CN107163169B - A kind of cumarin and carbazole type oxime ester compound and its preparation method and application - Google Patents
A kind of cumarin and carbazole type oxime ester compound and its preparation method and application Download PDFInfo
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- CN107163169B CN107163169B CN201710378833.5A CN201710378833A CN107163169B CN 107163169 B CN107163169 B CN 107163169B CN 201710378833 A CN201710378833 A CN 201710378833A CN 107163169 B CN107163169 B CN 107163169B
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- compound
- cumarin
- formula
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- oxime ester
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- -1 oxime ester compound Chemical class 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- PQMOXTJVIYEOQL-UHFFFAOYSA-N Cumarin Natural products CC(C)=CCC1=C(O)C(C(=O)C(C)CC)=C(O)C2=C1OC(=O)C=C2CCC PQMOXTJVIYEOQL-UHFFFAOYSA-N 0.000 title claims abstract description 17
- FSOGIJPGPZWNGO-UHFFFAOYSA-N Meomammein Natural products CCC(C)C(=O)C1=C(O)C(CC=C(C)C)=C(O)C2=C1OC(=O)C=C2CCC FSOGIJPGPZWNGO-UHFFFAOYSA-N 0.000 title claims abstract description 17
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 title abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 54
- 238000003847 radiation curing Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 230000000694 effects Effects 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 150000002923 oximes Chemical class 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- UEOHATPGKDSULR-UHFFFAOYSA-N 9h-carbazol-4-ol Chemical class N1C2=CC=CC=C2C2=C1C=CC=C2O UEOHATPGKDSULR-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000002837 carbocyclic group Chemical group 0.000 claims description 2
- 150000007942 carboxylates Chemical group 0.000 claims description 2
- 125000004122 cyclic 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
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 claims description 2
- 125000005647 linker group Chemical group 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims 1
- 150000001263 acyl chlorides Chemical class 0.000 claims 1
- 239000006185 dispersion Substances 0.000 claims 1
- 239000011592 zinc chloride Substances 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 238000009472 formulation Methods 0.000 abstract description 4
- 230000005855 radiation Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 29
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 17
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- 238000012512 characterization method Methods 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000001819 mass spectrum Methods 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 6
- 230000004224 protection Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 description 5
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 5
- 238000007711 solidification Methods 0.000 description 5
- 230000008023 solidification Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 2
- 229960000956 coumarin Drugs 0.000 description 2
- 235000001671 coumarin Nutrition 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 235000011167 hydrochloric acid Nutrition 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000003999 initiator Substances 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
- 108091008695 photoreceptors Proteins 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- UEMGWPRHOOEKTA-UHFFFAOYSA-N 1,3-difluorobenzene Chemical class FC1=CC=CC(F)=C1 UEMGWPRHOOEKTA-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- SBJACJNGROKNPT-UHFFFAOYSA-N 2-bromo-2,4,4-trimethylpentane Chemical class CC(C)(C)CC(C)(C)Br SBJACJNGROKNPT-UHFFFAOYSA-N 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BRASHVIUCBLPEG-QFMPWRQOSA-N CCCCC(CC)C[n](c(cc1)c2cc1C(/C(/CC)=N/OC(C)=O)=O)c(cc1)c2c(O2)c1C(C)=CC2=O Chemical compound CCCCC(CC)C[n](c(cc1)c2cc1C(/C(/CC)=N/OC(C)=O)=O)c(cc1)c2c(O2)c1C(C)=CC2=O BRASHVIUCBLPEG-QFMPWRQOSA-N 0.000 description 1
- SHDQFCSQOZRFRP-FDEZRRJOSA-N CCCCC(CC)C[n]1c2ccc(C(C)=CC(O3)=O)c3c2c2cc(C(/C(/CC)=N/OC(c3ccccc3)=O)=O)ccc12 Chemical compound CCCCC(CC)C[n]1c2ccc(C(C)=CC(O3)=O)c3c2c2cc(C(/C(/CC)=N/OC(c3ccccc3)=O)=O)ccc12 SHDQFCSQOZRFRP-FDEZRRJOSA-N 0.000 description 1
- SSVXZDLZTIYASI-BTERYNNVSA-N CCCCC(CC)C[n]1c2ccc(C(C)=CC([U]3)=O)c3c2c2cc(C(/C(/C(C)C)=N/OS(c3ccc(C)cc3)(=O)=O)=O)ccc12 Chemical compound CCCCC(CC)C[n]1c2ccc(C(C)=CC([U]3)=O)c3c2c2cc(C(/C(/C(C)C)=N/OS(c3ccc(C)cc3)(=O)=O)=O)ccc12 SSVXZDLZTIYASI-BTERYNNVSA-N 0.000 description 1
- 241000522215 Dipteryx odorata Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 241000233855 Orchidaceae Species 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
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000004075 acetic anhydrides Chemical class 0.000 description 1
- 239000002253 acid Substances 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
- 238000013019 agitation Methods 0.000 description 1
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 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
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical group CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000004775 coumarins Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000000990 laser dye Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003208 petroleum Substances 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
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229960002668 sodium chloride Drugs 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 125000002130 sulfonic acid ester group Chemical group 0.000 description 1
- SJGSVFXEXGQCCY-UHFFFAOYSA-N sulfuryl dichloride;trifluoromethylbenzene Chemical compound ClS(Cl)(=O)=O.FC(F)(F)C1=CC=CC=C1 SJGSVFXEXGQCCY-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/04—Ortho-condensed systems
- C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
- C07D491/052—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being six-membered
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
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Abstract
The present invention relates to new material organic chemicals technical fields, it is related to a kind of cumarin and carbazole type oxime ester compound and its preparation method and application, more particularly to the new compound of structure shown in formula (I) or (II), its chemical preparating process technology, its purposes as radiation curing photoinitiator, and its photocureable coating or ink that can be excited in radiation curable formulation product, especially UV Vis LED, wait the application of many occasions.
Description
【Technical field】
The present invention relates to new material organic chemicals technical field, more particularly to a new class of cumarin base oxime ester type structure
Compound, chemical preparating process technology, as the purposes of radiation curing photoinitiator and its match in radiation curing
Square product, the photocureable coating or ink that can be especially excited in UV-Vis-LED, waits the application purpose of many occasions.
【Background technology】
Photoinitiator compound is a kind of important Fine Organic Chemical product material.With ultraviolet light or visible (UV) light or
LED (i.e. Light-Emitting Diode) is the radiation curing technology field of light source, can be generated under light radiation parameter freely
The photoinitiator compound of base active specy is the key species for inducing the system of unsaturation containing alkene and carrying out efficient photopolymerization reaction, because
This is important one of radiation curable formulation component.Photocuring have energy conservation and environmental protection, efficiently quickly and time-space controllably etc. it is all
More advantages are widely used in the new high-tech products such as the traditional fields such as coating and printing ink, adhesive and 3D printing.With tradition
Ultraviolet light solidification compare, using light emitting diode (LED) as light source LED light solidification have capacity usage ratio height, thermal effect
Answer it is small, do not generate the remarkable advantages such as ozone.Photosensitive resin formula for photocuring usually contains photoinitiator, activity dilution
Agent, oligomer and various auxiliary agents, wherein photoinitiator are the key components of photocurable formulation, and activity directly affects photocuring speed
Rate, curing degree and end product performance.Traditional photoinitiator is mainly used for the shorter ultraviolet light solidification of wavelength, it is difficult to
LED light source matches, so being ground by the relationship between rational MOLECULE DESIGN and the Molecular Design and its performance of system
Study carefully, developing efficient LED light initiator has very big application prospect.
Cumarin (coumarin) derivative has also been widely studied and has drawn as visible light sensitive agent or visible light
It sends out agent and is applied to photopolymerization field.Cumarin is heterocycle compound, is widely present in black tonka-bean, in the plants such as orchid,
Molecular structural formula is as shown in Figure 1.As the chromophore of function admirable, cumarin is all widely used in many fields, such as：
Laser dye and fluorescence probe.However, the absorption collection of illustrative plates of cumarin itself is in ultraviolet region (λ=310nm；ε=5170L mol- 1cm-1), the Research Requirements of visible light initiator cannot be met.Therefore, it will usually some auxochromes are introduced on cumarin molecule
Or extend the length of its conjugated chain so that absorb peak position and red shift occurs, reach near ultraviolet band or visible light region.
The molecular structural formula of cumarin
In curing field, it is still the field to have high photosensitivity, stability height and easily prepared photoinitiator
Development it is preferred, the people of continuous improvement, Yi Jiguang with to(for) all kinds of requirements such as environmental protection, production safety consciousness and labour protections
The continuous development of polymerization technique, the exposure lamp source of the low energy consumption such as LED, LDI, high security and environmental protection become art technology and answer
With a kind of trend with development.
【Invention content】
It is an object of the invention to prepare a kind of novel coumarin and carbazyl oxime ester compound, radiation curing can be used as
Photoinitiator is related to the application of many occasions such as photocureable coating or the ink that UV-LED can be excited.
Technical solution of the present invention is：
One, this item application discloses novel coumarin and carbazyl oxime ester compound shown in logical formula (I) as follows or (II)：
In above-mentioned logical formula (I) and (II) compound structure：
(1)R1, R2It is each independently selected from C1-C20Linear or branched alkyl group, C3-C12Naphthenic base, cycloalkyl-alkyl, ring are miscellaneous
Alkyl-alkyl；
(2)R3And R4It is containing Y, R5, R6, R7, R8, R9Substituted aryl (as shown in above-mentioned general formula) or R10, R11, R12
Substituted tertiary alkyl,
Wherein R5, R6, R7, R8, R9Independent of each other is hydrogen, halogen atom, R, OR, SR, NRR ', CH2OH, CH2OR, or
CH2NRR ', wherein R or R ' independent of each other are (to be labeled as-C containing 1-24 carbon atom1-C24, similarly hereinafter) linear chain or branched chain
Alkyl or-C6-C121-6 discrete oxygen can be contained in aryl, R or R ' structures, nitrogen or element sulphur, R and R ' are deposited simultaneously
When can also form the ring system structure of a 3-6 member therebetween.
R10, R11, R12Independent of each other is R, and arbitrary the two among three can also form the carbocyclic ring knot of a 3-6 member
Structure, Y are that linking group is preferably-CH2,-CH2CH2,-CH2CH(OH)CH2,-CH2CH(OR)CH2,-CH2CH(OC(O)
R)CH2, etc..R3Preferably, CH3, CH2CH3, CH2CH(CH3)2,CH2Ph or Y=CH2Or vacancy (being directly connected to phenyl ring), R5
=R6=R8=R9=H, R7=CH3Or alkyl-cycloalkyl, cycloheteroalkyl alkyl structure；
The cycloalkyl-alkyl has following structure：
Wherein x=1~5, y=1~6；
The cycloheteroalkyl alkyl has following structures：
Wherein x=1~5, y=1~6, z indicate S, O, N；
(3) A is C=O (i.e. Formulas I or II compounds is carboxylate structure) or A is O=S=O (i.e. Formulas I or II compounds
It is sulfonic acid ester structure).
Two, cumarin shown in partial Formula (I) and (II) and carbazyl oxime ester compound are prepared, preparation method can lead to
The method for crossing following technical scheme realization：
Step 1, starting material as shown in the figure is in BiCl3Effect is lower to be obtained by the reaction compound (1) or (2), reacts item
Part is 100 DEG C, N2Protection, 72h, BiCl3ZnCl may be used2It substitutes
Step 2, step 1 products therefrom (1) or (2) are catalyzed with substance shown in (b) in figure in potassium iodide and 18- crown-s 6
It reacts to obtain (3) or (4) in the case of agent, reaction condition DMF, 100 DEG C, for 24 hours, DMF may be used acetone and heat back
Stream substitutes；
Substance shown in (c) is in AlCl in step 3, step 2 products therefrom (3) or (4) and figure3It reacts under effect
To (5) or (6), reaction condition is anhydrous CH2Cl2, 0 DEG C, N2Protection, 2h；
Oxime is obtained by the reaction with isoamyl nitrite in step 4, step 3 products therefrom (5) or (6), and (7) or (8) react item
Part is THF, room temperature, dense HCl, 5h；
Step 5, step 4 products therefrom (7) or (8) are arrived with what acid anhydrides or carboxylic acid halides reacted under triethylamine effect
Target product (I) or (II), reaction condition CH2Cl2, room temperature, N2Protection, is protected from light, 2h；Wherein, X as shown in the figure is halogen atom,
R4AX is corresponding carboxylic acid halides or sulfonyl halogen compound.
In the present invention, logical formula (I) and heterocycle oxime ester compound shown in (II) draw in photocurable formulation system as light
Send out the purposes of agent or other functional additive ingredients, and the purposes in chemical synthesis as intermediate or raw material or reagent.
Three, the present invention further disclose a kind of compound containing above-mentioned logical formula (I) and (II) can be (ultraviolet or can via light
Light-exposed or LED light or equal lamp-house) radiation curing mixture.
Such light radiation curing formula system is characterized in：
(1) contain compound described at least one logical formula (I) or (II) as photoinitiator or photoinitiator component
One of；
(2) contain at least one containing ethylene linkage (C=C) unsaturated compound.
Calculated with the every 100 parts of weight of the component of unsaturation containing ethylene linkage total amount in system, the logical formula (I) compound contained it is suitable
Amount be 0.01-30 parts by weight, preferred 0.5-10 parts by weight.Suitable Radiation-curing system include it is polymerizable containing ethylene linkage not
Saturation component is can be by compound or mixture that the Raolical polymerizable of the double bond is crosslinked, this insatiable hunger containing ethylene linkage
It can be aqueous point of monomer, oligomer or prepolymer or their mixture or copolymer or said components with component
Granular media.
It is as follows：(1) monomer is pressed：Photoinitiator：The mass ratio 100 of auxiliary agent：0.5~1：0~4.5 proportioning is former
Material；(2) stirring makes it fully dissolve；(3) polymerization system is irradiated with the light source of different wave length or different light intensity；(4) with online
The Changeement polymerisation conversion that infrared method passes through its characteristic peak；Wherein：Light source in step (3) can be LED (high pressure,
Middle pressure and low pressure) and launch wavelength be the LEDs of 365~425nm, LDI light sources.
Radiation-curing system described above can contain the inorganic or organic filler added according to actual needs
And/or colorant (such as pigments or dyes etc.) and other additives (such as ultra-violet absorber, light stabilizer are fire-retardant
Agent, levelling agent or antifoaming agent etc.) and any ingredients such as solvent.
The monomer of suitable free radical polymerization is such as polymerisable monomer containing ethylene linkage, including but not limited to (methyl) acrylic acid
Ester, methacrylaldehyde, alkene, conjugated diolefin, styrene, maleic anhydride, fumaric acid anhydride, vinyl acetate, vinyl pyrrolidone,
Vinyl imidazole, (methyl) acrylic acid, (methyl) acrylic acid derivative such as (methyl) acrylamide, vinyl halide are sub-
Vinyl halide etc..
Suitable prepolymer containing ethylene linkage and oligomer include but not limited to (methyl) propylene of (methyl) acryloyl functional group
Acid copolymer, polyurethane formic acid esters (methyl) acrylate, polyester (methyl) acrylate, unsaturated polyester (UP), polyethers (methyl)
The water solubility of acrylate, siloxanes (methyl) acrylate, epoxy resin (methyl) acrylate etc. and above-mentioned substance or
The analog of water dispersible.
It is above-mentioned either to contain alkene monomer or oligomer, prepolymer or copolymer, to this profession working technical staff
Speech, is all well known, is not particularly limited.
For the gist of the invention, we will further illustrate in conjunction with following series embodiments.
【Description of the drawings】
Fig. 1 is the UV-visible absorption spectrum of compound (1)
Fig. 2 is the polymerization curve of compound (1) photopolymerization TMPTA
Fig. 3 is the polymerization curve of compound (1) photopolymerization HDDA
【Specific implementation mode】
Embodiment one：
1, the preparation and representation of compound (1)
Parent material be 4- hydroxycarbazoles, by be acylated, esterification etc. with product is obtained by the reaction.Used in the preparation method
Synthetic route indicates as follows：
Detailed process is as follows：
Step 1, the synthesis of compound (A).In N2Under protection, 6.96g is added in the round-bottomed flask of 100mL
(0.038mol) 4- hydroxycarbazoles, 9.6mL (0.076mol) ethyl acetoacetate, 1.19g (0.0038mol) BiCl3, acutely stir
It mixes down after reacting 72h in 100 DEG C of oil baths, 500mL absolute ethyl alcohols, ultrasonic disperse, filtering, filter cake is added into reaction mixture
It is washed for several times with ethyl alcohol, obtains linen solid, be dried in vacuo at room temperature, obtain product (1) 5.84g yields：61.7%.Production
Object can be directly used for reacting in next step.
Step 2, the synthesis of compound (B).3.54g (14.20mmol) changes are sequentially added in the round-bottomed flask of 250mL
Close object (A), 2.74g (14.20mmol) bromo-iso-octanes and 3.92g (28.40mmol) potassium carbonate and a small amount of potassium iodide and 18-
Crown- 6 makees catalyst and 100mL DMF make solvent.Under agitation, it is reacted for 24 hours in 100 DEG C of oil baths, TLC is detected without raw material point
Reaction was completed in the presence of after, filters out inorganic salts, and filtrate is poured into 1000 milliliters of sodium-chloride water solutions, filters and solid is precipitated, slightly
Product silica gel chromatography, eluant, eluent PE/EA=2:1, obtain faint yellow solid compound 2.25g, yield 43.8%
Product structure is confirmed by nuclear magnetic resoance spectrum, and specific characterization result is as follows：
1H NMR(400MHz,CDCl3) δ 8.56 (d, J=7.7Hz, 1H), 7.54 (d, J=8.7Hz, 1H), 7.48-7.41
(m, 1H), 7.36 (d, J=8.2Hz, 1H), 7.27 (dt, J=13.5,3.2Hz, 1H), 7.19 (d, J=1.5Hz, 1H), 6.13
(d, J=1.1Hz, 1H), 4.18-4.04 (m, 2H), 2.43 (d, J=1.0Hz, 3H), 1.37-1.13 (m, 9H), 0.81 (m, J
=21.6,7.3Hz, 6H)13C NMR(101MHz,CDCl3)δ160.49,152.88,149.35,142.24,139.50,
125.04,122.80,120.54,120.02,119.43,110.52,109.68,109.23,108.15,104.77,46.66,
38.45,29.93,27.74,23.32,21.97,18.33,12.98,9.85.
Step 3, the synthesis of compound (C).N2Under protection 0.62g is sequentially added into the three-necked flask of 250mL
(1.7mmol) (B), 0.43g AlCl3(3.2mmol) and 15mL anhydrous methylene chlorides make solvent.Ice-water bath cools down, when temperature drops
When to 0 DEG C, be slowly added dropwise the solution that 0.32g (3.0mmol) n-butyryl chloride is dissolved in 5mL dichloromethane, temperature control 10 DEG C with
Under, about 1.5h is added, and continues to stir 2h.Reaction solution is poured into the dilute hydrochloric acid that 200g ice is made into 30ml concentrated hydrochloric acids, dichloromethane
Alkane extracts, and is washed with water and washs to pH value neutrality.Collected organic layer is dried with anhydrous sodium sulfate, and decompression rotary evaporation removes organic
After solvent, crude product is poured into petroleum ether, the precipitation for filtering precipitation is that sterling is yellow powdery solid, and 50 DEG C of vacuum are dried
It is dried in case for 24 hours, obtains product 0.62g, yield：84.9%.
Product structure is confirmed by nuclear magnetic resoance spectrum, and specific characterization result is as follows：
1H NMR (400MHz, DMSO) δ 8.87 (s, 1H), 8.17 (dd, J=8.7,1.3Hz, 1H), 7.82 (d, J=
8.7Hz, 1H), 7.71 (d, J=8.7Hz, 1H), 7.58 (d, J=8.7Hz, 1H), 6.33 (s, 1H), 4.32 (d, J=7.3Hz,
2H), 3.11 (t, J=7.1Hz, 2H), 2.51 (d, J=1.8Hz, 3H), 1.73 (h, J=7.3Hz, 2H), 1.37-1.11 (m,
9H), 1.00 (t, J=7.4Hz, 3H), 0.80 (dt, J=14.1,7.3Hz, 6H)13C NMR(101MHz,CDCl3)δ
199.00,159.86,152.58,149.23,142.78,142.05,129.31,125.22,123.60,121.27,119.50,
111.28,110.42,109.57,108.18,105.10,46.86,39.26,38.47,29.88,27.69,23.29,21.92,
18.34,17.01,12.99,12.95,9.83.
Step 4, the synthesis of compound (D).(C) of 0.62g (1.44mmol) is put into the three-necked flask of 250ml,
5h is stirred at room temperature in 10mL tetrahydrofurans, 0.6mL (7.2mmol) concentrated hydrochloric acid, 0.25g (2.1mmol) isoamyl nitrite.It will be anti-
It answers object to pour into 100ml water, is extracted using dichloromethane, anhydrous MgSO4It is dry.It is evaporated to obtain dope shape product addition oil
Solid is precipitated after ether, suction filtration obtains yellow product 0.48g, yield 73.2%.It is used directly for reacting in next step.
Step 5, the synthesis of target product (1).In darkroom, in N2Under gas shielded, put into successively in three-necked flask
0.18g (0.40mmol) compound (D), 10 milliliters of dichloromethane stir the triethylamine of addition 0.3mL after 5min, drop at room temperature
Add 0.10g acetic anhydrides (0.97mmol), about 30min is added dropwise, and continues to stir 2h.50 milliliters of deionizations are added in reaction system
The HCl of 2M, 5% NaHCO are used in water, dichloromethane extraction respectively3Aqueous solution is washed, and adjusts pH to neutrality；Anhydrous Na SO4It is dry, subtract
Solvent is distilled off in pressure；Silica gel chromatography is crossed, the polarity of eluant, eluent selects PE/EA=2:1, finally obtain yellow solid
Close object.Obtain product 0.14g, yield 70.1%.
Product structure is confirmed by nuclear magnetic resoance spectrum, and specific characterization result is as follows：
1H NMR(400MHz,CDCl3) δ 9.14 (d, J=1.4Hz, 1H), 8.18 (dd, J=8.7,1.5Hz, 1H), 7.57
(d, J=8.7Hz, 1H), 7.35 (d, J=8.7Hz, 1H), 7.23 (d, J=8.7Hz, 1H), 6.14 (s, 1H), 4.09 (d, J=
7.5Hz, 2H), 2.82 (q, J=7.6Hz, 2H), 2.42 (s, 3H), 2.29 (s, 3H), 1.24-1.10 (m, 11H), 0.80 (dt,
J=13.9,7.2Hz, 7H)13C NMR(101MHz,CDCl3)δ188.46,167.89,164.76,159.56,152.32,
149.23,142.85,142.76,127.49,127.12,126.96,121.60,119.80,111.55,110.71,109.63,
108.25,105.23,46.91,38.48,29.85,27.71,23.24,21.93,20.28,18.77,18.31,12.96,
9.82,9.56.
2, the uv-visible absorption spectra of compound (1) is tested
Test method：Then precise compound (1) product 0.001g thinks in volumetric flask as in 100ml volumetric flasks
It is added at acetonitrile to 100ml scales, is made into 10-5The solution of g/ml concentration carries out UV absorption test using spectrophotometer, surveys
Try curve such as attached drawing 1.As seen from the figure, the maximum absorption wavelength λ of the moleculemaxIt is light-initiated compared to tradition at 375nm
Agent has the UV absorption of more long wavelength, is more easy to match with the light source of long wavelength.
3, the photopolymerization that compound (1) carries out is tested
Test method (1)：Using single trimethylolpropane trimethacrylate (TMPTA) as monomer with it is single light-initiated
Agent is uniformly mixed post-exposure, trimethylolpropane trimethacrylate：Compound (1)=100：1；100 μm of coating thickness；It uses
FTIR online infrared survey its illumination wavelength be 365nm, 385nmLED as excitation light source, light intensity 30mW/cm2(by red
Monomer double bond changes to test the efficiency of photoinitiator in outer spectrogram) test photoreceptor activity, the double bond that REAL TIME INFRARED THERMAL IMAGE is surveyed turn
Rate is the maximum conversion ratio in 1min.As shown in Fig. 2.TMPTA viscosity is high, and crosslink density is big, both more than 50% conversion ratio
There is good solidification effect, it is seen that this photoinitiator of the invention has excellent photosensitive property.
Test method (2)：With single 1,6- hexanediyl esters (1,6-Hexanedioldiacrylate,
HDDA post-exposure, HDDA) are uniformly mixed with single photoinitiator as monomer：Compound (1)=100：1；100 μ of coating thickness
m；Using FTIR online infrared survey its illumination wavelength be 365nm, 385nm and 405nmLED as exposure light source, light intensity is
30mW/cm2(efficiency of photoinitiator is tested by the variation of monomer double bond in infrared spectrum) test photoreceptor activity, it is red in real time
Outer surveyed double bond conversion rate is the maximum conversion ratio in 1min.As shown in Fig. 3.HDDA is solid rapidly under 385nmLED excitations
Change, conversion ratio is close to 90%, and surface drying situation is good.Conversion ratio is in also above 80%, 405nmLED under 365nmLED excitations
The band edge of absorption, conversion ratio be not high.This is because HDDA viscosity compared with TMPTA is low, conversion ratio obtains under same conditions of exposure
To greatly improve, it is seen that this photoinitiator of the invention will produce not in different Photopolymer Systems according to the difference of formula
Same photopolymerization effect, but generally all there is excellent photosensitive property.
In conclusion the application performance containing cumarin and carbazole oxime ester lightlike initiating agent described in the present embodiment is excellent, have
Very high photosensitive property shows very bloom especially in a kind of low energy consumption that LED is light source in the case of the solidification of long wavelength
Curing performance has a wide range of applications.
Embodiment two：The preparation and representation of compound (2)
Using preparation method same as above-described embodiment one be made compound (2), only difference lies in：With to isoveryl chloride
It is raw material instead of n-butyryl chloride.The yield of the present embodiment target molecule is 66.3%.
Product structure is confirmed by nuclear magnetic resoance spectrum, and specific characterization result is as follows：
1H NMR(400MHz,CDCl3) δ 8.83 (s, 1H), 7.95 (t, J=8.0Hz, 1H), 7.52 (dd, J=8.6,
2.7Hz, 1H), 7.28 (d, J=8.7Hz, 1H), 7.16 (s, 1H), 6.07 (s, 1H), 4.05 (t, J=7.4Hz, 2H), 2.38
(s, 3H), 1.92-1.79 (m, 3H), 1.34-1.11 (m, 15H), 0.79 (dt, J=13.5,7.0Hz, 7H)13C NMR
(101MHz,CDCl3)δ188.82,159.34,152.29,149.02,143.13,142.86,142.73,127.37,
126.63,125.57,124.25,121.82,119.98,111.50,110.62,109.23,108.29,105.25,46.84,
38.46,35.88,29.83,27.66,23.24,22.51,21.91,18.26,16.11,12.94,9.79。
Embodiment three：The preparation and representation of compound (3)
Using the same preparation method with above-described embodiment one be made compound (3), only difference lies in：Use benzoyl oxide
It is raw material instead of acetic anhydride.The yield of the present embodiment target molecule is 80.2%,
Product structure is confirmed by mass spectrum, and specific characterization result is as follows：
HRMS(M+H)for C32H25F3NO3S4:656.0624(calculated),656.0619
(experimental)；(M+Na)for C32H24NaF3NO3S4:678.0443(calculated),678.0449
(experimental)。
Example IV：The preparation and representation of compound (4).
Using preparation method same as above-described embodiment three be made compound (4), only difference lies in：With to isoveryl chloride
It is raw material instead of n-butyryl chloride.The yield of the present embodiment target molecule is 70.8%
Product structure is confirmed by mass spectrum, and specific characterization result is as follows：
HRMS(M+H)for C32H25F3NO3S4:656.0624(calculated),656.0619
(experimental)；(M+Na)for C32H24NaF3NO3S4:678.0443(calculated),678.0449
(experimental)。
Embodiment five：The preparation and representation of compound (5)
Using preparation method same as above-described embodiment one be made compound (5), only difference lies in：With to isoveryl chloride
It is raw material to replace acetic anhydride by raw material, p-methyl benzene sulfonic chloride instead of n-butyryl chloride.The yield of the present embodiment target molecule
It is 75.8%.
Product structure is confirmed by mass spectrum, and specific characterization result is as follows：
HRMS(M+H)for C36H41N2O6S:629.2624(calculated),629.2619(experimental)；(M
+Na)for C36H40NaN2O6S:651.2643(calculated),651.2649(experimental)。
Embodiment six：The preparation and representation of compound (6)
Using preparation method same as above-described embodiment three be made compound (6), only difference lies in：With to isoveryl chloride
It is raw material to replace acetic anhydride by raw material, methylsufonyl chloride instead of n-butyryl chloride.The yield of the present embodiment target molecule is
79.8%.
Product structure is confirmed by mass spectrum, and specific characterization result is as follows：
HRMS(M+H)for C30H37N2O6S:553.2308(calculated),553.2309(experimental)；(M
+Na)for C30H36NaN2O6S:575.2313(calculated),575.2309(experimental)。
Embodiment seven：The preparation and representation of compound (7)
Compound (7) is made using preparation method same as above-described embodiment one, only difference lies in to trifluoromethyl
It is raw material that benzene sulfonyl chloride, which replaces acetic anhydride,.The yield of the present embodiment target molecule is 81.8%.
Product structure is confirmed by mass spectrum, and specific characterization result is as follows：
HRMS(M+H)for C35H36F3N2O6S:669.2234(calculated),669.2229(experimental)；
(M+Na)for C35H35NaF3N2O6S:691.2243(calculated),691.2249(experimental)。
Embodiment eight：The preparation and representation of compound (8)
Compound (8) is made using preparation method same as above-described embodiment one, only difference lies in 2,4- difluorobenzenes
It is raw material that sulfonic acid chloride, which replaces acetic anhydride,.The yield of the present embodiment target molecule is 81.8%.
Product structure is confirmed by mass spectrum, and specific characterization result is as follows：
HRMS(M+H)for C34H35F2N2O6S:637.2114(calculated),637.2119(experimental)；
(M+Na)for C34H34NaF2N2O6S:659.2123(calculated),659.2121(experimental)。
(9) preparation and representation of compound (9)
Compound (9) is made in preparation method same as above-described embodiment one, and only difference lies in replaced with 2- hydroxycarbazoles
4- hydroxycarbazoles, it is raw material to replace acetic anhydride with benzoyl oxide.The yield of the present embodiment target molecule is 77.6%.
Product structure is confirmed by mass spectrum, and specific characterization result is as follows：
HRMS(M+H)for C35H37N2O5:565.2624(calculated),565.2619(experimental)；(M+
Na)for C35H36NaN2O5:587.2743(calculated),587.2749(experimental)。
Embodiment ten：The preparation and representation of compound (10)
Compound (10) is made using preparation method same as above-described embodiment one, only difference lies in 2- hydroxyl clicks
It is raw material that azoles, which replaces 4- hydroxycarbazoles, is raw material with acetic anhydride is replaced to trifluoromethyl benzene sulfonyl chloride.The present embodiment target
The yield of molecule is 79.8%.
Product structure is confirmed by mass spectrum, and specific characterization result is as follows：
HRMS(M+H)for C35H36F3N2O6S:669.2234(calculated),669.2229(experimental)；
(M+Na)for C35H35NaF3N2O6S:691.2243(calculated),691.2249(experimental)。
It is emphasized that the above-mentioned embodiment enumerated only is some exemplary tests, it is not considered as limited examination
It tests or condition.The innovation range that the present patent application is covered should be subject to claims and record.
Claims (8)
1. a kind of cumarin and carbazyl oxime ester compound shown in logical formula (I) or (II), which is characterized in that its structural formula is：
In above-mentioned logical formula (I) or (II) compound structure：
(1)R1, R2It is each independently selected from C1-C20Linear or branched alkyl group, C3-C12Naphthenic base, cycloalkyl-alkyl, cycloheteroalkyl
Alkyl；
(2)R3And R4It is containing Y, R5, R6, R7, R8, R9Substituted aryl or R10, R11, R12Substituted tertiary alkyl is (such as above-mentioned logical
Shown in formula),
Wherein, Y is linking group, R5, R6, R7, R8, R9Independent of each other is hydrogen, halogen atom, R, OR, SR, NRR ', CH2OH,
CH2OR or CH2NRR’；The R or R ' independent of each other is (to be labeled as-C containing 1-24 carbon atom1-C24, similarly hereinafter) straight chain
Or the alkyl or-C of branch6-C12Containing 1-6 discrete oxygen, nitrogen or element sulphur in aryl, R or R ' structures, R and R ' are simultaneously
In the presence of therebetween also formed a 3-6 member ring system structure；R10, R11, R12Independent of each other is R, arbitrary the two among three
Form the carbocyclic ring structure of a 3-6 member；
(3) A is that (i.e. Formulas I or II compounds is sulphonic acid ester to C=O (i.e. Formulas I or II compounds is carboxylate structure) or O=S=O
Structure).
2. compound as described in claim 1, which is characterized in that (2) Y described in is-CH2,-CH2CH2,-CH2CH(OH)
CH2,-CH2CH(OR)CH2,-CH2CH(OC(O)R)CH2-。
3. compound as described in claim 1, which is characterized in that the cycloalkyl-alkyl has following structure：
Wherein x=1~5, y=1~6；
The cycloheteroalkyl alkyl has following structures：
Wherein x=1~5, y=1~6, z indicate S, O, N.
4. a kind of preparing cumarin and carbazyl oxime ester compound shown in logical formula (I) as described in claim 1 and (II)
Method, which is characterized in that preparation process is as follows：
Step 1,2- hydroxycarbazoles or 4- hydroxycarbazoles are in BiCl3For compound is obtained by the reaction under the catalyst action of representative
(1) or (2)；
Step 2, step 1 products therefrom (1) or (2) and substance, i.e. bromoalkane shown in (b) in figure, in potassium iodide and 18- crown-s 6
It reacts to obtain (3) or (4), solvent DMF in the case of making catalyst；
Step 3, step 2 products therefrom (3) or (4) and substance, i.e. acyl chlorides shown in (c) in figure, in AlCl3Effect is lower to be occurred instead
It should obtain (5) or (6)；
Step 4, step 3 products therefrom (5) or (6) and (d) substance, i.e. isoamyl nitrite in figure, under concentrated hydrochloric acid effect
Oxime (7) or (8) are obtained by the reaction；
Step 5, step 4 products therefrom (7) or (8) (e) to that indicated in the drawings substance, i.e. acid anhydrides or corresponding carboxylic acid halides, three
What is reacted under ethamine effect arrives target product (I) or (II), wherein X as shown in the figure is halogen atom, R4AX is corresponding
Carboxylic acid halides or sulfonyl halogen compound.
5. lead to the preparation method of cumarin and carbazyl oxime ester compound shown in formula (I) or (II) as claimed in claim 4,
It is characterized in that, the BiCl in step 13Using ZnCl2It substitutes.
6. lead to the preparation method of cumarin and carbazyl oxime ester compound shown in formula (I) or (II) as claimed in claim 4,
It is characterized in that, solvent is acetone in step 2.
7. lead to the preparation method of cumarin and carbazyl oxime ester compound shown in formula (I) or (II) as claimed in claim 4,
It is characterized in that, product oxime is to replace isoamyl nitrite reaction to be made with hydroxylamine hydrochloride in step 4, and hydroxylamine hydrochloride is direct at this time
Generate oxime with carbonyl reaction, lack a carbonyl in target molecular structure, oxime is directly connected to aromatic ring at this time, i.e., logical formula (I) with
(II) the C=O bases in are not present.
8. the application of cumarin and carbazyl oxime ester compound shown in a kind of logical formula (I) described in claim 1 or (II),
It is characterized in that, as the photoinitiator or one of photoinitiator component in light radiation curing system
Such light radiation curing formula system is characterized in：
(1) contain compound described at least one logical formula (I) as one of photoinitiator or photoinitiator component；
(2) contain at least one containing ethylene linkage (C=C) unsaturated compound；
It is calculated with the every 100 parts of weight of the component of unsaturation containing ethylene linkage total amount in system, the suitable amount of the logical formula (I) compound contained
It is 0.5-10 parts by weight；
The polymerizable component of unsaturation containing ethylene linkage that Radiation-curing system includes is the Raolical polymerizable quilt by the double bond
Crosslinked compound or mixture, this component of unsaturation containing ethylene linkage are monomer, oligomer or prepolymer or their mixing
The water-borne dispersions of object or copolymer or said components.
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| JP7475056B2 (en) * | 2019-01-30 | 2024-04-26 | 国立大学法人北陸先端科学技術大学院大学 | Method for producing photoresponsive nucleotide analogues |
| CN110054604A (en) * | 2019-04-30 | 2019-07-26 | 同济大学 | Oxime ester compound and its preparation method and application containing cumarin |
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| CN113727971A (en) * | 2019-09-10 | 2021-11-30 | 株式会社艾迪科 | Compound, acid generator, composition, cured product, pattern, and method for producing cured product and pattern |
| WO2021049470A1 (en) * | 2019-09-10 | 2021-03-18 | 株式会社Adeka | Compound, acid-generating agent, composition, cured product, pattern, and method for producing cured product and pattern |
| CN112961099B (en) * | 2021-02-18 | 2022-06-07 | 同济大学 | Bis-carbazole oxime ester photoinitiator, and preparation method and application thereof |
| CN112961165B (en) * | 2021-02-18 | 2022-02-01 | 同济大学 | Carbazole benzopyran compound and application thereof |
| CN114031622A (en) * | 2021-10-28 | 2022-02-11 | 同济大学 | Coumarin carbazole photosensitizer capable of being polymerized by cationic initiation, preparation method and application thereof |
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