CN115536589A - Imidazole ketoxime ester compound, preparation method, composition and application - Google Patents
Imidazole ketoxime ester compound, preparation method, composition and application Download PDFInfo
- Publication number
- CN115536589A CN115536589A CN202211366780.2A CN202211366780A CN115536589A CN 115536589 A CN115536589 A CN 115536589A CN 202211366780 A CN202211366780 A CN 202211366780A CN 115536589 A CN115536589 A CN 115536589A
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- Prior art keywords
- group
- carbons
- alkenyl
- alkyl
- amino
- Prior art date
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- -1 ester compound Chemical class 0.000 title claims abstract description 81
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title abstract description 40
- 239000000203 mixture Substances 0.000 title abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 10
- 239000006096 absorbing agent Substances 0.000 claims abstract 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 32
- 229910052736 halogen Inorganic materials 0.000 claims description 31
- 150000002367 halogens Chemical class 0.000 claims description 31
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 21
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 21
- 125000001424 substituent group Chemical group 0.000 claims description 18
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 17
- 125000003545 alkoxy group Chemical group 0.000 claims description 16
- 125000002252 acyl group Chemical group 0.000 claims description 14
- 125000003282 alkyl amino group Chemical group 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 8
- 125000000623 heterocyclic group Chemical group 0.000 claims description 8
- 125000004185 ester group Chemical group 0.000 claims description 7
- 125000004449 heterocyclylalkenyl group Chemical group 0.000 claims description 7
- 125000004415 heterocyclylalkyl group Chemical group 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000005251 aryl acyl group Chemical group 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- LBQAJLBSGOBDQF-UHFFFAOYSA-N nitro azanylidynemethanesulfonate Chemical group [O-][N+](=O)OS(=O)(=O)C#N LBQAJLBSGOBDQF-UHFFFAOYSA-N 0.000 claims 2
- 125000003277 amino group Chemical group 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 125000005343 heterocyclic alkyl group Chemical group 0.000 claims 1
- 125000000542 sulfonic acid group Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 47
- 238000000034 method Methods 0.000 abstract description 14
- 239000010802 sludge Substances 0.000 abstract description 14
- 150000002148 esters Chemical class 0.000 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 15
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 11
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 10
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 150000002431 hydrogen Chemical class 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 125000005018 aryl alkenyl group Chemical group 0.000 description 7
- 239000000852 hydrogen donor Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- 150000002923 oximes Chemical class 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- CGOJOQBYEAVATL-UHFFFAOYSA-N 3-(4-methoxyphenyl)prop-2-enoyl chloride Chemical compound COC1=CC=C(C=CC(Cl)=O)C=C1 CGOJOQBYEAVATL-UHFFFAOYSA-N 0.000 description 5
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 5
- 239000005695 Ammonium acetate Substances 0.000 description 5
- 235000019257 ammonium acetate Nutrition 0.000 description 5
- 229940043376 ammonium acetate Drugs 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 5
- AFDXODALSZRGIH-QPJJXVBHSA-N (E)-3-(4-methoxyphenyl)prop-2-enoic acid Chemical compound COC1=CC=C(\C=C\C(O)=O)C=C1 AFDXODALSZRGIH-QPJJXVBHSA-N 0.000 description 4
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 description 4
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 125000002757 morpholinyl group Chemical group 0.000 description 4
- AFDXODALSZRGIH-UHFFFAOYSA-N p-coumaric acid methyl ether Natural products COC1=CC=C(C=CC(O)=O)C=C1 AFDXODALSZRGIH-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000003107 substituted aryl group Chemical group 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229940124543 ultraviolet light absorber Drugs 0.000 description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 4
- LEFOGMKQWGWBOC-UHFFFAOYSA-N 2-(2-chlorophenyl)-1-hydroxy-4,5-diphenylimidazole Chemical compound ON1C(C=2C(=CC=CC=2)Cl)=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 LEFOGMKQWGWBOC-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LSTFKZJERJEYIA-UHFFFAOYSA-N C=CC(=O)ON1C(=C(N=C1C2=CC=CC=C2Cl)C3=CC=CC=C3)C4=CC=CC=C4 Chemical compound C=CC(=O)ON1C(=C(N=C1C2=CC=CC=C2Cl)C3=CC=CC=C3)C4=CC=CC=C4 LSTFKZJERJEYIA-UHFFFAOYSA-N 0.000 description 3
- NPKSPKHJBVJUKB-UHFFFAOYSA-N N-phenylglycine Chemical compound OC(=O)CNC1=CC=CC=C1 NPKSPKHJBVJUKB-UHFFFAOYSA-N 0.000 description 3
- YYSJQGMYYITBTB-UHFFFAOYSA-N ON=C1N=CC=N1 Chemical class ON=C1N=CC=N1 YYSJQGMYYITBTB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- VTESCYNPUGSWKG-UHFFFAOYSA-N (4-tert-butylphenyl)hydrazine;hydrochloride Chemical compound [Cl-].CC(C)(C)C1=CC=C(N[NH3+])C=C1 VTESCYNPUGSWKG-UHFFFAOYSA-N 0.000 description 2
- XUVKSPPGPPFPQN-UHFFFAOYSA-N 10-Methyl-9(10H)-acridone Chemical compound C1=CC=C2N(C)C3=CC=CC=C3C(=O)C2=C1 XUVKSPPGPPFPQN-UHFFFAOYSA-N 0.000 description 2
- BNGOFPJWZUXKNR-UHFFFAOYSA-N 2-oxo-2-phenylacetyl chloride Chemical compound ClC(=O)C(=O)C1=CC=CC=C1 BNGOFPJWZUXKNR-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- CPDBPHBPPKVCGQ-UHFFFAOYSA-N C1=CC=C(C=C1)C2=C(N(C(=N2)C3=CC=CC=C3Cl)C4=CC=CC=C4C(=O)O)C5=CC=CC=C5 Chemical compound C1=CC=C(C=C1)C2=C(N(C(=N2)C3=CC=CC=C3Cl)C4=CC=CC=C4C(=O)O)C5=CC=CC=C5 CPDBPHBPPKVCGQ-UHFFFAOYSA-N 0.000 description 2
- LDOCKIYEVBFNKS-UHFFFAOYSA-N CC(=O)C(=O)ON1C(=C(N=C1C2=CC=CC=C2Cl)C3=CC=CC=C3)C4=CC=CC=C4 Chemical compound CC(=O)C(=O)ON1C(=C(N=C1C2=CC=CC=C2Cl)C3=CC=CC=C3)C4=CC=CC=C4 LDOCKIYEVBFNKS-UHFFFAOYSA-N 0.000 description 2
- AOSPQASUERYQHG-UHFFFAOYSA-N CC(=O)ON1C(=C(N=C1C2=CC=CC=C2Cl)C3=CC=CC=C3)C4=CC=CC=C4 Chemical compound CC(=O)ON1C(=C(N=C1C2=CC=CC=C2Cl)C3=CC=CC=C3)C4=CC=CC=C4 AOSPQASUERYQHG-UHFFFAOYSA-N 0.000 description 2
- CVZIHBVAAQUYPL-UHFFFAOYSA-N CCCCCCCCCCCCCCCCCC(=O)ON1C(=C(N=C1C2=CC=CC=C2Cl)C3=CC=CC=C3)C4=CC=CC=C4 Chemical compound CCCCCCCCCCCCCCCCCC(=O)ON1C(=C(N=C1C2=CC=CC=C2Cl)C3=CC=CC=C3)C4=CC=CC=C4 CVZIHBVAAQUYPL-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229920001651 Cyanoacrylate Polymers 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000005257 alkyl acyl group Chemical group 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 2
- 229960003328 benzoyl peroxide Drugs 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 125000003884 phenylalkyl group Chemical group 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 2
- MAOBFOXLCJIFLV-UHFFFAOYSA-N (2-aminophenyl)-phenylmethanone Chemical class NC1=CC=CC=C1C(=O)C1=CC=CC=C1 MAOBFOXLCJIFLV-UHFFFAOYSA-N 0.000 description 1
- YNANGXWUZWWFKX-UHFFFAOYSA-N 1,2-bis(4-methoxyphenyl)ethane-1,2-dione Chemical compound C1=CC(OC)=CC=C1C(=O)C(=O)C1=CC=C(OC)C=C1 YNANGXWUZWWFKX-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical class C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- AQFXIWDRLHRFIC-UHFFFAOYSA-N 1-[5-phenyl-3-(trifluoromethyl)pyrazol-1-yl]ethanone Chemical group CC(=O)N1N=C(C(F)(F)F)C=C1C1=CC=CC=C1 AQFXIWDRLHRFIC-UHFFFAOYSA-N 0.000 description 1
- DJQUGRDXHMJDTJ-UHFFFAOYSA-N 1-chloro-10h-acridin-9-one Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl DJQUGRDXHMJDTJ-UHFFFAOYSA-N 0.000 description 1
- QPNUYUBATRFUSC-UHFFFAOYSA-N 1-naphthalen-2-yl-2-phenylethane-1,2-dione Chemical compound C=1C=C2C=CC=CC2=CC=1C(=O)C(=O)C1=CC=CC=C1 QPNUYUBATRFUSC-UHFFFAOYSA-N 0.000 description 1
- YJHZXKQYHAYVOU-UHFFFAOYSA-N 1-phenyl-2-pyridin-2-ylethane-1,2-dione Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=N1 YJHZXKQYHAYVOU-UHFFFAOYSA-N 0.000 description 1
- QFDDZIRGHKFRMR-UHFFFAOYSA-N 10-butylacridin-9-one Chemical compound C1=CC=C2N(CCCC)C3=CC=CC=C3C(=O)C2=C1 QFDDZIRGHKFRMR-UHFFFAOYSA-N 0.000 description 1
- RNIPJYFZGXJSDD-UHFFFAOYSA-N 2,4,5-triphenyl-1h-imidazole Chemical compound C1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 RNIPJYFZGXJSDD-UHFFFAOYSA-N 0.000 description 1
- YSFBEAASFUWWHU-UHFFFAOYSA-N 2,4-dichlorobenzaldehyde Chemical group ClC1=CC=C(C=O)C(Cl)=C1 YSFBEAASFUWWHU-UHFFFAOYSA-N 0.000 description 1
- PKZJLOCLABXVMC-UHFFFAOYSA-N 2-Methoxybenzaldehyde Chemical compound COC1=CC=CC=C1C=O PKZJLOCLABXVMC-UHFFFAOYSA-N 0.000 description 1
- OLBYFEGTUWWPTR-UHFFFAOYSA-N 2-hydroxyimino-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=NO)C(=O)C1=CC=CC=C1 OLBYFEGTUWWPTR-UHFFFAOYSA-N 0.000 description 1
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical class C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 description 1
- AUUTXOKCFQTKPL-UHFFFAOYSA-N 2-oxopropanoyl chloride Chemical group CC(=O)C(Cl)=O AUUTXOKCFQTKPL-UHFFFAOYSA-N 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- ULIBQSDNJYRNHR-UHFFFAOYSA-N 3-chloro-4-(dimethylamino)benzaldehyde Chemical group CN(C)C1=CC=C(C=O)C=C1Cl ULIBQSDNJYRNHR-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- PAGKSZOBDCPRNK-UHFFFAOYSA-N C1=CC=C(C=C1)C2=C(C(=C(C=C2)C(=O)OC3=NC=CN3)C4=CC=CC=C4)C5=CC=CC=C5 Chemical class C1=CC=C(C=C1)C2=C(C(=C(C=C2)C(=O)OC3=NC=CN3)C4=CC=CC=C4)C5=CC=CC=C5 PAGKSZOBDCPRNK-UHFFFAOYSA-N 0.000 description 1
- XDJVFMZAWLWYLG-UHFFFAOYSA-N C1=CC=C(C=C1)C2=C(N(C(=N2)C3=C(C=C(C=C3)Cl)Cl)C4=CC=CC=C4C(=O)O)C5=CC=CC=C5 Chemical compound C1=CC=C(C=C1)C2=C(N(C(=N2)C3=C(C=C(C=C3)Cl)Cl)C4=CC=CC=C4C(=O)O)C5=CC=CC=C5 XDJVFMZAWLWYLG-UHFFFAOYSA-N 0.000 description 1
- CWMGITUHWBUWEV-UHFFFAOYSA-N CN(C)C1=CC(=C(C=C1)C(=O)O)N2C(=C(N=C2C3=CC=CC=C3Cl)C4=CC=CC=C4)C5=CC=CC=C5 Chemical compound CN(C)C1=CC(=C(C=C1)C(=O)O)N2C(=C(N=C2C3=CC=CC=C3Cl)C4=CC=CC=C4)C5=CC=CC=C5 CWMGITUHWBUWEV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- BRHJUILQKFBMTL-UHFFFAOYSA-N [4,4-bis(dimethylamino)cyclohexa-1,5-dien-1-yl]-phenylmethanone Chemical compound C1=CC(N(C)C)(N(C)C)CC=C1C(=O)C1=CC=CC=C1 BRHJUILQKFBMTL-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001251 acridines Chemical class 0.000 description 1
- FZEYVTFCMJSGMP-UHFFFAOYSA-N acridone Chemical class C1=CC=C2C(=O)C3=CC=CC=C3NC2=C1 FZEYVTFCMJSGMP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 125000001743 benzylic group Chemical group 0.000 description 1
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- 239000007805 chemical reaction reactant Substances 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
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- 238000007599 discharging Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
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- 125000004366 heterocycloalkenyl group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- LQNUZADURLCDLV-IDEBNGHGSA-N nitrobenzene Chemical group [O-][N+](=O)[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 LQNUZADURLCDLV-IDEBNGHGSA-N 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Substances [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- WTBAHSZERDXKKZ-UHFFFAOYSA-N octadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCCCC(Cl)=O WTBAHSZERDXKKZ-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 1
- 229940038597 peroxide anti-acne preparations for topical use Drugs 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000002165 photosensitisation Effects 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000004897 thiazines Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 125000001834 xanthenyl group Chemical class C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
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- C08F2/00—Processes of polymerisation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- 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
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
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- 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
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Abstract
The present invention relates to novel imidazolone oxime ester compounds, methods of preparation, compositions and uses in photoinitiators, photosensitizers, light absorbers, or photosensitizers. The imidazolone oxime ester compound simultaneously has the structural characteristics of an imidazole photoinitiator (such as BCIM) and a ketoxime ester photoinitiator (such as 0 XE-1). On the one hand, the compounds of the invention improve the disadvantage of sludge formation in imidazole photoinitiators. On the other hand, the compound improves the problem of poor thermal stability of ketoxime ester photoinitiators and increases the convenience of operation.
Description
Technical Field
The invention relates to novel imidazolone oxime ester compounds, and synthesis and application thereof in photoinitiation or light absorption. The Imidazole ketoxime ester compound has the structural characteristics of functional groups of Imidazole photoinitiators (such as BCIM) and ketoxime ester photoinitiators (such as OXE-1). The compound or composition of the present invention, which is used in the photocuring, optical or electronic industries.
Background
Photoinitiators are important chemicals in the photocuring industry, such as in the fields of coatings, inks, adhesives, photoresists, and the like. The light curing material monomer can activate the unsaturated groups in the light curing material to perform polymerization reaction under the irradiation of a light source with a certain wavelength by adding a photoinitiator, and the light curing material is cured. Good photoinitiators are key to the success of photocuring techniques. Traditional photoinitiators include benzoins, acetophenones, benzophenones, thioxanthones, acylphosphine oxides, aromatic diazo salts, ferrocenes, triazines, hexaarylbisimidazoles, oxime esters, and the like. Of these, the hexaarylbisimidazoles and oxime esters are of particular interest. However, since most of these conventional photoinitiators have disadvantages, their use is greatly limited.
For example, the most representative compound of the hexaaryldiimidazoles, 2,2' -bis (2-chlorophenyl) -4,4',5,5' -tetraphenyl 1,2-diimidazole (BCIM), is generally sensitive to ultraviolet light of shorter wavelength (UVmax: 255 to 275 nm). In practical applications, the BCIM of the two-unit body must be used with a sensitizer or/and a hydrogen donor to achieve better effect (US 4622286, US4162162, US 4459394). Further, BCIM causes a residue accumulation which generates sludge (sludge) in the developer solution during the process of producing printed circuits, and the accumulation of sludge shortens the lifetime of the developer, which is a serious problem. In addition, the novel ketoxime ester photoinitiators, such as typical photoinitiator OXE-1 (CN 99108598 and CN 02811675), can be applied to the manufacture of components of large-screen LCD displays, but have the problems of low melting point (42 ℃) and poor thermal stability, and are unfavorable for transportation and operation.
In view of the above, development of a photoinitiator having high stability, good workability, low sludge, high sensitivity, and reduced use of a sensitizer and/or a hydrogen donor has been the main problem in the industry related to photocuring.
The imidazolone oxime ester compounds of the present invention have never been found to have photoinitiating properties or other optical applications. Imidazolone oxime esters have been found to have pesticidal use (WO 2005108374). Nitro-substituted 2,4,5-triphenyl-benzoyloxy-imidazole oxime compounds were synthesized as CASPLUS (AN 1971, dn 74 125561. A2-methyl-substituted pyridinylacryloyl imidazole compound has been synthesized as CASPLUS (AN 1972. The application is a reaction monomer of polypropylene-styrene (CAS RN 38779-88-3). None of the above compounds disclose photoinitiating properties or other optical applications and all are excluded from the compound claims. CASRN:1674371-29-9, a compound of formula (III) of the present invention, recorded in the CAS Client Services/Source of Registration) of the STN CAS registry database. CASRN:1674371-29-9 is registered by the applicant of the present invention and never leaks any manufacturing or use data. Therefore, the novelty and the creativity of the present invention are not affected at all.
Disclosure of Invention
The imidazolone oxime ester compound simultaneously has the structural characteristics of imidazole photoinitiator (such as BCIM) and ketoxime ester photoinitiator (such as OXE-1) functional groups. On one hand, the imidazole ketoxime ester compound improves the problem of poor thermal stability of a general ketoxime ester (OXE-1) photoinitiator, and increases the operation convenience. On the other hand, the imidazolone oxime ester compounds of the present invention improve the sludge-bearing disadvantage of BCIM photoinitiators. The compound of the present invention has high stability, good workability, low sludge and high maintenance sensitivity. The amount of sensitizer and/or hydrogen donor used can also be reduced.
The structure of the imidazolone oxime ester compound or the salt thereof is shown as the formula (I):
wherein R is 1 ～R 4 Is one or more and is each independently selected from the group consisting of hydrogen, hydroxyl, oxy, thio, halogen, amino, nitro, nitroso, cyano, carboxyl, unsubstituted or substituted straight or branched alkyl of 1 to 20 carbons, alkenyl, alkynyl, aryl, heterocyclyl, carbonyl, acyl, alkylamino, alkoxy, alkylthio, arylalkyl, heterocyclylalkyl, arylalkenyl, heterocyclylalkenyl. Wherein oxy or thio means any group attached to the imidazole or ketoxime ester via oxygen or sulfur. Preferably, R 1 Is unsubstituted or substituted straight or branched chain alkyl, alkenyl, carbonyl, aryl, heterocyclyl, arylalkyl, heterocyclylalkyl, arylalkenyl, heterocyclylalkenyl, alkylamino, alkoxy, alkylacyl, arylacyl or heterocyclylacyl containing 1 to 20 carbons; r is 2 ～R 4 Is one or more and is each independently selected from hydrogen, hydroxyl, thio, halogen, amino, nitro, nitroso, cyano, carboxyl, sulfonic, sulfuric, phosphoric, phosphonic, the same or different unsubstituted or substituted straight or branched alkyl groups containing 1 to 20 carbons, alkenyl, aryl, heterocyclyl, arylalkyl, heterocyclylalkyl, arylalkenyl, or heterocyclylalkenyl; r 1 ～R 4 Is one or more and is each independently selected from the group consisting of hydroxy, halogen, amino, nitro, nitroso, cyano, carboxy, sulfo, sulfato, phospho, phosphono, unsubstituted or substituted phenyl, morpholino, benzoyl, unsubstituted or substituted straight or branched C 1 ～C 10 Alkyl radical, C 1 ～C 10 Alkenyl radical, C 1 ～C 10 Acyl radical, C 1 ～C 10 Carbonyl group, OR 5 、SR 5 、SO 2 R 5 、SO 3 R 5 、COOR 5 、COR 5 、OCOR 5 、C(O)NR 6 R 7 、SO 2 NR 6 R 7 Or NR 6 R 7 Wherein R is 5 、R 6 、R 7 Independently of one another, hydrogen, phenyl, straight-chain or branched C 1 ～C 6 Alkyl of (C) 1 ～C 6 Alkenyl or C 1 ～C 6 Alkoxy group of (2). More preferably, R 1 Is unsubstituted or substituted C1-C12 straight or branched chain alkyl, alkenyl, carbonyl, phenyl, biphenyl, alkoxy, alkylamino, alkanoyl, phenylacyl, or biphenylacyl; r 2 、R 3 Is the same or different unsubstituted or substituted aryl group containing 1 to 12 carbons; r 4 Is an unsubstituted or substituted aryl group of 1 to 12 carbons. R 1 -R 4 Is one or more and is each independently selected from the group consisting of hydroxy, halogen, amino, nitro, nitroso, cyano, carboxy, sulfo, sulfato, phospho, phosphono, unsubstituted or substituted phenyl, morpholinyl, benzoyl, unsubstituted or substituted straight or branched C 1 ～C 6 Alkyl radical, C 1 ～C 6 Alkenyl radical, C 1 ～C 6 Acyl radical, C 1 ～C 6 Carbonyl group, OR 5 、SR 5 、SO 2 R 5 SO 3 R 5 、COOR 5 、COR 5 、OCOR 5 、C(O)NR 6 R 7 、SO 2 NR 6 R 7 Or NR 6 R 7 Wherein R is 5 、R 6 、R 7 Independently of one another, hydrogen, phenyl, straight-chain or branched C 1 ～C 6 Alkyl of (C) 1 ～C 6 Alkenyl or C 1 ～C 6 Alkoxy group of (2). Particularly preferably, R 1 Is unsubstituted or substituted C 1～6 Alkyl radical, C 1～6 Alkenyl, phenyl, phenylalkyl, phenylalkenyl, C 1～4 Alkyl acyl, phenyl acyl; r 2～4 Is phenyl; r 1 -R 4 The substituent is hydroxyl, halogen, amino, nitro, cyano, carboxyl, sulfonic group, sulfuric acid group, C 1～6 Alkyl radical, C 1～6 Alkenyl radical, C 1～6 Alkylamino radical, or C 1～6 An alkoxy group. Particularly preferably, R 1 Is C 1 ～C 6 Alkyl of (C) 1 ～C 6 The substituents of which are one or more and are each independently selected from the group consisting of hydroxy, halogen, amino, nitro, nitroso, cyano, sulfonic, sulfuric, phosphoric, phosphonic, carbonyl of 1-6 carbons, ester, acyl, carboxy, alkylamino, alkoxy; r 4 Is phenyl, R 4 The substituents being one or more halogens, or/and C 1 ～C 12 Alkenyl, or/and C 1 ～C 4 Alkoxy, or/and C 1 ～C 12 Alkylamino radical, or/and C 1 ～C 12 Alkyl, wherein the substituents of the alkenyl group are one or more and each is independently selected from the group consisting of hydroxyl, halogen, amino, nitro, nitroso, cyano, sulfonic, sulfuric, phosphoric, phosphonic, carbonyl of 1-6 carbons, ester, acyl, carboxyl, alkylamino, alkoxy, alkyl, alkenyl. Or, R 4 The substituents being one or more halogens, or/and C 1 ～C 6 Alkenyl, or/and C 1 ～C 6 Alkoxy, or/and C 1 ～C 6 Alkylamino radical, or/and C 1 ～C 6 Alkyl, wherein the substituents of the alkenyl group are one or more and each is independently selected from the group consisting of hydroxy, halogen, amino, nitro, nitroso, cyano, carboxy, phosphate, phosphonate, sulfonate, sulfate, C 1～6 Carbonyl group, C 1～6 Ester group, C 1～6 Acyl radical, C 1～6 Alkylamino radical, C 1～6 Alkoxy radical, C 1～6 Alkyl radical, C 1～6 An alkenyl group. Or, R 4 The substituents being one or more halogens, or/and C 1 ～C 4 Alkenyl, or/and C 1 ～C 4 Alkoxy, or/and C 1 ～C 4 Alkylamino radical, or/and C 1 ～C 4 Alkyl, wherein the substituents of the alkenyl group are one or more and each is independently selected from the group consisting of hydroxy, halogen, amino, nitro, nitroso, cyano, carboxy, phosphate, phosphonate, sulfonate, sulfate, C 1～4 Carbonyl group, C 1～4 Ester group, C 1～4 Acyl radical, C 1～4 Alkylamino radical, C 1～4 Alkoxy radical, C 1～4 Alkyl radical, C 1～4 An alkenyl group.
The invention is a compound of formula (II),
R 1 is one or more and is each independently selected from unsubstituted or substituted straight or branched chain alkyl, alkenyl, carbonyl, aryl, biphenyl, heterocyclyl, arylalkyl, heterocyclylalkyl, arylalkenyl, heterocyclylalkenyl, alkylamino, alkoxy, alkanoyl, arylacyl or heterocyclylacyl of 1 to 20 carbons; r 4 Each independently selected from unsubstituted or substituted C1-C20 linear or branched alkyl, alkenyl, aryl, heterocyclyl, arylalkyl, heterocyclylalkyl, arylalkenyl, or heterocyclylalkenyl, 4 but R is not nitrobenzene；R 8 Is one or more and is each independently selected from the group consisting of hydrogen, hydroxy, halogen, amino, nitro, nitroso, cyano, carboxy, sulfonic, sulfuric, phosphoric, phosphonic, unsubstituted or substituted phenyl, morpholinyl, benzoyl, unsubstituted or substituted straight or branched C 1 ～C 10 Alkyl radical, C 1 ～C 10 Alkenyl radical, C 1 ～C 10 Acyl radical, C 1 ～C 10 Carbonyl group, OR 5 、SR 5 、SO 2 R 5 、SO 3 R 5 、COOR 5 、COR 5 、OCOR 5 、C(O)NR 6 R 7 、SO 2 NR 6 R 7 Or NR 6 R 7 Wherein R is 5 、R 6 、R 7 Independently of one another, hydrogen, phenyl, straight-chain or branched C 1 ～C 6 Alkyl of (C) 1 ～C 6 Alkenyl or C of 1 ～C 6 Alkoxy group of (2).
Preferably, R 1 Is unsubstituted or substituted C1-C17 straight or branched chain alkyl, alkenyl, carbonyl, aryl, biphenyl, alkoxy, alkylamino, alkanoyl, phenylacyl, biphenylacyl, arylalkenyl; r 4 Of 1 to 12 carbonsUnsubstituted or substituted aryl. R 1 And R 4 Is one or more and is each independently selected from the group consisting of hydroxy, halogen, amino, nitroso, cyano, carboxy, sulfonic, sulfuric, phosphoric, phosphonic, unsubstituted or substituted phenyl, morpholinyl, benzoyl, unsubstituted or substituted straight or branched C 1 ～C 10 Alkyl radical, C 1 ～C 10 Alkenyl radical, C 1 ～C 10 Acyl radical, C 1 ～C 10 Carbonyl group, OR 5 、SR 5 、SO 2 R 5 、SO 3 R 5 、COOR 5 、COR 5 、OCOR 5 、C(O)NR 6 R 7 、SO 2 NR 6 R 7 Or NR 6 R 7 Wherein R is 5 、R 6 、R 7 Independently of one another, hydrogen, phenyl, straight-chain or branched C 1 ～C 6 Alkyl of (C) 1 ～C 6 Alkenyl or C 1 ～C 6 Alkoxy group of (2). More preferably, R is 1 Is unsubstituted or substituted C1-C12 straight or branched chain alkyl, alkenyl, phenylalkenyl, heterocycloalkenyl, carbonyl, phenyl, biphenyl, alkoxy, alkylamino, alkanoyl, phenylacyl, biphenylacyl; r 4 Is an unsubstituted or substituted aryl group of 1 to 12 carbons. R 1 And R 4 Is one or more and is each independently selected from the group consisting of hydroxy, halogen, amino, nitroso, cyano, carboxy, sulfonic, sulfuric, phosphoric, phosphonic, unsubstituted or substituted phenyl, morpholinyl, benzoyl, unsubstituted or substituted straight or branched C 1 ～C 10 Alkyl radical, C 1 ～C 10 Alkenyl radical, C 1 ～C 10 Acyl radical, C 1 ～C 10 Carbonyl group, OR 5 、SR 5 、SO 2 R 5 、SO 3 R 5 、COOR 5 、COR 5 、OCOR 5 、C(O)NR 6 R 7 、SO 2 NR 6 R 7 Or NR 6 R 7 Wherein R is 5 、R 6 、R 7 Independently of one another, hydrogen, phenyl, or naphthylChain or branch C 1 ～C 6 Alkyl of (C) 1 ～C 6 Alkenyl or C 1 ～C 6 Alkoxy group of (2). Particularly preferably, R 1 Is unsubstituted or substituted C 1～6 Alkyl radical, C 1～6 Alkenyl, phenyl, phenylalkyl, phenylalkenyl, C 1～4 Alkanoyl, phenylacyl; r 2～4 Is unsubstituted or substituted phenyl; r 1 And R 4 The substituent is hydroxyl, halogen, amino, nitro, cyano, carboxyl, sulfonic group, sulfuric acid group, C 1～6 Alkyl radical, C 1～6 Alkenyl radical, C 1～6 Alkylamino radical, or C 1～6 An alkoxy group; r 2～4 Is phenyl, R 4 The substituents being one or more halogens, or/and C 1 ～C 12 Alkenyl, or/and C 1 ～C 4 Alkoxy, or/and C 1 ～C 12 Alkylamino radical, or/and C 1 ～C 12 Alkyl, wherein the substituents of the alkenyl group are one or more and each is independently selected from the group consisting of hydroxyl, halogen, amino, nitro, nitroso, cyano, sulfonic, sulfuric, phosphoric, phosphonic, carbonyl of 1-6 carbons, ester, acyl, carboxyl, alkylamino, alkoxy, alkyl, alkenyl. Or, R 4 The substituents being one or more halogens, or/and C 1 ～C 6 Alkenyl, or/and C 1 ～C 6 Alkoxy, or/and C 1 ～C 6 Alkylamino radical, or/and C 1 ～C 6 Alkyl, wherein the substituents of the alkenyl group are one or more and each is independently selected from the group consisting of hydroxy, halogen, amino, nitro, nitroso, cyano, carboxy, phosphate, phosphonate, sulfonate, sulfate, C 1～6 Carbonyl group, C 1～6 Ester group, C 1～6 Acyl radical, C 1～6 Alkylamino radical, C 1～6 Alkoxy radical, C 1～6 Alkyl radical, C 1～6 An alkenyl group. Or, R 4 The substituents being one or more halogens, or/and C 1 ～C 4 Alkenyl, or/and C 1 ～C 4 Alkoxy, or/and C 1 ～C 4 Alkylamino radical, or/and C 1 ～C 4 Alkyl, wherein the substituents of the alkenyl are one or moreAnd each independently selected from hydroxy, halogen, amino, nitro, nitroso, cyano, carboxyl, phosphate, phosphonate, sulfonate, sulfate, C 1～4 Carbonyl group, C 1～4 Ester group, C 1～4 Acyl radical, C 1～4 Alkylamino radical, C 1～4 Alkoxy radical, C 1～4 Alkyl radical, C 1～4 An alkenyl group.
Compounds of importance in the examples of the present invention are compounds of formula (III), (IV), (V), (VI) or (VII):
the invention also relates to a preparation method of the imidazolone oxime ester compound shown as the formula (I), which is characterized by comprising the following reaction formula:
wherein R is 1 ～R 4 Is one or more and is each independently selected from the group consisting of hydrogen, hydroxyl, oxy, thio, halogen, amino, nitro, nitroso, cyano, carboxyl, unsubstituted or substituted straight or branched alkyl of 1 to 20 carbons, alkenyl, alkynyl, aryl, heterocyclyl, carbonyl, acyl, alkylamino, alkoxy, alkylthio, arylalkyl, heterocyclylalkyl, arylalkenyl, heterocyclylalkenyl. X is a leaving group. Preferably, X is OR 13 Halogen, or sulfonate. More preferably, R 13 Is C 1 ～C 10 Alkyl, particularly preferably, R 13 Is C 1 ～C 4 Alkyl, most preferably, R 13 Is methyl. Preferably, halogen is chlorine or bromine, more preferably, halogen is chlorine. The detailed synthesis steps are shown in synthesis reactions 1-5.
The invention also relates to a composition comprising at least one compound of formula (I). The compositions may be used as photoinitiating, light absorbing, photosensitizing, or photosensitizing agents. The composition of the present invention may include a hydrogen donor, a photosensitizer, or various stabilizers.
Suitable hydrogen donors of the present invention include, but are not limited to, organic thiols, 2-mercaptobenzoxazoles, 2-mercaptobenzimidazoles, secondary amines, N-phenylglycine, 1,1-dimethyl-3,5-cyclohexanedione, ethers, esters, alcohols, allyl-or benzylic hydrogen-containing compounds, acetals, aldehydes, and amides. The hydrogen donors can be used singly or in combination.
Suitable photosensitizers for use in the present invention include leuco dyes, polycyclic aromatic species, xanthenes, cyanines, thiazines, acridines, anthraquinones, squaric acids, acridones, chloroacridone, N-methylacridone, N-butylacridone, coumarins, thioxanthones, arylaminones, aromatic ring-or heterocycle-substituted amine-based compounds, disubstituted amino benzophenone-based compounds, or p-dialkylamino-substituted aromatic ring-or heterocycles. The above-mentioned photosensitizers may be used singly or in combination of one or more.
In addition, the compounds of the present invention all have typical optical absorption properties, such as in FIG. 2. Can be used as an ultraviolet light absorber without additives such as monomers, particularly as an ultraviolet light absorber in the UVa-2 waveband, and has industrial applicability. Furthermore, the compounds of the present invention may be used in combination with other photoinitiators, as secondary initiators or photosensitizers. For example, BCIM compounds have a maximum absorption wavelength of 255 to 275nm, and the compounds of the present invention have a light absorption band complementary to the maximum absorption wavelength of the BCIM compounds, and therefore, can be used in combination with BCIM.
Drawings
FIG. 1 is an MS spectrum of 2- (2-chlorophenyl) -4,5-diphenyl-1H-imidazole-1-benzoate, a compound of example 3 of this invention;
FIG. 2 is a graph of the UV absorbance of the compound 2- (2-chlorophenyl) -3-p-methoxycinnamate-4,5-diphenylimidazole of example 9 of the present invention.
Detailed Description
Specific embodiments of the present invention will be described below, but the present invention is not limited to these embodiments.
Synthesis reaction 3 is a process for preparing the compound (V) of example 9. First, methoxybenzaldehyde reacts with ethyl acetate to form p-methoxycinnamic acid. Then reacts with thionyl chloride to form p-methoxy cinnamoyl chloride. And then reacting the 2-o-chlorophenyl-3-hydroxy-4,5-diphenyl imidazole with p-methoxy cinnamoyl chloride to obtain the target compound (V).
Synthesis reaction 4 is a process for preparing compound (VII) of example 17. First, benzoylformic acid and thionyl chloride are reacted to benzoylformyl chloride. 2- (2-chlorophenyl) -4,5-diphenyl-1H-imidazol-1-ol imidazole oxime was then added to benzoyl chloride (VII).
The synthesis reaction 5 is a preparation method of the alkyl and/or phenyl substituted imidazolone oxime ester compound. Firstly, alkyl diketone reacts with benzaldehyde, hydroxylamine hydrochloride and ammonium acetate to obtain imidazole oxime. And then reacting imidazole oxime with acetyl chloride to obtain the imidazolone oxime ester compound. Compounds having the structural features of imidazolone oxime esters, such as those of formula (XVII), can generally have photoinitiation or the like. Thus, various imidazolone oxime esters can be obtained by reacting various alkyldione starting materials with various phenyl aldehydes or alkyl aldehydes, and further reacting with various acid chlorides.
The above synthesis reactions 1,2, 3, 4 and 5 are specific embodiments of the present invention, but the present invention is not limited to these embodiments. The reaction starting material is not limited to a phenylenedione or an alkyldione. Various diketones can be used as starting materials, for example Tetrahedron Letters (1997), 38 (1), 7-10, journal of Organic Chemistry (1999), 64 (16), 6102-6105. Then, the imidazole oxime ester photoinitiators with the formulas (I), (II), (III), (IV), (V), (VI) and (VII) are synthesized according to the method of the synthesis reactions 1-5. Furthermore, various triphenyl-benzoyloxy-imidazole compounds are available via the reaction of triphenyl-imidazole with peroxides such as Benzoyl peroxide. For example, a 2- (2-chlorophenyl) -4,5-diphenyl-1H-imidazole-1-benzoate compound can be obtained by reacting a 2- (2-chlorophenyl) -4,5-diphenyl-1H-imidazole compound with a peroxide such as benzoylperoxide, zeitschrifufuerChemie (1971), 11 (2), pp.62-3.
Example 1
2- (hydroxyimino) -1,2-diphenylethan-1-one
Into a 1000ml reaction flask were charged 210g of diphenylethanedione (BE), 500ml of sodium carbonate 132.5g of methanol, and 71.4g of hydroxylamine hydrochloride. Refluxing at 70 deg.C, and refluxing for 4 hr under heat preservation. After the reaction is finished, concentrating under reduced pressure to obtain viscous BE oxime. After recrystallization, the melting point is 82-84 ℃.
Example 2
2- (2-chlorophenyl) -4,5-diphenyl-1H-imidazol-1-ol imidazole oxime
A1000 ml one-necked flask was charged with 500g of acetic acid to dissolve 235g of BE oxime. 121g of ammonium acetate and 147.6g of o-chlorobenzaldehyde are added. The temperature is increased for reflux, and the reflux temperature is started to be 120 ℃. Materials are separated out along with the reaction, and the mixture is refluxed, kept warm and sampled for analysis. After the reaction is finished, pouring the mixture into water, heating to about 40 ℃, and stirring to disperse. 30 ～ Washing with water at 40 ℃ gave the imidazole oxime (94%, UV 254 nm). The compound was decomposed at 270 ℃ (DSC).
Example 3
2- (2-chlorophenyl) -4,5-diphenyl-1H-imidazole-1-benzoic acid ester
Into a 1000ml four-necked reaction flask were charged 200g of imidazole oxime (XVIII), 500g of dichloroethane, and 65.6g of triethylamine, and 82g of benzoyl chloride was added dropwise. After the benzoyl chloride was added dropwise, the dichloroethane was evaporated to dryness. Obtaining a solid, recrystallizing, cooling, separating out and discharging to obtain a white powder solid (III). Melting point 136-138 deg.C, MS [ M + H ]] + 451.1。
Example 4
2- (2-chlorophenyl) -4,5-diphenyl-1H-imidazol-1-yl-4-dimethylamino-benzoate
Following the procedure of example 3, but substituting 4-dimethylaminobenzoyl chloride for benzoyl chloride, 2- (2-chlorophenyl) -5-phenyl-4- (pyridin-2-yl) -1H-imidazol-1-yl-4-dimethylcarbamate (VIII) was obtained. MS [ M + H ]] + 494.2。
Example 5
2- (2-chlorophenyl) -4,5-diphenyl-1H-imidazol-1-yl dibenzoate
According to the examplesProcess 3, but replacing the benzoyl chloride with 4-bibenzoyl chloride, gives 2- (2-chlorophenyl) -5-phenyl-4- (pyridin-2-yl) -1H-imidazol-1-yl bibenzoate (IX). MS [ M + H ]] + 527.1。
Example 6
2- (4- (2-acetoxy-2-cyanovinyl) -2-chlorophenyl) -4,5-diphenyl-1H-imidazole-1-benzoic acid ester
A500 ml reaction flask was charged with 22.5g of BE oxime, 23g of ethyl p-cyanoacrylate benzaldehyde, 15.4g of ammonium acetate and 200g of acetic acid, and subjected to a reflux reaction for 6 hours. The temperature is reduced to 60 ℃, and solid is filtered out. Washing with methanol, and oven drying. 4.4g of the dried solid is taken and put into a 250ml reaction bottle, 50g of dichloroethane and 2g of triethylamine are added and stirred. A solution of 1.4g of benzoyl chloride in dichloroethane is added dropwise at 15 ℃. After 30 minutes, the mixture is kept warm for one hour. The solid was filtered directly and washed with water to give a yellow solid powder. MS [ M + H ]] + 574.1。
Example 7
P-methoxy cinnamic acid
A1000 ml reaction flask was charged with 360 g of toluene, 100 g of anhydrous ethyl acetate, and 40.9 g of sodium methoxide. 68 g of p-methoxybenzaldehyde in ethyl acetate are added dropwise under nitrogen and sampled for analysis. Cooling and acidifying in sulfuric acid water solution. And recovering the solvent. Adding sodium hydroxide into the concentrate, heating for hydrolysis, cooling and neutralizing with dilute sulfuric acid. Filtering, washing with water, washing with methanol, and drying to obtain yellowish p-methoxycinnamic acid powder.
Example 8
P-methoxy cinnamoyl chloride
9.8 g of p-methoxycinnamic acid, 20g of dichloroethane and 13.1 g of thionyl chloride were added to a 250ml reaction flask and the mixture was heated to reflux. The reaction was maintained at reflux for 3 hours, and unreacted thionyl chloride and dichloroethane were distilled off.
To obtain the p-methoxy cinnamoyl chloride. The concentrate was dissolved in 40 g of dichloroethane and directly subjected to the next synthesis.
Example 9
2- (2-chlorophenyl) -3-p-methoxycinnamate-4,5-diphenylimidazole
After 17.4 g of 2- (2-chlorophenyl) -3-hydroxy-4,5-diphenylimidazole (XVIII), 5.9 g of triethylamine and 120g of dichloroethane were added to a 250ml reaction flask, the newly synthesized p-methoxycinnamoyl chloride was added dropwise. The addition is completed within 1.5 hours, and the dropping temperature is 5-10 ℃. After washing with water, the solvent was recovered. 90 g of methanol are added at 50 ～ Stirring at 60 ℃ for 1 hour, cooling to 10-20 ℃, filtering, and washing with a small amount of methanol to obtain a pale yellow solid (XV), melting point: 161-162 ℃.
Example 10
2- (2-chlorophenyl) -4,5-diphenyl-1H-imidazol-1-yl acetate
According to the method of example 3, 200g of dried imidazoloxime (XVIII), 500g of dichloroethane, 65.6g of triethylamine were charged into a 1000ml four-necked reaction flask, and 45.5g of acetyl chloride was added dropwise. To give 2- (2-chlorophenyl) -4,5-diphenyl-1H-imidazol-1-yl acetate (X). MS [ M + H ]] + 389.1。
Example 11
2- (2-chlorophenyl) -4,5-diphenyl-1H-imidazol-1-yl stearate
According to the method of example 3, 200g of directly dried imidazole oxime (XVIII), 500g of dichloroethane, 65.6g of triethylamine and 175.1g of stearoyl chloride were charged into a 1000ml four-necked reaction flask. To give 2- (2-chlorophenyl) -4,5-diphenyl-1H-imidazol-1-yl stearate (XI). MS [ M + H ]] + 613.4。
Example 12
2- (2-chlorophenyl) -5-phenyl-4- (pyridin-2-yl) -1H-imidazole-1-benzoic acid ester
The procedure of example 3 was followed except that 1-phenyl-2- (pyridin-2-yl) ethane-1,2-dione was used in place of BE ketone.
To obtain 2- (2-chlorphenyl) -5-phenyl-4- (pyridine-2-yl) -1H-imidazole-1-benzoic acid ester (XII).
Example 13
2- (2-chlorophenyl) -4,5-bis (4-methoxyphenyl) -1H-imidazole-1-benzoic acid ester
The procedure of example 3 was followed except that 1,2-bis (4-methoxyphenyl) ethane-1,2-dione was used in place of BE ketone.
2- (2-chlorophenyl) -4,5-bis (4-methoxyphenyl) -1H-imidazole-1-benzoic acid ester (XIII) is obtained.
Example 14
2- (2-chlorophenyl) -4- (naphthalen-2-yl) -5-phenyl-1H-imidazole-1-benzoic acid ester
The procedure of example 3 was followed, but 1- (naphthalen-2-yl) -2-phenylethane-1,2-dione was used instead of BE ketone. 2- (2-chlorophenyl) -5-phenyl-4- (pyridin-2-yl) -1H-imidazole-1-benzoic acid ester (XIV) is obtained.
Example 15
2- (2-chlorophenyl) -4,5-diphenyl-1H-imidazol-1-yl acrylate
According to the method of example 3, 200g of oven-dried imidazole oxime (XVIII), 500g of dichloroethane, 65.6g of triethylamine and 52.2g of acryloyl chloride were charged into a 1000ml four-necked reaction flask. After the acryloyl chloride is dripped off, the dichloroethane is evaporated to dryness. 2- (2-chlorophenyl) -4,5-diphenyl-1H-imidazol-1-yl acrylate (XV) is obtained. MS [ M + H ]] + 401.1。
Example 16
2- (2,4-dichlorophenyl) -4,5-diphenyl-1H-imidazole-1-benzoic acid ester
The procedure of example 3 was followed except that o-chlorobenzaldehyde was replaced with 2,4 dichlorobenzaldehyde. 2- (2,4-dichlorophenyl) -4,5-diphenyl-1H-imidazole-1-benzoic acid ester (XVI) is obtained.
Example 17
2- (2,4-dichlorophenyl) -4,5-diphenyl-1H-imidazole-1-benzoic acid ester 2-oxo-2-benzoate
120g of benzoylformic acid and 50ml of thionyl chloride were added to a reaction vessel, and the reaction was stirred under reflux. After 2 hours, the mixture was distilled under reduced pressure to obtain benzoyl chloride. Into a 1000ml four-necked reaction flask, 200g of 2- (2-chlorophenyl) -4,5-diphenyl-1H-imidazol-1-ol imidazoxime (XVIII) obtained in example 2, 500g of dichloroethane, 65.6g of triethylamine and 82g of benzoyl chloride were added dropwise. 2- (2,4-dichlorophenyl) -4,5-diphenyl-1H-imidazole-1-benzoic acid ester-2-oxo-2-benzoate (VII) is obtained. MS [ M + H ]] + 479.1。
Example 18
2- (4- (2-methylamino) phenyl) -4,5-diphenyl-1H-imidazole-1-benzoic acid ester
Following the procedure of example 3, but substituting 3-chloro-4- (dimethylamino) benzaldehyde for o-chlorobenzaldehyde, 2- (4- (2-methylamino) phenyl) -4,5-diphenyl-1H-imidazole-1-benzoic acid ester was obtained. MS [ M + H ]] + 494.2。
Example 19
2- (2-chlorophenyl) -4,5-diphenyl-1H-imidazol-1-yl 2-oxopropanoate
Following the procedure of example 17, but substituting 2-oxopropionyl chloride for benzoylcarbonyl chloride. To give 2- (2-chlorophenyl) -4,5-diphenyl-1H-imidazol-1-yl 2-oxopropanoate. MS [ M + H ]] + 417.1。
TABLE 1 Compounds synthesized in examples 3-6,9-19
EXAMPLE 20 comparative operability of the example Compounds with OXE 01 ketoxime ester
IRGACURE OXE 01, chemical name 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl ] -1,2-octanedione, or the solid compound of examples 3-19, was taken at room temperature and placed in a clear glass container and filled. After 24 hours of standing, the compound was decanted and the container was observed for residue. The residual amount can be expressed directly as the transmittance, or diluted after dissolving in a solvent, and the UV absorption value (UV-VIS spectrophotometry) is measured. Higher transmittance indicates less residual amount. The residual amount represents the handling property. The more residual amount means the worse the operation performance. The residual amounts were classified into the following grades: 0= very small residue, 1= small residue, 2= medium residue, 3= large residue.
TABLE 2 Room temperature operability
| Examples 3-19 Compounds | IRGACURE OXE 01 | |
| Residue is remained | 0-1 | 2 |
| Operability of | Jia | Not good at |
EXAMPLE 21 comparison of the thermal stability of the example Compounds with OXE 01 ketoxime ester
Samples of the compounds of examples 3-19 or the control IRGACURE OXE 01, each 5mg, were taken and compared for thermal stability under a thermogravimetric analyzer (TGA) nitrogen atmosphere. The conditions are that the heating rate is 10 ℃/min, the initial temperature is 25 ℃, and the finishing temperature is 200 ℃. Greater weight loss represents less stability. As a result, the weight loss of the exemplified compound was less than 5% and the weight loss of IRGACURE OXE 01 was greater than 9%.
TABLE 3 thermal stability test results
Example 22 sludge (flattest) to sensitization test comparison of example compound to BCIM 3.0% of an example photoinitiating compound or a control compound BCIM (photo 900, eutec co dissolved in tetrahydrofuran), 0.15% of N-phenylglycine hydrogen donor (photo NPG, eutec co), 0.3% of 4,4-bis (N, N' -dimethyl-amino) benzophenone (photo EAB, eutec co), 36.5% of a difunctional acrylate monomer and 60% of an acrylate oligomer were mixed. The above photosensitive composition was coated on a copper sheet or a polyester sheet, dried, and irradiated with a high-pressure UV lamp to perform sludge and photosensitive tests (table 4). The sludge test involves placing the copper sheet in a developer solution and allowing it to stand until the sample dissolves. The developer solution was prepared by dissolving 20g of sodium carbonate in 2 liters of water and adding 1.5ml of a nonionic surfactant of polyoxyethylene/polyoxypropylene copolymer. The precipitation amount was classified by the following scale: 0= no light yellow precipitate, 1= a small amount of finely divided pale yellow, 2= a medium amount of pale yellow, 3= a large solid layer of pale yellow on the bottom. The accumulation of sludge shortens the lifetime of the developer. The more sludge, the worse the result. The film produced above was subjected to dry to touch (dry to touch) to record the number of exposures to achieve good surface hardness. The lower the number of exposures, the better the photosensitivity.
Table 4 sludge test results
| Examples 3-19 Compounds | Control group BCIM compound | |
| Sludge grade | 0-1 | 2-3 |
| Number of exposures | 4-5 | 5 |
Example 23 absorption experiments
Example compounds 3-6,9-19 all had typical optical absorption properties, such as the compound of example 7 (fig. 2). The transmittance of BCIM compounds of the examples and the comparative examples is measured by a UV-VIS spectrometer by taking equal amount of acetonitrile as a solvent. It is shown that the compound can be used as an ultraviolet light absorber without additives such as monomers, particularly as an ultraviolet light absorber in the UVa waveband, and has industrial applicability.
The foregoing is only a preferred embodiment of the present invention. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope of the invention. Such modifications and variations are considered to be within the scope of the invention.
Claims (2)
1. An application of imidazolone oxime ester compound or salts thereof in a photoinitiator, a photosensitizer, a light absorber or a photosensitizer is characterized in that the structural formula of the imidazolone oxime ester compound is shown as the formula (I):
wherein R is 1 Is unsubstituted or substituted, and contains C1-20 straight chain or branched chain alkyl, C1-20 alkenyl, C1-20 carbonyl, C1-20 aryl, C1-20 heterocyclic radical, C1-20 arylalkyl, C1-20 heterocyclic alkyl, C1-20 arylalkenylA heterocyclylalkenyl group of carbons, an alkylamino group of 1-20 carbons, an alkoxy group of 1-20 carbons, an alkanoyl group of 1-20 carbons, an arylacyl group of 1-20 carbons, or a heterocyclylacyl group of 1-20 carbons; r 2 -R 4 Is one or more and is independently selected from hydrogen, hydroxyl, halogen, amino, nitro, cyano, carboxyl, sulfonic acid group, unsubstituted or substituted straight or branched alkyl group having 1 to 12 carbons, alkenyl group having 1 to 12 carbons, aryl group having 1 to 12 carbons, heterocyclic group having 1 to 12 carbons, arylalkyl group having 1 to 12 carbons, heterocyclylalkyl group having 1 to 12 carbons, wherein R is 1 -R 4 Is one or more and is each independently selected from the group consisting of hydroxy, halogen, amino, nitro, cyano, carboxy, sulfo, phenyl, morpholino, benzoyl, straight or branched C 1～ C 10 Alkyl radical, C 1～ C 10 Acyl radical, C 1～ C 10 Carbonyl group, OR 5 、COOR 5 、COR 5 、C(O)NR 6 R 7 Or NR 6 R 7 Wherein R is 5 、R 6 、R 7 Independently of one another, hydrogen, phenyl, straight-chain or branched C 1～ C 6 Alkyl of (C) 1～ C 6 Alkenyl or C 1～ C 6 And unsubstituted or substituted C 1～ C 10 Alkenyl, wherein the substituent of alkenyl is one or more and each is independently selected from hydroxyl, halogen, amino, nitro, cyano, sulfonic acid group, carbonyl group of 1-6 carbons, ester group of 1-6 carbons, acyl group of 1-6 carbons, carboxyl group of 1-6 carbons, alkylamino group of 1-6 carbons, alkoxy group of 1-6 carbons, alkyl group of 1-6 carbons, alkenyl group of 1-6 carbons.
2. Use of the imidazolone oxime ester compound according to claim 1, R 1 Is unsubstituted or substituted C 1～ C 17 Alkyl of (C) 1～ C 6 Is one or more and is independently selected from hydroxyl, halogen, amino, nitro, cyano, sulfonic acid group, carbonyl group of 1-6 carbons, ester group of 1-6 carbons, acyl group of 1-6 carbons, carboxyl group of 1-6 carbonsAlkyl amino with 1-6 carbon atoms and alkoxy with 1-6 carbon atoms; r 4 Is unsubstituted or substituted phenyl, R 4 The substituents being one or more halogens, or/and C 1～ C 4 Alkenyl, or/and C 1～ C 4 Alkoxy, or/and C 1～ C 4 Alkylamino radical, or/and C 1～ C 4 And an alkyl group, wherein the substituent of the alkenyl group is one or more and each is independently selected from the group consisting of a hydroxyl group, a halogen group, an amino group, a nitro group, a cyano group, a sulfonic group, a carbonyl group having 1 to 6 carbons, an ester group having 1 to 6 carbons, an acyl group having 1 to 6 carbons, a carboxyl group having 1 to 6 carbons, an alkylamino group having 1 to 6 carbons, an alkoxy group having 1 to 6 carbons, an alkyl group having 1 to 6 carbons, and an alkenyl group having 1 to 6 carbons.
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| CN101525393A (en) * | 2009-04-02 | 2009-09-09 | 优缔精细化工（苏州）有限公司 | Oxime ester photoinitiator and preparation method thereof |
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| EP0239868A1 (en) * | 1986-03-20 | 1987-10-07 | BASF Aktiengesellschaft | Photochromic system, layer prepared thereof and its use |
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