556 for m/e; the experimental results are as follows: 621.2584(M + H)+)。
8, yield 64%, yellow solid. HR-MS (C)33H35F3N2O6S): 644.2168 for m/e; the experimental results are as follows: 645.2153(M + H)+)。
9, 68% yield, yellow solid. HR-MS (C)28H36N2O6S): 528.2294 for m/e; the experimental results are as follows: 529.2302(M + H)+)。
10, yield 64%, yellow solid. HR-MS (C)29H38N2O6S): 542.2451 for m/e; the experimental results are as follows: 543.2432(M + H)+)。
11, 59% yield, yellow solid. HR-MS (C)32H36N2O6S): 576.2294 for m/e; the experimental results are as follows: 577.2264(M + H)+)。
13, 56% yield, yellow solid. HR-MS (C)30H40N2O6S): 556.2607 for m/e; the experimental results are as follows: 557.2617(M + H)+)。
14, yield 61%, yellow solid. HR-MS (C)34H40N2O6S): 604.2607 for m/e; the experimental results are as follows: 605.2632(M + H)+)。
15, yield 55%, yellow solid. HR-MS (C)33H38N2O6S): 590.2451 for m/e; the experimental results are as follows: 591.2465(M + H)+)。
16, yield 57% yellow solid. HR-MS (C)34H40N2O6S): 604.2607 for m/e; the experimental results are as follows: 605.2623(M + H)+)。
17, yield 48%, yellow solid. HR-MS (C)37H38N2O6S): 638.2451 for m/e; the experimental results are as follows: 639.2466(M + H)+)。
20, yield 57% yellow solid. HR-MS (C)38H37F3N2O6S): 706.2324 for m/e; the experimental results are as follows: 707.2333(M + H)+)。
Example 3: preparation of initiators 5, 7, 12, 18, 19
The difference between the preparation method of these initiators and the preparation method of the initiator in example 1 is that the substituent has methyl or chlorine atom on the benzene ring, the methyl on the benzene ring is changed into benzyl bromide during NBS bromination, and the chlorine atom is also substituted during the reaction with diethylamine, so that these initiators are prepared by synthesizing the structure of amine in step (d) and step (e) and then preparing the structure of oxime ester, so that the steps are in the order of (a), (d), (e), (b), (c) and (f). And in step (a), Heck reaction using 4-bromophenyl alkyl ketone the same as or different from (1) to produce distyryl alkyl ketone, for example, (5), (7) in accordance with (1), (18), (19) using 4-bromophenyl benzyl ketone, and (12) using 1- (4-bromophenyl) -2- (p-tolyl) ethanone. The following steps (d), (e), (b) are exactly the same as the preparation of (1), and the stilbene ketoxime with amino group is prepared. In the next step (c), the same or different acid chlorides as (1) are reacted with oximes to produce the respective different desired products, for example (12) corresponding to (1), (5), (18) using 4-methylbenzoyl chloride, (7), (19) using 4-chlorobenzoyl chloride. The next step (f) is completely the same as (1), and finally the distyryl oxime ester type water-soluble photoinitiator with different electron withdrawing and electron pushing group ketones is prepared. Specific yields and mass spectral characterization results are as follows:
5, yield56% yellow solid. HR-MS (C)33H38N2O6S): 590.2451 for m/e; the experimental results are as follows: 591.2462(M + H)+)。
7, yield 55%, yellow solid. HR-MS (C)32H35ClN2O6S): 610.1904 for m/e; the experimental results are as follows: 611.1922(M + H)+)。
12, yield 57%, yellow solid. HR-MS (C)33H38N2O6S): 590.2451 for m/e; the experimental results are as follows: 591.2466(M + H)+)。
18, yield 60%, yellow solid. HR-MS (C)38H40N2O6S): 652.2607 for m/e; the experimental results are as follows: 653.2631(M + H)+)。
19, 58% yield, yellow solid. HR-MS (C)37H37ClN2O6S): 672.2601 for m/e; the experimental results are as follows: 673.2632(M + H)+)。
Example 4: thin film polymerization
The photocuring test samples were formulated according to the following weight percentages: 28 parts of epoxy acrylate; 32 parts of polyester acrylate; 6 parts of hexanediol diacrylate; 24 parts of pentaerythritol triacrylate; 16 parts of titanium dioxide dye; 4 parts of the selected photoinitiator in example 1.
And taking part of the mixture, fully grinding the mixture uniformly, coating the mixture on a white ABS substrate, and forming a pattern layer of about 20 micrometers under air. Irradiation was carried out with a 385nm LED curing tester (light, Guangzhou) 2 cm from the sample, at a conveyor speed of 20 m/min. And judging the complete curing condition of the coating by finger-pressing and scraping. The photoinitiators in the compounds of the above examples all initiate complete curing of the film layer, and show good photoinitiation performance.
Example 5: thick film polymerization
The formulation was the same as in example 4.
A portion of the above mixture was ground thoroughly to a thickness of about 200 μm under air on a white ABS substrate. Irradiation was carried out with a 385nm LED curing tester (light, Guangzhou) 2 cm from the sample, at a conveyor speed of 10 m/min. And judging the complete curing condition of the coating by pressing and scraping. The photoinitiators in the compounds of the above examples all initiate complete curing of the film layer, and show good photoinitiation performance.
Example 6: aqueous polymerization
The photocuring test samples were formulated according to the following weight percentages: 12 parts of acrylamide; 70 parts of deionized water; 16 parts of titanium dioxide dye; 2 parts of the selected photoinitiator of example 1.
A portion of the above mixture was ground thoroughly to a thickness of about 200 μm under air on a white ABS substrate. Irradiation was carried out with a 385nm LED curing tester (light, Guangzhou) 2 cm from the sample, at a conveyor speed of 10 m/min. And judging the complete curing condition of the coating by pressing and scraping. The photoinitiators in the compounds of the above examples all initiate complete curing of the film layer, and show good photoinitiation performance.
Example 7: aqueous polymerization
By mixing hydroxyethyl methacrylate HEMA (0.5M), maleimido polyethylene glycol monomethyl ether mtthoxy PEGMA (0.2M, Mn ≈ 300) and polyethylene glycol dimethacrylate PEGDMA (0.02M, Mn ≈ 2000) in water andby the initiator in example 1To construct a hydrogel (1% w/w at room temperature). The mixture was stirred and poured into a mold for crosslinking for 3 hours. The resulting hydrogel was extracted with fresh PBS to remove unreacted monomers and residual chemicals, and then tested after placing the hydrogel in PBS for further stabilization in the dark for 48 hours.
The test shows that the polymerization conversion rate of the hydrogel is 83.3 percent, the dynamic equilibrium water content is 87.2 percent, wherein the calculation formula of the polymerization conversion rate is
Wherein m is0Is the mass of all monomers and initiators, mdryIs the actual quality of the hydrogel obtained.
The calculation formula of the dynamic Equilibrium Water Content (EWC) is
Wherein m iswetIs the actual mass of the hydrogel, mdryThe mass was obtained after the hydrogel was dried by blotting the surface water with filter paper.
Hydrogel samples after equilibration with PBS for at least 48 hours were cut into cylinders of 20mm diameter. The dynamic viscoelasticity of the hydrogels was measured at 25 ℃ on a stress control rheometer (HAAKE MARS III) using a 20mm parallel plate. The gap between the upper plate and the sample plate was set by first moving the upper plate about 2mm above the sample surface. The upper plate descends very slowly (5 μms)-1) The normal force was monitored simultaneously and stopped at a limit normal force of 100 mN. Dynamic stress and frequency sweep rheology experiments were performed on the hydrogels. A stress sweep was first performed to explore the linear viscoelastic region (LVER) at a constant frequency of 1Hz over a stress range of 1-100 Pa. The frequency sweep oscillation test was recorded in constant stress (10pa) mode and controlled in the frequency range of 0.1-50 Hz to keep the measurements in the linear range. The values of G' and G "are determined at 1 Hz. The final test results were 1563.2Pa G "168.3 Pa.
It is emphasized that the above-described examples are merely illustrative of some tests and are not to be considered as limiting tests or conditions. The scope of the innovation covered by this application is defined by the claims.
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| CN107344918A (en) * | 2017-05-26 | 2017-11-14 | 同济大学 | A kind of oxime ester compound containing talan and its preparation method and application |
| CN110806676A (en) * | 2018-08-06 | 2020-02-18 | 常州强力先端电子材料有限公司 | Photosensitive resin composition and application thereof |
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| CN110806676A (en) * | 2018-08-06 | 2020-02-18 | 常州强力先端电子材料有限公司 | Photosensitive resin composition and application thereof |
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| CN114163313A (en) * | 2021-12-14 | 2022-03-11 | 中山大学 | Method for selectively synthesizing EZ-stilbene by coupling aryl diazonium salt and cinnamic acid under catalysis of ruthenium |
| CN114163313B (en) * | 2021-12-14 | 2023-11-03 | 中山大学 | A method for the selective synthesis of EZ-stilbene through the coupling of ruthenium-catalyzed aryldiazonium salts and cinnamic acid |
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