CN101941939A - Polyfunctional carbazole derivative oxime ester compound and preparation method and light polymerization initiator thereof - Google Patents
Polyfunctional carbazole derivative oxime ester compound and preparation method and light polymerization initiator thereof Download PDFInfo
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- CN101941939A CN101941939A CN 201010233220 CN201010233220A CN101941939A CN 101941939 A CN101941939 A CN 101941939A CN 201010233220 CN201010233220 CN 201010233220 CN 201010233220 A CN201010233220 A CN 201010233220A CN 101941939 A CN101941939 A CN 101941939A
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- Prior art keywords
- carbazole
- ester compound
- oxime ester
- deriving
- polyfunctional group
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- -1 carbazole derivative oxime ester compound Chemical class 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000003505 polymerization initiator Substances 0.000 title 1
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 50
- 125000003118 aryl group Chemical group 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 150000001350 alkyl halides Chemical class 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 5
- 238000005917 acylation reaction Methods 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- DQQYORZGTHOZKE-UHFFFAOYSA-N 1-(6-nitro-9h-carbazol-3-yl)ethanone Chemical compound C1=C([N+]([O-])=O)C=C2C3=CC(C(=O)C)=CC=C3NC2=C1 DQQYORZGTHOZKE-UHFFFAOYSA-N 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- 238000007306 functionalization reaction Methods 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 241000534944 Thia Species 0.000 claims description 3
- 230000010933 acylation Effects 0.000 claims description 3
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- 150000001348 alkyl chlorides Chemical class 0.000 claims description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 238000006396 nitration reaction Methods 0.000 claims description 2
- 150000002924 oxiranes Chemical class 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 17
- 239000003999 initiator Substances 0.000 abstract description 3
- 239000002585 base Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 0 *c(cc1)cc2c1[n]c1c2cccc1 Chemical compound *c(cc1)cc2c1[n]c1c2cccc1 0.000 description 7
- 239000003513 alkali Substances 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- CNILDPCFXDESRI-UHFFFAOYSA-N 1-(9h-carbazol-3-yl)ethanone Chemical compound C1=CC=C2C3=CC(C(=O)C)=CC=C3NC2=C1 CNILDPCFXDESRI-UHFFFAOYSA-N 0.000 description 4
- 206010034972 Photosensitivity reaction Diseases 0.000 description 4
- 238000003810 ethyl acetate extraction Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 4
- 230000036211 photosensitivity Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002923 oximes Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940125797 compound 12 Drugs 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LKVNIMHCAHVWOZ-UHFFFAOYSA-N 1-sulfonylcarbazole Chemical compound S(=O)(=O)=C1C=CC=C2C3=CC=CC=C3N=C12 LKVNIMHCAHVWOZ-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- JGFJDDMRCMCZMU-UHFFFAOYSA-N 3-(trifluoromethyl)-9h-carbazole Chemical compound C1=CC=C2C3=CC(C(F)(F)F)=CC=C3NC2=C1 JGFJDDMRCMCZMU-UHFFFAOYSA-N 0.000 description 1
- LTBWKAYPXIIVPC-UHFFFAOYSA-N 3-bromo-9h-carbazole Chemical compound C1=CC=C2C3=CC(Br)=CC=C3NC2=C1 LTBWKAYPXIIVPC-UHFFFAOYSA-N 0.000 description 1
- CABSFELLEWZIAK-UHFFFAOYSA-N 3-chloro-9h-carbazole Chemical compound C1=CC=C2C3=CC(Cl)=CC=C3NC2=C1 CABSFELLEWZIAK-UHFFFAOYSA-N 0.000 description 1
- IEUMYICVZHBVAV-UHFFFAOYSA-N 3-fluoro-9h-carbazole Chemical compound C1=CC=C2C3=CC(F)=CC=C3NC2=C1 IEUMYICVZHBVAV-UHFFFAOYSA-N 0.000 description 1
- OYIGWMXXIFYAGD-UHFFFAOYSA-N 3-iodo-9h-carbazole Chemical compound C1=CC=C2C3=CC(I)=CC=C3NC2=C1 OYIGWMXXIFYAGD-UHFFFAOYSA-N 0.000 description 1
- ZYNHZTIMNJKVLK-UHFFFAOYSA-N 3-nitro-9h-carbazole Chemical compound C1=CC=C2C3=CC([N+](=O)[O-])=CC=C3NC2=C1 ZYNHZTIMNJKVLK-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical class CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 1
- 229910021617 Indium monochloride Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical class COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 238000006957 Michael reaction Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 150000001716 carbazoles Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- POCFBDFTJMJWLG-UHFFFAOYSA-N dihydrosinapic acid methyl ester Natural products COC(=O)CCC1=CC(OC)=C(O)C(OC)=C1 POCFBDFTJMJWLG-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- QHDUJTCUPWHNPK-UHFFFAOYSA-N methyl 7-methoxy-2h-indazole-3-carboxylate Chemical compound COC1=CC=CC2=C(C(=O)OC)NN=C21 QHDUJTCUPWHNPK-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical class CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Indole Compounds (AREA)
Abstract
The invention discloses a polyfunctional carbazole derivative oxime ester compound shown in the structural general formula I, a preparation method thereof and application of the compound used as a light initiator.
Description
[technical field]
The present invention relates to the light trigger technical field, particularly is some polyfunctional group novel oxime ester compounds, their preparation method, and be the Photoepolymerizationinitiater initiater that contains ethylene linkage unsaturated compound system of effective constituent with this compound.
[background technology]
Oxime ester compound at the existing bibliographical information (EuropeanPolymer Journal, 1970,6,933) of the seventies in last century, and business-like product such as Quantacure PDO have occurred as light trigger.Though the light-initiated activity of this compounds is outstanding, has limited its widespread use owing to thermostability is usually not good enough.It should be noted that in this compounds in the past few years to obtain again paying attention to, particularly in containing the unsaturated system of ethylene linkage, form photosensitive composite as photopolymerization initiating activity composition.These photosensitive composites are at light-curable ink, the photosensitive printing version, and recording materials, fields such as photo-resist are widely used.
The oxime ester compound Recent study is active, and technical paper and patent documentation report are more, for example: Macromol.Symp.2004,217,77; Patent CN101014569A, CN101321727A, CN101679394A, CN101687794A, CN99108598, CN02811675, CN1800885A, CN1928716A, CN101158812A, CN101525393A, CN101634807A, and WO2008138733A1, WO0052530A1, WO2007071497A1, WO2009019173A1, WO2009147031A2, it is A that WO2009147033A1 etc. have described some general structures, B, the oxime ester side chain dimer type compound of C and dependency structure.Business-like oxime ester compound light trigger OXE-1 and OXE-2 have appearred on this basis, the photosensitivity system that these compounds are formed particularly has the sensitive response to 405 or 365 nanometer light, in the BM and the RGB making field of giant-screen LCD display important application is arranged.
Patent CN101528694A, CN101528682A, and CN101508744A is A to the said structure general formula respectively, B, the oxime ester compound of C has proposed important improvement, is D thereby disclosed general structure, E, the oxime ester compound of F, wherein structure type D and E find that the suitable replacement of nitro on aromatic nucleus can produce more highly sensitive Photoepolymerizationinitiater initiater, and structure type F is by modifying the Photoepolymerizationinitiater initiater that side chain has obtained solubility property and thermal stability application preferably.
But, research and develop the new highly sensitive that has concurrently, the light trigger of excellent solvability and thermostability remains the problem that needs solution.
What be worth paying special attention to is, though with general structure A-F compound and related derivatives is that the light trigger of representative has disclosed on molecular skeleton a plurality of zones and carries out the possibility that multiple substituting group changes, but known document and patent are not inquired into any dimerization or poly type polyfunctional group oxime ester compound that makes up from carbazole nitrogen-atoms surveyor's chain, these compounds are novel structures, these compounds are to optimizing the photosensitivity of oxime ester compound, strengthen its solvability and thermostability, improve the environment and the healthy friendly of photopolymerization process, particularly reduce volatile organic compounds remnants in postdevelopment bake (Post-development Baking) process, new technology solution route is provided.
[summary of the invention]
The invention provides the class polyfunctional group novel carbazole oxime ester compound of deriving, the compound that this class is new
Have following general structure I:
In general formula I, the integer of n value 2 to 6, preferred 2,3 and 4; X is NO
2, F, Cl, Br, I, PPh
2, O=PPh
2, SPh, SOPh, or SO
2Ph; R
1And R
2Be hydrogen independently of one another, or CN, or CF
3, or CF
2R
3, or CFR
3R
4Or carbonatoms is side chain or the straight chain of 1-24, contains or do not contain the alkyl of ring system structure, and this alkyl can be for being no more than 8 nitrogen, sulphur, or Sauerstoffatom is interrupted; Or carbonatoms is the aromatic base of 6-36, and this aromatic base can contain 1-6 substituent R independent of each other
5, R
5Can be R
3, OR
3, SR
3, COR
3, Br, F, Cl, I, CN, or NO
2Here R
3And R
4Be that carbonatoms is the alkyl of 1-16 independently of one another, aromatic base, or azepine, thia, the assorted aromatic base of oxa-; Q is a n valency connecting group, and it can be via polynary haloalkane, polyvalent alcohol, and polynary epoxy, or polyprotonic acid is derived.
The invention allows for the derive preparation method of oxime ester compound of above-mentioned polyfunctional group novel carbazole, its general synthesis technique comprises following five steps:
The first step: carbazole parent nucleus functionalization;
Second step: acylations
The 3rd step: connectionization
The 4th step: oximate
The 5th step: esterification
The novel cpd that the present invention proposes has high photosensitivity, can systematically regulate and control its solvability and thermostability via nitrogenous side chain connecting group easily simultaneously, therefore, can be applied to prepare " personalization " high sensitivity light trigger with various kinds of resin system performance compatibility.In addition, they have more polar group and higher molecular weight owing to connecting, thereby can significantly reduce the remnants of volatile organic compounds in the postdevelopment bake process.
[embodiment]
The invention provides a class formation general formula and be the oxime ester compound of deriving of the polyfunctional group novel carbazole shown in (I), the compound that this class is new has following general structure I:
In general formula I, the integer of n value 2 to 6, preferred 2,3 and 4; X is NO
2, F, Cl, Br, I, PPh
2, O=PPh
2, SPh, SOPh, or SO
2Ph; R
1And R
2Be hydrogen independently of one another, or CN, or CF
3, or CF
2R
3, or CFR
3R
4Or carbonatoms is side chain or the straight chain of 1-24, contains or do not contain the alkyl of ring system structure, and this alkyl can be for being no more than 8 nitrogen, sulphur, or Sauerstoffatom is interrupted; Or carbonatoms is the aromatic base of 6-36, and this aromatic base can contain 1-6 substituent R independent of each other
5, R
5Can be R
3, OR
3, SR
3, COR
3, Br, F, Cl, I, CN, or NO
2Here R
3And R
4Be that carbonatoms is the alkyl of 1-16 independently of one another, aromatic base, or azepine, thia, the assorted aromatic base of oxa-; Q is a n valency connecting group, and it can be via polynary haloalkane, polyvalent alcohol, and polynary epoxy, or polyprotonic acid is derived.
When Q derives via polynary haloalkane and when coming, these haloalkanes are preferably as follows the alkyl chloride or the bromoalkane of structure:
When Q is when polyol derivative comes, these alcohol are preferably as follows structure:
When Q derives and when coming, these acrylate are preferably as follows structure from multicomponent methacrylate:
When Q derives and when coming, these carboxylic acids are preferably as follows structure from polycarboxylic acid:
When Q is when coming from polynary oxirane derivative, these oxyethane are preferably as follows structure:
Because the existence of the two keys of C=N may produce cis-trans-isomer, they usually can directly use without separating the oxime ester compound of general structure I in preparation process.
The invention allows for the preparation method of above-claimed cpd, its general synthesis technique comprises five following steps:
The first step: carbazole parent nucleus functionalization
Many carbazole 3-position is that document is known by the carbazole functionalization compound 1 that the X group replaces, be the commercially available prod or can be easily via known technology preparation, for example 3-nitro carbazole [SupramolecularChemistry, 20 (4), 357-361; 2008], 3-chloro carbazole [Journal of the Chemical SocietySection C:Organic, (16), 2775-7; 1971], 3-bromo carbazole [Synthesis, (10), 1619-1624; 2005], 3-fluoro carbazole [Journal of Organic Chemistry, 73 (13), 5022-5028; 2008], 3-iodo carbazole [Journal of the American Chemical Society, 131 (47), 17452-17463; 2009], 3-cyano group carbazole [Journal ofthe Chemical Society, 500-4; 1942], 3-trifluoromethyl carbazole [Journal of Organic Chemistry, 74 (13), 4720-4726; 2009], 3-benzene sulfuryl carbazole [Tetrahedron, 45 (16), 5059-64; 1989], 3-diphenyl phosphine carbazole [Advanced Synthesis﹠amp; Catalysis, 346 (7), 743-754; 2004].
Second step: acylations
Carbazole compound 1 that X replaces and suitable acyl chlorides R
1C (O) Cl carries out friedel-crafts acylation reaction under Louis's acid type reagent promotes can make intermediate 2, and the Lewis acid that can select for use comprises AlCl
3, ZnCl
2, FeCl
3, InCl
3, rare earth trifluoromethyl sulfonic acid La (OTf)
3, Sc (OTf)
3, or In (OTf)
3Deng.
The 3rd step: connectionization
Intermediate 2 can with polynary connective element Q via multiple reaction key and.Union body Q with divalence is an example, and binary halides 3 or dibasic alcohol deutero-p-methyl benzenesulfonic acid 4 and 2 carry out nucleophilic substitution reaction and can make 5 under alkali promotes, the alkali that can select for use comprises K
2CO
3, CsCO
3, MeONa, EtONa, NaH etc.; The amidation condensation takes place di-carboxylic acid 6 and 2 can make 7; The epoxy ring-opening reaction takes place binary epoxy 8 and 2 can make 9; Michael reaction takes place and can make 11 in binary acrylate 10 and 2 under organic or inorganic alkali promotes.
The 4th step: oximate
Senior intermediate 5,7,9,11 after the Q connectionization and oxammonium hydrochloride condensation in intensive polar solvent can make oxime compound 12, the preferred N of reaction solvent, dinethylformamide, methane amide, dioxane, ethanol, methyl alcohol, ethylene glycol, or the suitable proportion mixture of these solvents and water.
The 5th step: esterification
Oxime compound 12 and acyl chlorides R that the last step makes
2Esterification takes place and promptly makes final product oxime ester 13 (being the general formula I target compound) in C (O) Cl under alkali promotes, employed alkali can be organic bases or mineral alkali, preferred triethylamine, pyridine, propylene oxide, or K
2CO
3
Execution order that it should be noted that these steps can be done suitable adjustment according to the particular case of institute's synthetic compound.For example, for 3-nitro 6-ethanoyl-carbazole synthetic,, for obtaining yield preferably, suitablely on the carbazole ring, carry out acylation reaction earlier, carry out nitration reaction again, thereby obtain target product because nitro is the group of the deactivated aromatics stronger than ethanoyl.
The preferred embodiment of the oxime ester compound of representing as above-mentioned general formula I can list following compound structure:
The new compound that the present invention proposes can be used as unsaturated allyl compound or contains the light trigger of light polymerization of the mixture of unsaturated allyl compound.Below be the specific examples that is used as light trigger:
Embodiment: (1E, 1 ' E)-1-(9-(2-(3-((E)-1-(acetyl oxygen imines) ethyl)-6-nitro-9H-carbazole-9-yl) ethyl)-6-nitro-9H-carbazole-3-yl) ethyl ketone-oxygen-ethyl oxime
The first step: 3,9-diacetyl group carbazole and 3-ethanoyl carbazole synthetic:
Get 55.2 gram carbazoles and place 1 liter of exsiccant dithiocarbonic anhydride, add 88.0 gram aluminum trichloride (anhydrous)s, under powerful mechanical stirring, 62.2 gram Acetyl Chloride 98Min.s are added in batches.Finishing reaction system refluxed 6 hours; pour in frozen water and the dilute hydrochloric acid, isolate organic phase, water is used the equal-volume ethyl acetate extraction 2 times again; merge organic phase; wash 2 times, dried over mgso, solvent is spin-dried for; resistates obtains 44.8 grams with the methylene dichloride wash-out on a funnel that is filled with silica gel; the product 3 of 54% yield, 9-diacetyl group carbazole, grey chlorine look solid.
Proton nmr spectra
1H MR (CDCl
3, ppm unit):
8.87(s，1H)，8.18(d，1H，J＝8.4Hz)，8.04-8.00(m，3H)，7.58-7.52(t，1H)，7.45-7.40(m，1H)，2.92(s，3H)，2.76(s，3H)；
Synthesizing of 3-ethanoyl carbazole: 3, the hydrolysis in the dilute sulphuric acid of 2N of 9-diacetyl group carbazole promptly can be converted into 3-ethanoyl carbazole fast, colourless blocks of solid, fusing point 226-228 ℃.
Second step: 3-ethanoyl-6-nitro carbazole synthetic:
Get 62.8 gram 3-ethanoyl carbazoles and place 1 liter acetate, under powerful mechanical stirring, the urea nitrate [HNO of equivalent
3O=C (NH
2)
2] slowly add, mixed solution continues to stir, and with tlc tracking monitor reaction process, after the reaction in about 4 hours, reaction solution pours in the big water gaging, separates out a large amount of precipitations, filter, washing, drying, thick product recrystallization in acetate obtains pure product.
1H?NMR(d
6-DMSO，ppm)：12.27(br，1H)，10.08(dd，2H)，9.13(s，1H)，8.81-8.20(m，1H)，7.66-7.46(m，1H)，7.44-7.26(m，1H)，2.77(s，3H)。
High resolution mass spectrum HRMS (M+H): C
14H
11N
2O
3, theoretical value 255.0770, measured value 255.0775.
The 3rd step: 1,1 '-(9,9 '-(butane-1,4-two bases) two (6-nitro-9H-carbazole-9,3-two bases)) diethyl ketone synthetic:
Under nitrogen protection; get 13.9 gram 3-ethanoyl-6-nitro carbazoles and place 160 milliliters of exsiccant DMF; add 2.7 gram sodium hydrides (60% mineral oil disperses thing) in batches; stirring reaction half an hour; Dropwise 5 .8 gram 1; the solution of 4-dibromobutane in 15 milliliters of dry DMF, the mixture stirring reaction spends the night.Reaction solution is poured in 600 ml waters, with 400 milliliters of ethyl acetate extractions 3 times, merge organic phase, respectively wash 1 time with saturated aqueous common salt and water, dried over mgso, solvent is spin-dried for, and resistates on silica gel column chromatography is that eluent wash-out purifying obtains 7.8 gram dimerization products, 51% yield with the ethyl acetate/hexane.
High resolution mass spectrum HRMS (M+H): C
32H
27N
4O
6, theoretical value 563.1931, measured value 563.1936.
The 4th step: under nitrogen protection; get the above-mentioned dimer 1 of 7.4 grams; 1 '-(9; 9 '-(butane-1; 4-two bases) two (6-nitros-9H-carbazole-9; 3-two bases)) diethyl ketone placed 40 milliliters of dimethyl formamides, adds the 4 dust molecular sieves that 2.8 gram oxammonium hydrochlorides and 2.0 restrain thermal activation in advance, 80 ℃ of stirring reactions 3 hours; pour in 200 ml waters after being cooled to room temperature; with equal-volume ethyl acetate extraction 3 times, merge organic phase, respectively wash 1 time with saturated aqueous common salt and water; dried over mgso; solvent is spin-dried for, residual solid directly and 3.3 gram diacetyl oxides is mixed in 60 milliliters of butylacetates, 90 ℃ of stirring reactions 2 hours.Reaction system is cooled to room temperature, and to neutral, the same usefulness 200 ml waters dilute with 5% dilute sodium hydroxide aqueous solution regulation system, and ethyl acetate extraction separates the thick product Crystallization Separation in ethyl acetate that obtains and obtains 5.5 gram pure compounds, 62% yield.
1H NMR (d
6-DMSO, ppm unit): 9.04 (d, 2H), 8.50 (d, 2H), 8.38 (dd, 2H), 8.10 (dd, 2H), 7.52 (d, 2H), 7.42 (d, 2H), 4.46 (t, 4H), 2.52 (s, 6H), 2.36 (t, 6H), 1.61 (t, 4H).
High resolution mass spectrum HRMS (M+H): C
36H
33N
6O
8, theoretical value 677.2360, measured value 677.2363.
C/H ultimate analysis: C
36H
32N
6O
8:
Theoretical value: C 63.90%, H 4.77%; Measured value: C 63.94%, H 4.85%.
Light sensitivity and the test of remaining smell:
Sensitivity test sample making: with 20 weight percents (down together) methacrylic acid, 15 parts of methacrylic acid hydroxyl ethyl esters, 10 parts of methyl methacrylates, and 55 parts of butyl methacrylate and 300 parts of ethyl cellosolves mixing, add 1 part of AIBN 70 degrees centigrade of reactions 5 hours, obtain the multipolymer of aforesaid propylene acid system.Next step is got 65 parts of these acrylic copolymers and 5 parts of dipentaerythritol acrylates and 30 parts of acetone and mixes.Under the gold-tinted protection; the light trigger that in this mixture, adds 2 parts; stirring and dissolving; get a little this sample application on aluminium sheet; slowly dry 40 minutes except that desolvating at 65 degrees centigrade; cover cellulose acetate film; 21 GTG standard test egative films of different optical density(OD) are set; use metal halide lamp in 60 centimeters with time of locking exposure (40 seconds and 80 seconds); thereafter develop with 1% yellow soda ash alkali lye, develop high gray number that the back keeps because of polymerizing curable of observation is judged the photosensitivity of initiator system.
Remaining smell evaluation: the sample panel after will developing places airtight vial, and this vial of baking is 1 minute in 100 degrees centigrade of baking ovens, and 7 people estimate the smell rank respectively independently, and evaluating standard is as follows with figure denote:
0 grade: do not have smell;
1 grade: very slight smell;
2 grades: slight smell;
3 grades: tangible smell;
4 grades: the intensive smell;
5 grades: unusual intensive smell.
The result who provides by 5 bifunctional initiators of embodiment synthetic is as follows:
Claims (10)
1. structure is the polyfunctional group carbazole of general formula (I) oxime ester compound of deriving,
In general formula I, the integer of n value 2 to 6; X is NO
2, F, Cl, Br, I, PPh
2, O=PPh
2, SPh, SOPh, or SO
2Ph; R
1And R
2Be hydrogen independently of one another, or CN, or CF
3, or CF
2R
3, or CFR
3R
4Or carbonatoms is side chain or the straight chain of 1-24, contains or do not contain the alkyl of ring system structure, and this alkyl can be for being no more than 8 nitrogen, sulphur, or Sauerstoffatom is interrupted; Or carbonatoms is the aromatic base of 6-36, and this aromatic base can contain 1-6 substituent R independent of each other
5, R
5Can be R
3, OR
3, SR
3, COR
3, Br, F, Cl, I, CN, or NO
2Here R
3And R
4Be that carbonatoms is the alkyl of 1-16 independently of one another, aromatic base, or azepine, thia, the assorted aromatic base of oxa-; Q is a n valency connecting group, and it can be via polynary haloalkane, polyvalent alcohol, and polynary epoxy, or polyprotonic acid is derived.
2. the described polyfunctional group carbazole of claim 1 oxime ester compound of deriving, wherein: the n value is preferred 2,3, or 4.
3. the described polyfunctional group carbazole of claim 1 oxime ester compound of deriving, wherein: when Q derives via polynary haloalkane and when coming, these haloalkanes are preferably as follows the alkyl chloride or the bromoalkane of structure:
4. the described polyfunctional group carbazole of claim 1 oxime ester compound of deriving, wherein: when Q is when polyol derivative comes, these alcohol are preferably as follows structure:
5. the described polyfunctional group carbazole of claim 1 oxime ester compound of deriving, wherein: when Q derives and when coming, these acrylate are preferably as follows structure from multicomponent methacrylate:
6. the described polyfunctional group carbazole of claim 1 oxime ester compound of deriving, wherein: when Q derives and when coming, these carboxylic acids are preferably as follows structure from polycarboxylic acid:
7. the described polyfunctional group carbazole of claim 1 oxime ester compound of deriving, wherein: when Q is when coming from polynary oxirane derivative, these oxyethane are preferably as follows structure:
8. the described carbazole of claim 1 preparation method of oxime ester compound that derives, it comprises following five steps:
The first step: carbazole parent nucleus functionalization;
Second step: acylations
The 3rd step: connectionization
The 4th step: oximate
The 5th step: esterification
9. the described carbazole of claim 1 preparation method of oxime ester compound that derives, wherein: for 3-nitro 6-ethanoyl-carbazole synthetic, on the carbazole ring, carry out acylation reaction earlier, carry out nitration reaction again.
10. the carbazole of general structure (I) purposes of oxime ester compound of deriving as light trigger.
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Denomination of invention: Polyfunctional carbazole derived oxime ester compounds, preparation method and photopolymerization initiator thereof Effective date of registration: 20201102 Granted publication date: 20130529 Pledgee: Industrial and Commercial Bank of China Limited Shenzhen gaoxinyuan sub branch Pledgor: Shenzhen Youwei Technology Holding Co.,Ltd. Registration number: Y2020980007427 |
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Granted publication date: 20130529 Pledgee: Industrial and Commercial Bank of China Limited Shenzhen gaoxinyuan sub branch Pledgor: Shenzhen Youwei Technology Holding Co.,Ltd. Registration number: Y2020980007427 |
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Application publication date: 20110112 Assignee: Hubei Youyi New Material Technology Co.,Ltd. Assignor: Shenzhen Youwei Technology Holding Co.,Ltd. Contract record no.: X2024980003537 Denomination of invention: Multifunctional carbazole derived oxime ester compounds, their manufacturing methods, and their photopolymerization initiators Granted publication date: 20130529 License type: Exclusive License Record date: 20240328 |