WO2020252628A1 - Oxime ester photoinitiators containing five-membered heteroaromatic ring structure, and preparation and use thereof - Google Patents
Oxime ester photoinitiators containing five-membered heteroaromatic ring structure, and preparation and use thereof Download PDFInfo
- Publication number
- WO2020252628A1 WO2020252628A1 PCT/CN2019/091563 CN2019091563W WO2020252628A1 WO 2020252628 A1 WO2020252628 A1 WO 2020252628A1 CN 2019091563 W CN2019091563 W CN 2019091563W WO 2020252628 A1 WO2020252628 A1 WO 2020252628A1
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- WO
- WIPO (PCT)
- Prior art keywords
- alkyl
- group
- aryl
- cycloalkyl
- halogen
- Prior art date
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- -1 Oxime ester Chemical class 0.000 title claims abstract description 171
- 238000002360 preparation method Methods 0.000 title abstract description 30
- 125000001072 heteroaryl group Chemical group 0.000 title abstract 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 137
- 125000003118 aryl group Chemical group 0.000 claims description 103
- 229910052736 halogen Inorganic materials 0.000 claims description 75
- 150000002367 halogens Chemical class 0.000 claims description 75
- 125000000217 alkyl group Chemical group 0.000 claims description 59
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 50
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 39
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 125000004104 aryloxy group Chemical group 0.000 claims description 35
- 125000005110 aryl thio group Chemical group 0.000 claims description 33
- 238000005886 esterification reaction Methods 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 32
- 238000006146 oximation reaction Methods 0.000 claims description 31
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 30
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 claims description 29
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 29
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 claims description 28
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 claims description 22
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 22
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 20
- 238000006467 substitution reaction Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 125000002947 alkylene group Chemical group 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- 230000032050 esterification Effects 0.000 claims description 13
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 12
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 12
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 claims description 12
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 11
- 125000004414 alkyl thio group Chemical group 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 125000004149 thio group Chemical class *S* 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 8
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 8
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 8
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 8
- 125000003282 alkyl amino group Chemical group 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 6
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 6
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- 125000004890 (C1-C6) alkylamino group Chemical group 0.000 claims description 4
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 239000012374 esterification agent Substances 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 claims description 3
- JQJPBYFTQAANLE-UHFFFAOYSA-N Butyl nitrite Chemical compound CCCCON=O JQJPBYFTQAANLE-UHFFFAOYSA-N 0.000 claims description 3
- QQZWEECEMNQSTG-UHFFFAOYSA-N Ethyl nitrite Chemical compound CCON=O QQZWEECEMNQSTG-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- SKRDXYBATCVEMS-UHFFFAOYSA-N isopropyl nitrite Chemical compound CC(C)ON=O SKRDXYBATCVEMS-UHFFFAOYSA-N 0.000 claims description 3
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 claims description 3
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012312 sodium hydride Substances 0.000 claims description 3
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- 125000005270 trialkylamine group Chemical group 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 150000002923 oximes Chemical class 0.000 claims description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims 2
- NTHGIYFSMNNHSC-UHFFFAOYSA-N 3-methylbutyl nitrate Chemical compound CC(C)CCO[N+]([O-])=O NTHGIYFSMNNHSC-UHFFFAOYSA-N 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 14
- 239000000178 monomer Substances 0.000 abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 4
- 230000031700 light absorption Effects 0.000 abstract description 3
- 239000003504 photosensitizing agent Substances 0.000 abstract description 3
- 238000001723 curing Methods 0.000 description 23
- 125000004432 carbon atom Chemical group C* 0.000 description 21
- 239000012074 organic phase Substances 0.000 description 21
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 16
- 229910052753 mercury Inorganic materials 0.000 description 16
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- SEEVRZDUPHZSOX-WPWMEQJKSA-N [(e)-1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino] acetate Chemical compound C=1C=C2N(CC)C3=CC=C(C(\C)=N\OC(C)=O)C=C3C2=CC=1C(=O)C1=CC=CC=C1C SEEVRZDUPHZSOX-WPWMEQJKSA-N 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 11
- 229940125904 compound 1 Drugs 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 229940125807 compound 37 Drugs 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- IUSARDYWEPUTPN-OZBXUNDUSA-N (2r)-n-[(2s,3r)-4-[[(4s)-6-(2,2-dimethylpropyl)spiro[3,4-dihydropyrano[2,3-b]pyridine-2,1'-cyclobutane]-4-yl]amino]-3-hydroxy-1-[3-(1,3-thiazol-2-yl)phenyl]butan-2-yl]-2-methoxypropanamide Chemical compound C([C@H](NC(=O)[C@@H](C)OC)[C@H](O)CN[C@@H]1C2=CC(CC(C)(C)C)=CN=C2OC2(CCC2)C1)C(C=1)=CC=CC=1C1=NC=CS1 IUSARDYWEPUTPN-OZBXUNDUSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000007639 printing Methods 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000006210 lotion Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 125000003544 oxime group Chemical group 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 4
- LFOIDLOIBZFWDO-UHFFFAOYSA-N 2-methoxy-6-[6-methoxy-4-[(3-phenylmethoxyphenyl)methoxy]-1-benzofuran-2-yl]imidazo[2,1-b][1,3,4]thiadiazole Chemical compound N1=C2SC(OC)=NN2C=C1C(OC1=CC(OC)=C2)=CC1=C2OCC(C=1)=CC=CC=1OCC1=CC=CC=C1 LFOIDLOIBZFWDO-UHFFFAOYSA-N 0.000 description 4
- 206010034972 Photosensitivity reaction Diseases 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- GVOISEJVFFIGQE-YCZSINBZSA-N n-[(1r,2s,5r)-5-[methyl(propan-2-yl)amino]-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](N(C)C(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 GVOISEJVFFIGQE-YCZSINBZSA-N 0.000 description 4
- 230000036211 photosensitivity Effects 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- HBENZIXOGRCSQN-VQWWACLZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-[(2S)-2-hydroxy-3,3-dimethylpentan-2-yl]-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol Chemical compound N1([C@@H]2CC=3C4=C(C(=CC=3)O)O[C@H]3[C@@]5(OC)CC[C@@]2([C@@]43CC1)C[C@@H]5[C@](C)(O)C(C)(C)CC)CC1CC1 HBENZIXOGRCSQN-VQWWACLZSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000003848 UV Light-Curing Methods 0.000 description 3
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 3
- 239000012346 acetyl chloride Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 229940126540 compound 41 Drugs 0.000 description 3
- 238000004455 differential thermal analysis Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- RENRQMCACQEWFC-UGKGYDQZSA-N lnp023 Chemical compound C1([C@H]2N(CC=3C=4C=CNC=4C(C)=CC=3OC)CC[C@@H](C2)OCC)=CC=C(C(O)=O)C=C1 RENRQMCACQEWFC-UGKGYDQZSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- ASQOQJYHIYYTEJ-GBESFXJTSA-N (1r,7s,9as)-7-decyl-2,3,4,6,7,8,9,9a-octahydro-1h-quinolizin-1-ol Chemical compound O[C@@H]1CCCN2C[C@@H](CCCCCCCCCC)CC[C@H]21 ASQOQJYHIYYTEJ-GBESFXJTSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910020366 ClO 4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000002015 acyclic group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
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- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/323—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F122/00—Homopolymers 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
- C08F122/10—Esters
- C08F122/12—Esters of phenols or saturated alcohols
- C08F122/20—Esters containing oxygen in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
Definitions
- the present invention relates to oxime ester compounds containing a five-membered aromatic heterocyclic structure.
- the invention also relates to the preparation of the oxime ester compound and its use as a photoinitiator in a photopolymerization composition.
- Photoinitiator also known as photosensitizer or photocuring agent, is a kind of energy that can absorb a certain wavelength of energy in the ultraviolet region (250-400nm) or visible region (400-600nm) to generate free radicals, cations, etc., thereby initiating monomer polymerization Cross-linked and cured compound.
- photoinitiators In light curing systems, photoinitiators generally account for 3-5%. Although the content is low, it is a key component and determines the speed of light curing. It is related to whether the oligomer and diluent can be quickly cross-linked and solidified when the formula system is irradiated with light, thereby changing from liquid to solid.
- photoinitiators must meet the needs of different light curing conditions and applications.
- the main goals are: improve light sensitivity, improve surface curing efficiency (anti-oxidation inhibition), improve deep curing performance, improve the solubility of photoinitiators in monomers and resins, and reduce toxicity and odor , Reduce the migration of uncured initiator after curing, reduce yellowing.
- Oxime ester photoinitiators have become a class of photoinitiators that have gradually received attention in recent years due to their excellent photosensitivity.
- BASF's products OXE-01 and OXE-02 are two representative products of oxime esters that are common on the market. These two products have high photosensitivity, but their ultraviolet absorption wavelength is too short (250-350nm), which is not suitable for ultraviolet-visible LED light source (emission wavelength 365nm, 385nm, 395nm, 405nm, 420nm, 430nm, 450nm).
- ultraviolet-visible LED light source emission wavelength 365nm, 385nm, 395nm, 405nm, 420nm, 430nm, 450nm.
- CN10277552A discloses a diphenyl sulfide ketoxime ester photoinitiator and its preparation method
- CN102492059A discloses a substituted diphenyl sulfide ketoxime ester photoinitiator. Agent and so on.
- most initiators have UV absorption wavelengths of 250-350nm, which cannot match the increasingly developed LED light sources, which greatly limits the application of oxime ester photoinitiators.
- LED point light sources, line light sources, and surface light sources have begun to be used in the light curing industry. Compared with traditional UV curing equipment, LED light sources have absolute advantages.
- the service life of the mercury lamp is only 800-3000 hours, and the service life of the UV-LED ultraviolet curing system can reach 20,000-30000 hours.
- the LED method can be lit instantaneously only when ultraviolet light is needed.
- the traditional mercury lamp curing equipment is working, because the mercury lamp starts slowly and the opening and closing affects the life of the bulb, it must be lit all the time, which not only causes unnecessary power consumption, but also shortens the working life of the mercury lamp.
- the traditional mercury lamp curing machine uses a mercury lamp to emit light. There is mercury in the bulb, which makes the waste disposal and transportation very troublesome, and improper handling can cause serious pollution to the environment.
- the LED curing machine uses semiconductors to emit light and has no environmental pollution factors. Therefore, the use of LED curing machine is more environmentally friendly.
- each illuminating head emits light independently, and the illuminating energy is not affected by the increase in the channel, and always remains at the maximum. Because of its super concentrated illuminance, compared with mercury lamps, UV-LED shortens the irradiation time of the operation and improves the production efficiency.
- UV-LED method Low energy consumption.
- the effective luminous efficiency of UV-LED method is more than 10 times higher than that of mercury lamp method.
- the UV-LED method consumes power only during irradiation, and almost zero power consumption during standby.
- the oxime ester photoinitiator OXE-02 currently on the market has relatively high photoinitiation activity, but its stability is generally poor, especially in photopolymer monomers.
- the photosensitive composition is not suitable for long-term storage and transportation, which brings certain difficulties to practical applications.
- the oxime ester compound containing a five-membered aromatic heterocyclic structure has excellent light absorption at 350-450nm, and can initiate the polymerization of acrylate monomers at low concentrations. It has excellent thermal stability and is a kind of oxime ester photoinitiator with good stability suitable for UV-visible LED light source.
- an object of the present invention is to provide an oxime ester compound containing a five-membered aromatic heterocyclic structure.
- the absorption wavelength of this compound is not only suitable for UV-visible LED light source radiation curing, but also has good thermal stability. Sex.
- Another object of the present invention is to provide a method for preparing the oxime ester compound containing the five-membered aromatic heterocyclic structure of the present invention.
- Another object of the present invention is to provide the use of the oxime ester compound containing the five-membered aromatic heterocyclic structure of the present invention as a photoinitiator or photosensitizer.
- n is an integer of 0-8;
- n and n’ are the same and are 0 or 1;
- a 1 and A 2 are the same or different, and each independently represents O, S and NR a, wherein R a is H or C 1 -C 6 alkyl;
- R 1 , R 2 , R 3 , and R 4 are the same or different, and independently represent hydrogen, halogen, nitro, amino, cyano, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, mono C 1 -C 12 alkylamino, di C 1 -C 12 alkylamino, C 6 -C 18 aryloxy or C 6 -C 18 arylthio, wherein the aforementioned C 6
- the aryl groups in the -C 18 aryloxy and C 6 -C 18 arylthio groups may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, NH 2 , cyano, C 1 -C 6 alkyl, C 1 -C 6 alkoxy and C 1 -C 6 alkylthio;
- R 5 is hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, C 6 -C 18 aryl, C 6- C 18 aryl C 1 -C 6 alkyl, C 6 -C 18 aryl C 1 -C 6 alkylene, C 6 -C 18 aryloxy, C 6 -C 18 arylthio, 9H-carbazole -9 group-C 1 -C 6 alkyl group, 9H-carbazol-9 group-C 1 -C 6 alkylene group, 9H-fluoren-9 group-C 1 -C 6 alkyl group or 9H-fluoren-9 group -C 1 -C 6 alkylene group, wherein the aforementioned C 6 -C 18 aryl group, C 6 -C 18 aryl group, C 1 -C 6 alkyl group, C 6 -C 18 aryl group, C 1 -
- R 6 and R 6 ′ are the same or different, and independently represent H, cyano, C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkyl alkyl, C 4 -C 10 alkyl cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl or C 7 -C 20 alkyl aryl, wherein the aforementioned C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkyl alkyl, C 4 -C 10 alkyl cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkane Alkylaryl is optionally substituted with one or more groups independently selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 alkylthio, C 1 -C 6
- R 7 and R 7 ' are the same or different, and independently represent C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkyl alkyl, C 4 -C 10 alkyl Cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl or C 7 -C 20 alkyl aryl, wherein the aforementioned C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkylalkyl, C 4 -C 10 alkylcycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkyl aryl are optional Ground is substituted by one or more groups independently selected from the following group: C 1 -C 6 alkyl, C 1 -C 6 alkylthio, C 1 -C 6 alkoxy, halogen,
- R a is H or C 1 -C 4 alkyl; preferably is, m of A 1 and A 2 identical to each other, and represent O, S or NR a, wherein R a is H or C 1 -C 4 alkyl, preferably H, methyl or ethyl.
- R 1 , R 2 , R 3 , R 4 are the same or different, and independently represent hydrogen, halogen, nitro, amino, cyano, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, mono C 1 -C 6 alkylamino, di C 1 -C 6 alkylamino, C 6 -C 10 aryloxy or C 6 -C 10 arylthio, wherein the aforementioned C 6
- the aryl groups in the -C 10 aryloxy and C 6 -C 10 arylthio groups may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, NH 2 , cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1 -C 4 alkylthio;
- R 1 , R 2 , R 3 , and R 4 are the same or different, and independently represent hydrogen, halogen, nitro, amino, cyano, C 1 -C 4 alkyl, C 1 -C 4 alkane Oxy, C 1 -C 4 alkylthio, mono C 1 -C 4 alkylamino, di C 1 -C 4 alkylamino, phenoxy or phenylthio, wherein the aforementioned phenoxy and phenylthio
- the phenyl group in the group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, NH 2 , cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1 -C 4 alkylthio.
- R 5 represents hydrogen, halogen, nitro, cyano, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 6 -C 13 aryl, C 6- C 13 aryl, C 1 -C 4 alkyl, C 6 -C 13 aryl, C 1 -C 4 alkylene, C 6 -C 13 aryloxy, C 6 -C 13 arylthio, 9H-carbazole -9 group-C 1 -C 4 alkyl group, 9H-carbazol-9 group-C 1 -C 4 alkylene group, 9H-fluoren-9 group-C 1 -C 4 alkyl group or 9H-fluoren-9 group -C 1 -C 4 alkylene, wherein the aforementioned C 6 -C 13 aryl, C 6 -C 13 aryl C 1 -C 4 alkyl, C 6 -C 13 aryl C 1 -C 4 alkylene
- R 5 represents hydrogen, halogen, nitro, cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, phenyl, C 6 -C 13 aryl C 1 -C 2 alkyl, C 6 -C 13 aryl C 1 -C 2 alkylene, C 6 -C 10 aryloxy, C 6 -C 10 arylthio, 9H-carbazole- 9 group-C 1 -C 2 alkyl group, 9H-carbazol-9 group-C 1 -C 2 alkylene group, 9H-fluoren-9 group-C 1 -C 2 alkyl group or 9H-fluoren-9 group- C 1 -C 2 alkylene group, wherein the aforementioned phenyl group, C 6 -C 13 aryl group C 1 -C 2 alkyl group, C 6 -C 13 aryl group C 1 -C 2 alkylene group, C
- R 6 and R 6 ′ are the same or different, and independently represent H, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkyl alkyl, C 4 -C 8 alkyl cycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl or C 7 -C 11 alkyl aryl, wherein the aforementioned C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl, and C 7 -C 11 alkane Alkylaryl is optionally substituted with one or more groups independently selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkylthio, C 1 -C 4
- R 6 and R 6 ′ are the same or different and independently represent H, cyano, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl or C 3 -C 6 cycloalkyl C 1 -C 2 alkyl, wherein the aforementioned C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl and C 3 -C 6 cycloalkyl C 1 -C 2 alkyl are optionally separated by one or more Substitution by a group selected from the following group: C 1 -C 4 alkyl, C 1 -C 4 alkylthio, C 1 -C 4 alkoxy, halogen, nitro, amino, mono (C 1 -C 4 Alkyl)amino, di(C 1 -C 4 alkyl)amino and mercapto.
- R 7 and R 7 ' are the same or different, and independently represent C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkyl alkyl, C 4 -C 8 alkyl Cycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl or C 7 -C 11 alkyl aryl, wherein the aforementioned C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl and C 7 -C 11 alkyl aryl optionally Ground is substituted by one or more groups independently selected from the following group: C 1 -C 4 alkyl, C 1 -C 4 alkylthio, C 1 -C 4 alkoxy, halogen,
- R 7 and R 7 ′ are the same or different, and independently represent C 1 -C 4 alkyl or phenyl, wherein the aforementioned C 1 -C 4 alkyl and phenyl are optionally substituted by one or more Substitution groups independently selected from the following group: C 1 -C 4 alkyl, C 1 -C 4 alkylthio, C 1 -C 4 alkoxy, halogen, nitro, amino, mono (C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkyl)amino and mercapto.
- a method for preparing the compound as claimed in any one of items 1-8 comprising the following steps:
- a 1 , A 2 , R 1 -R 4 and R 6 in formulas (III), (IV), (IIIa), (IVa), (IIIb) and (IVb), formulas (III), ( R 5 in IIIa) and (IIIb) and R 6 ′ in formulas (IV), (IVa) and (IVb) are as defined in any one of items 1-8; and
- the oximation reaction is carried out in the presence of sodium acetate, pyridine, piperidine, triethylamine, tetramethylammonium hydroxide or a mixture thereof; and/or, the oximation reaction is carried out in ethanol or water It is carried out in the presence of ethanol as a solvent; and/or, the temperature of the oximation reaction is 60-120°C; and/or, the oximation reaction time is 0.1-20 hours, preferably 0.5-10 hours; and/or, formula (III) The molar ratio of each of and (IV) compound to a compound selected from hydroxylamine and/or hydroxylamine hydrochloride is 1:1.5-1.5:1, preferably 1:1.2-1.2:1;
- the oximation reaction is carried out in the presence of 20-40% concentrated hydrochloric acid; and/or, the oximation reaction is carried out in the presence of tetrahydrofuran, ethanol or water-containing ethanol as a solvent; and/or, oxime
- the temperature of the reaction is -30 to 20°C, preferably 5-20°C; and/or, the oximation reaction time is 0.1-20 hours, preferably 0.5-10 hours; and/or, compounds of formula (III) and (IV)
- the molar ratio of each to the compound selected from nitrous acid, nitrite and/or alkyl nitrite is 1:1.5-1.5:1, preferably 1:1.2-1.2:1.
- step (2) is carried out using an esterification reagent selected from the following formulas (Va), IVb) and (Vc):
- X is halogen, especially chlorine, and R 7 is as defined by R 7 and R 7 ′ in any one of items 1-8.
- each of the compounds of formula (I) and (II) as required by any one of items 1-8 as photoinitiators especially the use as photoinitiators in UV-LED light curing systems, especially It is used as a photoinitiator in a light curing system with a radiation wavelength of 350-450nm, especially 365-420nm.
- Figure 1 is a schematic diagram of Ugra printing test strips, where
- Figure 2 is the UV absorption spectrum of Compound 1.
- Fig. 3 is a differential thermal analysis result spectrum of compound 1 and the commercially available photoinitiator OXE-02 in TPGDA.
- Figure 4 is a graph showing the relationship between the conversion rate of TPGDA under different concentrations of photoinitiator and the irradiation time under a 365nm LED light source.
- Figure 5 is a graph showing the relationship between the conversion rate of TPGDA under different concentrations of photoinitiator and the irradiation time under a 395nm LED light source.
- Figure 6 is a graph showing the relationship between the conversion rate of TPGDA under different concentrations of photoinitiator and the irradiation time under a 405nm LED light source.
- an oxime ester compound containing an unsaturated five-membered aromatic heterocyclic structure of formula (I) and (II) is provided:
- n is an integer of 0-8;
- n and n’ are the same and are 0 or 1;
- a 1 and A 2 are the same or different, and each independently represents O, S and NR a, wherein R a is H or C 1 -C 6 alkyl;
- R 1 , R 2 , R 3 , and R 4 are the same or different, and independently represent hydrogen, halogen, nitro, amino, cyano, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, mono C 1 -C 12 alkylamino, di C 1 -C 12 alkylamino, C 6 -C 18 aryloxy or C 6 -C 18 arylthio, wherein the aforementioned C 6
- the aryl groups in the -C 18 aryloxy and C 6 -C 18 arylthio groups may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, NH 2 , cyano, C 1 -C 6 alkyl, C 1 -C 6 alkoxy and C 1 -C 6 alkylthio;
- R 5 is hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, C 6 -C 18 aryl, C 6- C 18 aryl C 1 -C 6 alkyl, C 6 -C 18 aryl C 1 -C 6 alkylene, C 6 -C 18 aryloxy, C 6 -C 18 arylthio, 9H-carbazole -9 group-C 1 -C 6 alkyl group, 9H-carbazol-9 group-C 1 -C 6 alkylene group, 9H-fluoren-9 group-C 1 -C 6 alkyl group or 9H-fluoren-9 group -C 1 -C 6 alkylene group, wherein the aforementioned C 6 -C 18 aryl group, C 6 -C 18 aryl group, C 1 -C 6 alkyl group, C 6 -C 18 aryl group, C 1 -
- R 6 and R 6 ′ are the same or different, and independently represent H, cyano, C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkyl alkyl, C 4 -C 10 alkyl cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl or C 7 -C 20 alkyl aryl, wherein the aforementioned C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkyl alkyl, C 4 -C 10 alkyl cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkane Alkylaryl is optionally substituted with one or more groups independently selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 alkylthio, C 1 -C 6
- R 7 and R 7 ' are the same or different, and independently represent C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkyl alkyl, C 4 -C 10 alkyl Cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl or C 7 -C 20 alkyl aryl, wherein the aforementioned C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkylalkyl, C 4 -C 10 alkylcycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkyl aryl are optional Ground is substituted by one or more groups independently selected from the following group: C 1 -C 6 alkyl, C 1 -C 6 alkylthio, C 1 -C 6 alkoxy, halogen,
- the compounds of formula (I) and (II) contain both at least one five-membered aromatic heterocyclic structure part and an oxime ester structure part. These compounds have strong light absorption in the 350-450nm range. After absorbing light energy, they can quickly transfer energy and continue to initiate polymerization. They have obvious advantages in photosensitivity and pattern integrity, and are very suitable for UV-LED light sources. Safe and non-toxic can be used in food packaging and other fields. In addition, the compounds of formula (I) and (II) also have good thermal stability.
- C n -C m indicates that the number of carbon atoms contained in the group is nm.
- Halogen refers to fluorine, chlorine, bromine and iodine. In the present invention, it is preferable that the halogen includes F, Cl or a combination thereof.
- C n -C m alkyl group as used herein means having nm number, for example 1-20, preferably 1-12, more preferably 1-8, particularly preferably 1-6, especially preferably 1-4 Branched or unbranched saturated hydrocarbon groups with three carbon atoms, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1 -Dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3
- C 3 -C m cycloalkyl refers to a saturated alicyclic monocyclic group having 3 to m, such as 3 to 20, preferably 3 to 8, and more preferably 5 to 6 carbon atoms. Groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.
- C 4 -C m cycloalkylalkyl means an alkyl group substituted by a cycloalkyl group and contains a total of 4 to m carbon atoms, for example 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms, more preferably 4-6 carbon atoms, of which alkyl and cycloalkyl apply as defined herein, such as cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopropylbutyl, cyclobutylmethyl, cyclobutyl Cycloethyl, cyclobutylpropyl, cyclobutylbutyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, Cyclohexylpropyl, cyclohexylmethyl
- C 4 -C 10 alkylcycloalkyl means a cycloalkyl substituted by an alkyl group and contains a total of 4 to m carbon atoms, for example 4 to 10 carbon atoms, preferably 4 to 8 carbon atoms, more preferably 4-6 carbon atoms, of which alkyl and cycloalkyl apply as defined herein, such as methylcyclopropyl, ethylcyclopropyl, propylcyclopropyl, butylcyclopropyl, methylcyclobutyl, ethyl Cyclobutyl, propylcyclobutyl, butylcyclobutyl, methylcyclopentyl, ethylcyclopentyl, propylcyclopentyl, butylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl , Butylcyclohexyl, etc.
- C 6 -C m aryl refers to a monocyclic, bicyclic, tricyclic or more containing 6-m carbon atoms, such as 6-18 or 6-15, preferably 6-10 carbon atoms Ring aromatic hydrocarbon group.
- C 6 -C m aryl groups mention may be made of phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, xylyl, methylethylphenyl, diethylphenyl, methyl Group.
- C 7 -C 20 aralkyl means an alkyl group substituted by an aryl group and contains 7-20 carbon atoms in total, for example 7-15 or 7-12, preferably 7-10 carbon atoms, more preferably 7-8 carbon atoms, of which alkyl and aryl are defined herein, such as benzyl, phenethyl, naphthylmethyl, naphthylethyl, fluorenylmethyl, fluorenylethyl and the like.
- C 7 -C 20 alkylaryl means an aryl group substituted by an alkyl group and contains a total of 7-20 carbon atoms, for example 7-12, preferably 7-10 carbon atoms, more preferably 7-8 Carbon atoms, in which alkyl and aryl groups are defined herein, such as methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, methyl Naphthyl, ethylnaphthyl, etc.
- C n -C m alkoxy and “C n -C m alkylthio" mean that any carbon atom of the open chain C n -C m alkane corresponding to the C n -C m alkyl group is bonded to any carbon atom A C n -C m alkyl group with an oxygen atom or a sulfur atom as the linking group, for example, a C 1 -C 20 alkoxy (or thio) group, preferably a C 1 -C 12 alkoxy (or thio) group, more preferably A C 1 -C 8 alkoxy (or thio) group, particularly preferably a C 1 -C 6 alkoxy (or thio) group, and particularly preferably a C 1 -C 4 alkoxy (or thio) group.
- C 1 -C 8 alkoxy can be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, pentoxy, isopentoxy Group, hexyloxy, heptyloxy, octyloxy, isooctyloxy and its isomers.
- the C 1 -C 8 alkylthio group can be methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, 2-butylthio, tert-butylthio, pentylthio, isoamylthio Group, hexylthio, heptylthio, octylthio, isooctylthio and its isomers.
- C 6 -C m aryloxy and "arylthio C 6 -C m” refers to the -C m any aromatic carbon atoms in the aromatic C 6 -C aryl group m corresponding to C 6
- the C 6 -C m aryl group to which an oxygen atom or a sulfur atom is bonded as a linking group such as phenylthio, phenoxy, tolyloxy, tolylthio, naphthylthio, naphthyloxy and the like.
- m is an integer of 0-8, preferably an integer of 0-4, and more preferably 0, 1, or 2.
- m A 1 s may be the same or different.
- a 1 and A 2 may be the same or different.
- m of A 1 and A 2 are the same or different, and each independently represents O, S and NR a, wherein R a is H or C 1 -C 6 alkyl.
- m of A 1 and A 2 are the same or different, and each independently represents O, S and NR a, wherein R a is H or C 1 -C 4 alkyl.
- R 1 , R 2 , R 3 , and R 4 independently represent hydrogen, halogen, nitro, amino, cyano, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, mono C 1 -C 12 alkylamino, di C 1 -C 12 alkylamino, C 6 -C 18 aryloxy or C 6 -C 18 arylthio, wherein the aforementioned C 6
- the aryl groups in the -C 18 aryloxy and C 6 -C 18 arylthio groups may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, NH 2 , cyano, C 1 -C 6 alkyl, C 1 -C 6 alkoxy and C 1 -C 6 alkylthio.
- R 1 , R 2 , R 3 , and R 4 independently represent hydrogen, halogen, nitro, amino, cyano, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, mono-C 1 -C 6 alkylamino, di-C 1 -C 6 alkylamino, C 6 -C 10 aryloxy or C 6 -C 10 arylthio, wherein the aforementioned C 6-
- the aryl groups in the C 10 aryloxy and C 6 -C 10 arylthio groups may be optionally substituted with one or more groups independently selected from the following group: halogen, nitro, hydroxyl, mercapto, NH 2. Cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1 -C 4 alkylthio.
- R 1 , R 2 , R 3 , and R 4 independently represent hydrogen, halogen, nitro, amino, cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1- C 4 alkylthio, mono C 1 -C 4 alkylamino, di C 1 -C 4 alkylamino, phenoxy or phenylthio, wherein the benzene in the aforementioned phenoxy and phenylthio groups
- the group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, NH 2 , cyano, C 1 -C 4 alkyl, C 1 -C 4 alkane Oxy and C 1 -C 4 alkylthio.
- R 5 represents hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, C 6 -C 18 aryl Group, C 6 -C 18 aryl, C 1 -C 6 alkyl, C 6 -C 18 aryl, C 1 -C 6 alkylene, C 6 -C 18 aryloxy, C 6 -C 18 arylthio , 9H-carbazol-9yl-C 1 -C 6 alkyl, 9H-carbazol-9yl-C 1 -C 6 alkylene, 9H-fluoren-9yl-C 1 -C 6 alkyl or 9H -Fluoren-9 group-C 1 -C 6 alkylene group, wherein the aforementioned C 6 -C 18 aryl group, C 6 -C 18 aryl group C 1 -C 6 alkyl group, C 6 -C 18 aryl group
- R 5 represents hydrogen, halogen, nitro, cyano, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 6 -C 13 aryl , C 6 -C 13 aryl C 1 -C 4 alkyl, C 6 -C 13 aryl, C 1 -C 4 alkylene, C 6 -C 13 aryloxy, C 6 -C 13 arylthio, 9H-carbazol-9 group-C 1 -C 4 alkyl group, 9H-carbazol-9 group-C 1 -C 4 alkylene group, 9H-fluoren-9 group-C 1 -C 4 alkyl group or 9H- Fluoren-9yl-C 1 -C 4 alkylene group, wherein the aforementioned C 6 -C 13 aryl group, C 6 -C 13 aryl group C 1 -C 4 alkyl group, C 6 -C 13 aryl group C
- R 5 represents hydrogen, halogen, nitro, cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, phenyl, C 6- C 13 aryl C 1 -C 2 alkyl, C 6 -C 13 aryl C 1 -C 2 alkylene, C 6 -C 10 aryloxy, C 6 -C 10 arylthio, 9H-carbazole -9 group-C 1 -C 2 alkyl group, 9H-carbazol-9 group-C 1 -C 2 alkylene group, 9H-fluoren-9 group-C 1 -C 2 alkyl group or 9H-fluoren-9 group -C 1 -C 2 alkylene, wherein the aforementioned phenyl, C 6 -C 13 aryl C 1 -C 2 alkyl, C 6 -C 13 aryl C 1 -C 2 alkylene, C 6 -C 10 -C 10
- R 6 and R '6 are identical or different and each independently represents H, cyano, C 1 -C 20 alkyl, C 3 - C 10 cycloalkyl, C 4 -C 10 cycloalkyl Alkyl group, C 4 -C 10 alkyl cycloalkyl group, C 6 -C 20 aryl group, C 7 -C 20 aralkyl group or C 7 -C 20 alkyl aryl group, wherein the aforementioned C 1 -C 20 alkyl group , C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkyl alkyl, C 4 -C 10 alkyl cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C
- the 7 -C 20 alkyl aryl group is optionally substituted with one or more groups independently selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 alkyl
- R 6 and R 6 ' are the same or different, and independently represent H, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkyl alkane Group, C 4 -C 8 alkylcycloalkyl group, C 6 -C 10 aryl group, C 7 -C 11 aralkyl group or C 7 -C 11 alkyl aryl group, wherein the aforementioned C 1 -C 6 alkyl group, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl and C 7 -C 11 alkylaryl is optionally substituted with one or more groups independently selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkylthio, C 1
- R 6 and R 6 ′ are the same or different, and independently represent H, cyano, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl or C 3 -C 6 cycloalkyl.
- C 1 -C 2 alkyl wherein the aforementioned C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl and C 3 -C 6 cycloalkyl C 1 -C 2 alkyl are optionally substituted by one or more Substitution groups independently selected from the following group: C 1 -C 4 alkyl, C 1 -C 4 alkylthio, C 1 -C 4 alkoxy, halogen, nitro, amino, mono (C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkyl)amino and mercapto.
- R 7 and R 7 ′ are the same or different, and independently represent C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkyl alkyl, C 4 -C 10 alkyl cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl or C 7 -C 20 alkyl aryl, wherein the aforementioned C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkyl alkyl, C 4 -C 10 alkyl cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkane Alkylaryl is optionally substituted with one or more groups independently selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 alkylthio, C 1 -C 6 alk
- R 7 and R 7 ′ are the same or different, and independently represent C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkyl alkyl, C 4- C 8 alkyl cycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl or C 7 -C 11 alkyl aryl, wherein the aforementioned C 1 -C 6 alkyl, C 3 -C 8 Cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl, and C 7 -C 11 alkyl
- the aryl group is optionally substituted by one or more groups independently selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkylthio, C 1 -C 4 alkoxy,
- R 7 and R 7 ' are the same or different, and independently represent C 1 -C 4 alkyl or phenyl, wherein the aforementioned C 1 -C 4 alkyl and phenyl are optionally substituted by one or more Substitution by a group independently selected from the following group: C 1 -C 4 alkyl, C 1 -C 4 alkylthio, C 1 -C 4 alkoxy, halogen, nitro, amino, mono (C 1- C 4 alkyl) amino, di(C 1 -C 4 alkyl) amino and mercapto.
- the compounds of formula (I) and (II) are selected from compounds 1-65 listed below.
- m, A 1 , A 2 , R 1 -R 4 and R 6 in formula (III), (IV), (IIIa), (IVa), (IIIb) and (IVb), formula (III), R 5 in (IIIa) and (IIIb) and R 6 ′ in formulas (IV), (IVa) and (IVb) are as defined for the compounds of formula (I) and formula (II); and
- an oximation reaction is required to introduce an oxime group, and then the hydroxyl group in the oxime group is converted into the corresponding ester group through an esterification reaction to obtain the compound of the present invention.
- Oxime ester compound is required to introduce an oxime group, and then the hydroxyl group in the oxime group is converted into the corresponding ester group through an esterification reaction to obtain the compound of the present invention. Oxime ester compound.
- a 1, A 2, R 1 -R 4 and R 6, of formula (III) and (IIIa) and R 5 in formula ( R 6 ′ in IV) and (IVa) is as defined for the compounds of formula (I) and (II).
- hydroxylamine hydrochloride NH 2 OH.HCl
- hydroxylamine NH 2 OH
- a mixture thereof as an oximation reagent.
- the oximation reaction is usually carried out in an organic solvent, preferably in an organic polar solvent.
- Examples of usable solvents include ethanol or water-containing ethanol.
- a base such as sodium acetate, pyridine, piperidine, triethylamine, tetramethylammonium hydroxide, or a mixture thereof.
- pyridine, piperidine, and triethylamine can also be used as bases and/or solvents or co-solvents.
- the temperature of the oximation reaction is generally the reflux temperature of the solvent, and the temperature range is usually 60-120°C.
- the oximation reaction time is also not particularly limited, and it is usually carried out for 0.1-20 hours, preferably 0.5-10 hours.
- each compound of formula (III) and (IV) and the compound selected from hydroxylamine and/or hydroxylamine hydrochloride is not particularly limited. Generally speaking, they are used in approximately equimolar amounts, for example, the molar ratio of the two is 1:1.5 -1.5:1, preferably 1:1.2-1.2:1.
- m, A 1 , A 2 , R 1 -R 4 and R 6 in formulas (IIIb) and (IVb), R 5 in formula (IIIb) and R 6 'in formula (IVb) are the same as (I) and (II) as defined by compounds.
- nitrous acid, nitrite and/or alkyl nitrite as an oximation reagent. This reagent nitrosates the "active" (methylene) methyl group ( ⁇ -(methylene) methyl group, that is, the (methylene) group next to the non-cyclic carbonyl group).
- the alkyl nitrite may be a C 1 -C 6 alkyl nitrite, such as methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, and isoamyl nitrite.
- the oximation reaction is usually carried out in an organic solvent, preferably in an organic polar solvent. Examples of usable solvents include tetrahydrofuran, ethanol, or water-containing ethanol. In order to promote the completion of the oximation reaction, it is generally necessary to add concentrated hydrochloric acid, the concentration of which is usually 20-40%.
- Concentrated hydrochloric acid can also be used as acid and/or solvent or co-solvent.
- the temperature of the oximation reaction is a low temperature, and the temperature range is usually -30 to 20°C, preferably 5-20°C.
- the oximation reaction time is also not particularly limited, and it is usually carried out for 0.1-20 hours, preferably 0.5-10 hours.
- the relative amounts of the compounds of formula (III) and (IV) and the compound selected from the group consisting of nitrous acid, nitrite and/or alkyl nitrite are not particularly limited. Generally speaking, they are used in approximately equimolar amounts, such as two The molar ratio of these is 1:1.5-1.5:1, preferably 1:1.2-1.2:1.
- Each oxime ester group may have two configurations, (Z) type or (E) type.
- the isomers can be separated by conventional methods, but a mixture of isomers can also be used as the photoinitiating substance. Therefore, the present invention also relates to a mixture of respective configurational isomers of the compounds of formula (I) and (II).
- the esterification of compounds of formula (IIIa), (IIIb), (IVa) and (IVb) is conventional. Through this reaction, the hydroxyl group in the oxime group is converted into an ester group, thereby obtaining the compounds of formula (I) and (II).
- the esterification agent there is no particular limitation, as long as it can convert the hydroxyl group in the oxime group of the compounds of formula (IIIa), (IIIb), (IVa) and (IVb) into an ester group.
- the esterification reagent the corresponding acid halide, such as acid chloride, the corresponding carboxylic acid, and the corresponding acid anhydride can also be used. These compounds can be represented as formula (Va), (Vb) and (Vc) respectively:
- X is halogen, in particular chlorine, and R 7 are as defined for formula (I) and (II) compound R (II) R compound 7 and 7 'are defined.
- the above-mentioned esterification reaction is usually carried out in the presence of a catalyst suitable for the esterification reaction.
- a catalyst suitable for the esterification reaction.
- the catalyst either an acid catalyst or a basic catalyst may be used.
- the catalyst one or more selected from the group consisting of sulfuric acid, perchloric acid, zinc chloride, ferric chloride, pyridine, p-toluenesulfonic acid, sodium hydroxide, potassium hydroxide, sodium carbonate can be used , Sodium bicarbonate, sodium tert-butoxide, sodium ethoxide, sodium hydride, potassium hydride, calcium hydride and tertiary amines such as trialkylamines such as trimethylamine and triethylamine.
- the amount of catalyst used is conventional and can be determined by common sense in the field or through several routine preliminary experiments.
- the above-mentioned esterification reaction is usually carried out in a solvent, preferably in an organic solvent.
- a solvent preferably in an organic solvent.
- the type of solvent there is no particular restriction on the choice of the type of solvent, as long as it can dissolve the compound of formula (IIIa), (IIIb), (IVa) or (IVb) and the esterification reagent and is chemically inert to the esterification reaction, that is, it is not Just participate in the esterification reaction.
- the solvent tetrahydrofuran, benzene, toluene, N,N-dimethylformamide, dichloromethane and acetone can be mentioned.
- a single solvent may be used, or a mixture of two or more solvents may be used.
- the relative amount of the compound of formula (IIIa), (IIIb), (IVa) or (IVb) and the esterification agent selected from the group consisting of (Va), (Vb) and (Vc) is not particularly limited. Generally speaking, they are It is used in approximately equimolar amounts, for example, the molar ratio of the two is 1:1.5-1.5:1, preferably 1:1.2-1.2:1.
- the esterification reaction can be carried out in a very wide temperature range. According to the present invention, it is advantageous that the esterification reaction is carried out at a temperature of -10°C to 150°C, preferably 0°C to 100°C, preferably at room temperature.
- the esterification reaction time is also not particularly limited, and it is usually carried out for 1-24 hours, preferably 1-12 hours.
- the reaction mixture After the esterification reaction is completed, a reaction mixture containing the compound of formula (I) or formula (II) is obtained. Therefore, the reaction mixture needs to be post-treated to obtain a purified compound of formula (I) or formula (II).
- the reaction mixture obtained by the esterification reaction is filtered first, and the filtrate portion is taken out. Then, the filtrate is washed to remove the catalyst and unreacted raw materials.
- the washing liquid there is no particular limitation, as long as the catalyst and unreacted raw materials can be removed.
- dilute hydrochloric acid aqueous solution
- saturated sodium bicarbonate aqueous solution and water can be mentioned.
- the concentration of dilute hydrochloric acid is not particularly limited.
- dilute hydrochloric acid with a concentration of 5-12% is used. Washing with lotion can be done once or multiple times; in the case of multiple times, a single lotion can be used, or different lotions can be used in sequence. According to the present invention, it is advantageous that the filtrate obtained by filtering the reaction mixture obtained by the esterification reaction is washed successively with dilute hydrochloric acid, a saturated sodium bicarbonate aqueous solution and water. Of course, after each washing with a lotion, you need to pour off the water phase and then use the next lotion to wash the organic phase. After washing, it needs to be dried to remove residual water. For this reason, anhydrous sodium sulfate or magnesium sulfate can usually be used for drying.
- the remaining organic solvent is removed.
- the means for removing the organic solvent here is not particularly limited, and the organic solvent can usually be removed by distillation under reduced pressure. After removing the residual organic solvent, a crude product of the compound of formula (I) or (II) is obtained. If it is desired to further improve the purity of the compound of formula (I) or (II), the compound can be further purified, for example, by recrystallization.
- the selection of the recrystallization solvent is conventional and not particularly limited. According to the present invention, it is advantageous to use methanol to recrystallize the crude product of the compound of formula (I) or (II).
- the compounds of formula (I) and (II) of the present invention have longer absorption wavelengths, especially strong absorption in the wavelength range of 365-420 nm, so they can be applied to UV-LED light curing systems.
- each of the compounds of formula (I) and (II) of the present invention as a photoinitiator.
- the compounds of formula (I) and (II) of the present invention are each advantageously used as a photoinitiator in a UV-LED light curing system and can effectively initiate a curing reaction.
- Particularly preferred is the use of each of the compounds of formula (I) and (II) of the present invention as photoinitiators in photocuring systems with radiation wavelengths of 350-450 nm, especially 365-420 nm.
- the dosage is conventional or can be determined by routine preliminary tests.
- the synthesis method of the final compound 4 is similar to that of the final compound 1, except that the intermediate compound 1a is replaced with 4a.
- the NMR data of compound 4 are shown in the table below.
- 2,2'-Dithiophene (0.03mol, 4.98g) was dissolved in 75ml of acetic anhydride, and then 12 drops of 85% phosphoric acid were added dropwise to the reaction solution, and then heated and refluxed for 1 hour. The reaction was stopped, and the reaction liquid was poured into 500 g of ice water, and stirred until the acetic anhydride was completely hydrolyzed. The crude product was obtained by filtration, and then the crude product was recrystallized with 2,6-dioxane to obtain 5.8 g of light yellow solid with a yield of 77%.
- 2,2'-Dithiophene (0.027mol, 4.4g) was dissolved in 44ml of dichloroethane, and then N,N-dimethylformamide (0.106mol, 7.8g) was added, and the temperature was 0-5°C POCl 3 (0.084 mol, 12.6 g) was added dropwise to the resulting mixed solution, and then the reaction was stirred at room temperature for 5 hours. Then the reaction was stopped, and a saturated aqueous sodium bicarbonate solution was added to neutralize the reaction solution to neutrality. Then the organic phase was extracted with dichloromethane and dried with anhydrous magnesium sulfate.
- the synthesis method of the final compound 41 is similar to that of the final compound 37, except that the intermediate compound 37a is replaced with 41a.
- the NMR data of compound 41 are shown in the table below.
- DSC differential thermal analysis
- test results show that the initial temperature of compound 1 to initiate TPGDA polymerization is 175°C, the initial temperature of OXE-02 (see below for its structure) to initiate TPGDA polymerization is 105°C, and the initial temperature of COXE-15 (see below for its structure) to initiate TPGDA polymerization is 98°C.
- the stability of the compound 1-65 in the acrylate monomer according to the present invention is significantly higher than that of the commercial products OXE-02 and COXE-15, so the compound 1-65 of the present invention has better thermal stability Sex.
- the conversion rate of TPGDA under different concentrations of photoinitiator (compound 1) and irradiation time is shown in Fig. 4, Fig. 5 and Fig. 6, and the double bond conversion rate (compound 1 and 37) specific value summary when irradiated for 5 min In Table 2 below.
- Photo-DSC test results show that each of Compounds 1 and 37 can initiate the polymerization of acrylic monomers under three UV-LED light sources.
- the sections of the Ugra printed test strip are shown in Figure 1.
- the test strip of Ugra printing plate is divided into 5 control sections. From left to right, they are: continuous density ladder section (1); Yin and Yang micron contour concentric circle section (2); full-step adjustment dot section (3); heavy Shadow control section (4); highlight and dark control section (5).
- the first section The continuous density ladder section is divided into 13 gradients to control the exposure and development.
- the second section Concentric circles with yin and yang micrometer contours: Concentric circles with 12 yin and yang micrometer contours, 4, 6, 8, 10, 12, 15, 20, 25, 30, 40, 55, 70, used to detect the exposure and development of the PS plate.
- the third section Full-scale adjustment dot section: It is composed of 10%-100% and a range of 10%, and is arranged in two rows. It is used to measure the transfer of printing, proofing and printing. Measure and produce the change curve graph of film dot and printing, proofing and printing online shop.
- the fourth section ghost control section: It is composed of thin lines with a line width of 60 lines/cm and an area rate of 60%. It is divided into 4 small blocks, with lines arranged at three angles of 0°, 45°, and 90°, and there is 1 The D block of /4 is arranged in small short lines with 90° on both sides, 45° in the middle, and 90° up and down.
- the fifth segment highlight and dark tone control segment
- the fine dot segment is arranged by the small highlight dots and the dark deep dots correspondingly, which is used to finely control the accuracy of exposure and development.
- a photosensitive composition containing a photoinitiator is coated on an aluminum substrate, and then exposed and developed. The sensitivity is evaluated from the continuous scale of the obtained image, and the accuracy is evaluated from the micro-line test block area, thereby evaluating the advantages and disadvantages of the photosensitive composition formulation .
- the photoinitiator in the above composition is selected from compounds 1-65 of the present invention or photoinitiators known in the prior art (for comparison).
- Acrylic resin is a resin purchased from Shanghai Fushun International Trade Co., Ltd. under the trade name FS2600K, with a functionality of 2, and a number average molecular weight of 1400.
- Dipentaerythritol hexaacrylate is a product under the trade name GM66G0C purchased from Shanghai Fushun International Trade Co., Ltd.
- Crystal violet dye is a product purchased from Shanghai Sinopharm under the trade name of hexamethyl rose aniline hydrochloride. Photographic performance test
- Aluminum base size 1030mm ⁇ 800mm
- the photopolymerizable compound undergoes polymerization reaction in the presence of the initiator, and is insoluble in the developer, while the non-exposed area is soluble, so a negative image is obtained.
- the sensitivity of the photoinitiator was evaluated from the continuous scale of the obtained image.
- the sensitivity of the initiator system is characterized by the highest number of gray levels retained (ie, polymerized) after development. The higher the number of gray levels, the higher the sensitivity of the test system. The results are shown in Table 3.
- OXE-01 means 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime)
- OXE-02 means 1-(6 -O-methylbenzoyl-9-ethylcarbazol-3-yl)-(3-ethanone)-1-oxime acetate, the structural formulas are as follows:
- the number of gray levels at 365 nm, 385 nm, 395 nm and 405 nm of Compound 1-65 of the present invention is higher than that of the commercially available photoinitiators OXE-01 and OXE-02. That is to say, the oxime ester photoinitiator containing the five-membered aromatic heterocyclic structure of the present invention has better photosensitive performance at 365nm, 385nm, 395nm and 405nm wavelengths, and is suitable for use in 365nm, 385nm, 395nm, 405nm wavelengths. UV-LED light source.
- the oxime ester photoinitiator containing a five-membered aromatic heterocyclic structure represented by formulas (I) and (II) of the present invention has good photosensitive properties at wavelengths of 365nm, 385nm, 395nm and 405nm, and At this stage, ketoxime ester photoinitiators such as OXE-01 and OXE-02 are commercially available.
- the compound disclosed in the invention has a simple production process and a high yield, which is very suitable for industrial production. Such compounds have good compatibility with UV-LED light sources of 365nm, 385nm, 395nm, 405nm, and can be widely used in the fields involved in UV-LED light curing.
- the photoinitiators of the present invention can be used to promote green and environmentally friendly UV-LEDs
- the light source contributes to the wide application of UV curing industry.
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Abstract
Oxime ester compounds represented by formulas (I) and (II) containing an unsaturated five-membered heteroaromatic ring structure, wherein m, n, n', A1, A2, R1, R2, R3, R4, R5, R6, R6', R7, and R7' are defined in the specification. The compounds represented by the formulas (I) and (II) have excellent light absorption at 350-450 nm, can initiate the polymerization of acrylate-based monomers at low concentration, and have excellent thermal stability in the acrylate monomers, are oxime ester photoinitiators good in stability and suitable for an ultraviolet-visible LED light source. The present invention further provides preparation of the compounds represented by the formulas (I) and (II) and use of the compounds represented by the formulas (I) and (II) as photoinitiators or photosensitizers.
Description
本发明涉及包含五元芳杂环结构的肟酯类化合物。本发明还涉及所述肟酯类化合物的制备及其作为光引发剂在光聚合组合物中的用途。The present invention relates to oxime ester compounds containing a five-membered aromatic heterocyclic structure. The invention also relates to the preparation of the oxime ester compound and its use as a photoinitiator in a photopolymerization composition.
光引发剂又称光敏剂或光固化剂是一类能在紫外光区(250-400nm)或可见光区(400-600nm)吸收一定波长的能量，产生自由基、阳离子等，从而引发单体聚合交联固化的化合物。在光固化体系中，光引发剂一般占3-5％，含量虽低，却是其中的关键组分，对光固化速度起决定作用。它关系到配方体系在光辐照时，低聚物及稀释剂能否迅速交联固化，从而由液态转变为固态。目前，光固化技术已广泛应用在涂料、油墨、微电子、印刷等传统领域，另外还用于制备激光录像及三维元件等新型领域。作为光固化体系的重要组分，光引发剂必须满足不同光固化条件和应用的需要。在自由基光引发剂领域，主要目标是：提高光敏感度，提高表面固化效率(抗氧阻聚)，提高深层固化性能，提高光引发剂在单体及树脂中的溶解性，降低毒性和气味，降低固化后未固化引发剂的迁移性，降低黄变性。Photoinitiator, also known as photosensitizer or photocuring agent, is a kind of energy that can absorb a certain wavelength of energy in the ultraviolet region (250-400nm) or visible region (400-600nm) to generate free radicals, cations, etc., thereby initiating monomer polymerization Cross-linked and cured compound. In light curing systems, photoinitiators generally account for 3-5%. Although the content is low, it is a key component and determines the speed of light curing. It is related to whether the oligomer and diluent can be quickly cross-linked and solidified when the formula system is irradiated with light, thereby changing from liquid to solid. At present, light curing technology has been widely used in traditional fields such as coatings, inks, microelectronics, printing, etc. It is also used in the preparation of new fields such as laser video recording and three-dimensional components. As an important component of the light curing system, photoinitiators must meet the needs of different light curing conditions and applications. In the field of free radical photoinitiators, the main goals are: improve light sensitivity, improve surface curing efficiency (anti-oxidation inhibition), improve deep curing performance, improve the solubility of photoinitiators in monomers and resins, and reduce toxicity and odor , Reduce the migration of uncured initiator after curing, reduce yellowing.
肟酯类光引发剂因其具有优异的感光性能成为近年来逐渐受到重视的一类光引发剂，其中巴斯夫产品OXE-01和OXE-02是目前市场上常见的两种肟酯类代表性产品，这两种产品具有较高的光敏度，但是它们的紫外吸收波长偏短(250-350nm)，并不适用于紫外-可见LED光源(发射波长365nm、385nm、395nm、405nm、420nm、430nm、450nm)的需求。国内也有一些关于肟酯类光引发剂的专利，例如CN10277552A披露了一种二苯硫醚酮肟酯类光引发剂及其制备方法，CN102492059A公开了取代的二苯硫醚酮肟酯类光引发剂等等。但是大多数引发剂的紫外吸收波长在250-350nm，无法与日益发展的LED光源匹配，这就大大限制了肟酯类光引发剂的应用。Oxime ester photoinitiators have become a class of photoinitiators that have gradually received attention in recent years due to their excellent photosensitivity. Among them, BASF's products OXE-01 and OXE-02 are two representative products of oxime esters that are common on the market. These two products have high photosensitivity, but their ultraviolet absorption wavelength is too short (250-350nm), which is not suitable for ultraviolet-visible LED light source (emission wavelength 365nm, 385nm, 395nm, 405nm, 420nm, 430nm, 450nm). There are also some domestic patents on oxime ester photoinitiators. For example, CN10277552A discloses a diphenyl sulfide ketoxime ester photoinitiator and its preparation method, and CN102492059A discloses a substituted diphenyl sulfide ketoxime ester photoinitiator. Agent and so on. However, most initiators have UV absorption wavelengths of 250-350nm, which cannot match the increasingly developed LED light sources, which greatly limits the application of oxime ester photoinitiators.
LED点光源、线光源、面光源已开始应用于光固化行业，相对于传统UV固化设备，LED光源有着绝对的优势。LED point light sources, line light sources, and surface light sources have begun to be used in the light curing industry. Compared with traditional UV curing equipment, LED light sources have absolute advantages.
(1)使用寿命长。汞灯使用寿命只有800-3000小时，采用UV-LED紫外固化系统的使用寿命达到20000-30000小时。LED方式可以仅在需要紫外线时瞬间点亮，按DUIY＝1/5(准备时间＝照射时间*5＝1)时，LED方式的使用寿命相当于汞灯方式的30-40倍。因此，LED方式减少了更换灯泡的时间，提高了生产效率，同时也非常节能。而传统汞灯方式固化设备在工作时，由于汞灯启动慢、开闭影响灯泡寿命，必须一直点亮，不仅造成不必要的电力消耗，而且缩短了汞灯工作寿命。(1) Long service life. The service life of the mercury lamp is only 800-3000 hours, and the service life of the UV-LED ultraviolet curing system can reach 20,000-30000 hours. The LED method can be lit instantaneously only when ultraviolet light is needed. When DUIY=1/5 (preparation time=irradiation time*5=1), the service life of the LED method is equivalent to 30-40 times that of the mercury lamp method. Therefore, the LED method reduces the time to replace the bulb, improves production efficiency, and is also very energy-saving. When the traditional mercury lamp curing equipment is working, because the mercury lamp starts slowly and the opening and closing affects the life of the bulb, it must be lit all the time, which not only causes unnecessary power consumption, but also shortens the working life of the mercury lamp.
(2)无热辐射。高功率发光二极管没有红外线发出。被照射的产品表面温升仅在5℃以下，而传统汞灯方式的紫外线固化机一般都会使被照射的产品表面温度升高60-90℃，这会使产品的定位发生位移，造成产品不良。(2) No heat radiation. High-power LEDs do not emit infrared light. The surface temperature rise of the irradiated product is only below 5℃, while the traditional mercury lamp method of ultraviolet curing machine generally increases the surface temperature of the irradiated product by 60-90℃, which will cause the positioning of the product to shift and cause product failure .
(3)环保无污染。传统的汞灯方式固化机采用汞灯发光方式，灯泡内有水银，废品处理、运输非常麻烦，处理不当会对环境产生严重污染。而LED式固化机采用半导体放光，没有对 环境造成污染的因素。因此使用LED式固化机更加环保。(3) Environmental protection and no pollution. The traditional mercury lamp curing machine uses a mercury lamp to emit light. There is mercury in the bulb, which makes the waste disposal and transportation very troublesome, and improper handling can cause serious pollution to the environment. The LED curing machine uses semiconductors to emit light and has no environmental pollution factors. Therefore, the use of LED curing machine is more environmentally friendly.
(4)超强照度。采用大功率LED芯片和特殊的光学设计，使紫外光达到高精度、高强度照射；紫外光输出可达到8600mW/m
2的照射强度。采用最新的光学技术和制造工艺，实现了比传统汞灯照射方式更加优化的高强度输出与均匀性，几乎是传统汞灯方式照射光度的2倍，使UV粘合剂更快固化，缩短了生产时间，大幅度提高了生产效率。传统的汞灯方式点光源固化机在增加照射通道时，通道的增加会造成单个照射通道的输出能量减少。而采用LED式的照射，各个照射头独立发光，照射能量不受通道增加的影响，始终保持在最大值。因其超强集中的光照度，与汞灯相比，UV-LED缩短了作业的照射时间，提高了生产效率。
(4) Super illuminance. High-power LED chips and special optical design are used to achieve high-precision and high-intensity irradiation of ultraviolet light; ultraviolet light output can reach 8600mW/m 2 irradiation intensity. Using the latest optical technology and manufacturing process, it has achieved a higher intensity output and uniformity that is more optimized than the traditional mercury lamp irradiation method, which is almost twice the luminosity of the traditional mercury lamp method, which makes the UV adhesive cure faster and shorten Production time has greatly improved production efficiency. When the traditional mercury lamp type point light source curing machine increases the irradiation channel, the increase of the channel will cause the output energy of a single irradiation channel to decrease. With LED-style illumination, each illuminating head emits light independently, and the illuminating energy is not affected by the increase in the channel, and always remains at the maximum. Because of its super concentrated illuminance, compared with mercury lamps, UV-LED shortens the irradiation time of the operation and improves the production efficiency.
(5)能耗低。UV-LED方式较汞灯方式有效发光效率高10倍以上。同时，汞灯方式无论是否进行有效照射，汞灯都需要连续点灯工作，电力一直处于消耗状态。而UV-LED方式只在照射时才消耗电力，而在待机时电力消耗几乎为零。可以做一个简单的计算，每台点光源固化机节省的电能：270(瓦特)*8(小时)*365(天)＝800(千瓦时)由此可见，每台每年仅耗电费用就可以省千元。不仅如此，通过节省电能，每台每年可间接减少二氧化碳的排放量1.4吨，相当于一辆轿车一年的排气量。(5) Low energy consumption. The effective luminous efficiency of UV-LED method is more than 10 times higher than that of mercury lamp method. At the same time, no matter whether the mercury lamp is irradiated effectively or not, the mercury lamp needs to be continuously lit and the power is always consumed. The UV-LED method consumes power only during irradiation, and almost zero power consumption during standby. A simple calculation can be made. The energy saved by each point light source curing machine: 270 (watts) * 8 (hours) * 365 (days) = 800 (kilowatt hours). It can be seen that only the cost of electricity consumption per year is enough Thousands of savings. Not only that, by saving electric energy, each car can indirectly reduce carbon dioxide emissions by 1.4 tons per year, which is equivalent to the annual displacement of a car.
因此，仍旧需要一种吸收波长适合UV-LED光源(发射波长300-450nm、尤其365-420nm)并且热稳定性良好的光引发剂。Therefore, there is still a need for a photoinitiator with an absorption wavelength suitable for UV-LED light sources (emission wavelengths of 300-450 nm, especially 365-420 nm) and good thermal stability.
另外，目前市场在售的肟酯类光引发剂OXE-02，尽管光引发活性较高，但是稳定性一般，尤其是在可光聚合物单体中的稳定较差，因而由其配成的感光组合物不宜长时间存储及运输，这给实际应用带来一定的困难。In addition, the oxime ester photoinitiator OXE-02 currently on the market has relatively high photoinitiation activity, but its stability is generally poor, especially in photopolymer monomers. The photosensitive composition is not suitable for long-term storage and transportation, which brings certain difficulties to practical applications.
发明内容Summary of the invention
本发明人出人意料地发现，含有五元芳族杂环结构的肟酯类化合物在350-450nm有优异的光吸收，在低浓度下即可引发丙烯酸酯类单体聚合，并且在丙烯酸酯单体中具有优异的热稳定性，是一类适宜于紫外-可见LED光源的稳定性良好的肟酯类光引发剂。The inventors unexpectedly discovered that the oxime ester compound containing a five-membered aromatic heterocyclic structure has excellent light absorption at 350-450nm, and can initiate the polymerization of acrylate monomers at low concentrations. It has excellent thermal stability and is a kind of oxime ester photoinitiator with good stability suitable for UV-visible LED light source.
因此，本发明的一个目的是提供一种含有五元芳族杂环结构的肟酯类化合物，该类化合物的吸收波长不仅适用于紫外-可见LED光源辐射固化，而且还具有很好的热稳定性。Therefore, an object of the present invention is to provide an oxime ester compound containing a five-membered aromatic heterocyclic structure. The absorption wavelength of this compound is not only suitable for UV-visible LED light source radiation curing, but also has good thermal stability. Sex.
本发明的另一目的是提供制备本发明含有五元芳族杂环结构的肟酯类化合物的方法。Another object of the present invention is to provide a method for preparing the oxime ester compound containing the five-membered aromatic heterocyclic structure of the present invention.
本发明的再一目的是提供本发明含有本发明五元芳族杂环结构的肟酯类化合物作为光引发剂或光敏剂的用途。Another object of the present invention is to provide the use of the oxime ester compound containing the five-membered aromatic heterocyclic structure of the present invention as a photoinitiator or photosensitizer.
实现本发明上述目的的技术方案可以概括如下:The technical solutions for achieving the above-mentioned objects of the present invention can be summarized as follows:
1.式(I)和(II)的包含不饱和五元杂环结构的肟酯化合物：1. The oxime ester compounds of formula (I) and (II) containing an unsaturated five-membered heterocyclic structure:
其中among them
m为0-8的整数；m is an integer of 0-8;
n和n’相同并且为0或1；n and n’ are the same and are 0 or 1;
m个A
1以及A
2相同或不同，并且相互独立地表示O、S和NR
a，其中R
a为H或C
1-C
6烷基；
m of A 1 and A 2 are the same or different, and each independently represents O, S and NR a, wherein R a is H or C 1 -C 6 alkyl;
R
1、R
2、R
3、R
4相同或不同，并且相互独立地表示氢、卤素、硝基、氨基、氰基、C
1-C
20烷基、C
1-C
20烷氧基、C
1-C
20烷硫基、单C
1-C
12烷基氨基、二C
1-C
12烷基氨基、C
6-C
18芳氧基或C
6-C
18芳硫基，其中前述C
6-C
18芳氧基和C
6-C
18芳硫基基团中的芳基可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、NH
2、氰基、C
1-C
6烷基、C
1-C
6烷氧基和C
1-C
6烷硫基；
R 1 , R 2 , R 3 , and R 4 are the same or different, and independently represent hydrogen, halogen, nitro, amino, cyano, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, mono C 1 -C 12 alkylamino, di C 1 -C 12 alkylamino, C 6 -C 18 aryloxy or C 6 -C 18 arylthio, wherein the aforementioned C 6 The aryl groups in the -C 18 aryloxy and C 6 -C 18 arylthio groups may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, NH 2 , cyano, C 1 -C 6 alkyl, C 1 -C 6 alkoxy and C 1 -C 6 alkylthio;
R
5是氢、卤素、硝基、氰基、C
1-C
20烷基、C
1-C
20烷氧基、C
1-C
20烷硫基、C
6-C
18芳基、C
6-C
18芳基C
1-C
6烷基、C
6-C
18芳基C
1-C
6亚烷基、C
6-C
18芳氧基、C
6-C
18芳硫基、9H-咔唑-9基-C
1-C
6烷基、9H-咔唑-9基-C
1-C
6亚烷基、9H-芴-9基-C
1-C
6烷基或9H-芴-9基-C
1-C
6亚烷基，其中前述C
6-C
18芳基、C
6-C
18芳基C
1-C
6烷基、C
6-C
18芳基C
1-C
6亚烷基、C
6-C
18芳氧基、C
6-C
18芳硫基、9H-咔唑-9基-C
1-C
6烷基、9H-咔唑-9基-C
1-C
6亚烷基、9H-芴-9基-C
1-C
6烷基和9H-芴-9基-C
1-C
6亚烷基基团中的芳基可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、NH
2、氰基、C
1-C
6烷基、C
1-C
6烷氧基、C
1-C
6烷硫基和二苯基氨基，其中二苯基氨基中的苯基各自独立地任选包含一个或多个选自卤素、C
1-C
6烷基、C
1-C
6烷氧基和C
1-C
6烷硫基的取代基取代；
R 5 is hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, C 6 -C 18 aryl, C 6- C 18 aryl C 1 -C 6 alkyl, C 6 -C 18 aryl C 1 -C 6 alkylene, C 6 -C 18 aryloxy, C 6 -C 18 arylthio, 9H-carbazole -9 group-C 1 -C 6 alkyl group, 9H-carbazol-9 group-C 1 -C 6 alkylene group, 9H-fluoren-9 group-C 1 -C 6 alkyl group or 9H-fluoren-9 group -C 1 -C 6 alkylene group, wherein the aforementioned C 6 -C 18 aryl group, C 6 -C 18 aryl group, C 1 -C 6 alkyl group, C 6 -C 18 aryl group, C 1 -C 6 alkylene group , C 6 -C 18 aryloxy group, C 6 -C 18 arylthio group, 9H-carbazol-9 group-C 1 -C 6 alkyl group, 9H-carbazol-9 group-C 1 -C 6 alkylene Group, 9H-fluoren-9 group-C 1 -C 6 alkyl group and 9H-fluoren-9 group-C 1 -C 6 alkylene group in the aryl group can be optionally selected by one or more independently Substitution from the following group: halogen, nitro, hydroxyl, mercapto, NH 2 , cyano, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio and two Phenylamino, wherein each of the phenyl groups in the diphenylamino group independently optionally contains one or more selected from halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy and C 1 -C 6 alkane Substituent substitution of thio group;
R
6与R
6’相同或不同，并且相互独立地表示H、氰基、C
1-C
20烷基、C
3-C
10环烷基、C
4-C
10环烷基烷基、C
4-C
10烷基环烷基、C
6-C
20芳基、C
7-C
20芳烷基或C
7-C
20烷基芳基，其中前述C
1-C
20烷基、C
3-C
10环烷基、C
4-C
10环烷基烷基、C
4-C
10烷基环烷基、C
6-C
20芳基、C
7-C
20芳烷基和C
7-C
20烷基芳基任选地被一个或多个独立地选自下组的基团取代：C
1-C
6烷基、C
1-C
6烷硫基、C
1-C
6烷氧基、卤素、硝基、氨基、单(C
1-C
6烷基)氨基、二(C
1-C
6烷基)氨基和巯基；以及
R 6 and R 6 ′ are the same or different, and independently represent H, cyano, C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkyl alkyl, C 4 -C 10 alkyl cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl or C 7 -C 20 alkyl aryl, wherein the aforementioned C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkyl alkyl, C 4 -C 10 alkyl cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkane Alkylaryl is optionally substituted with one or more groups independently selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 alkylthio, C 1 -C 6 alkoxy, halogen, Nitro, amino, mono(C 1 -C 6 alkyl)amino, di(C 1 -C 6 alkyl)amino, and mercapto; and
R
7与R
7’相同或不同，并且相互独立地表示C
1-C
20烷基、C
3-C
10环烷基、C
4-C
10环烷基烷基、C
4-C
10烷基环烷基、C
6-C
20芳基、C
7-C
20芳烷基或C
7-C
20烷基芳基，其中前述C
1-C
20烷基、C
3-C
10环烷基、C
4-C
10环烷基烷基、C
4-C
10烷基环烷基、C
6-C
20芳基、C
7-C
20芳烷基和C
7-C
20烷基芳基任选地被一个或多个独立地选自下组的基团取代：C
1-C
6烷基、C
1-C
6烷硫基、C
1-C
6烷氧基、卤素、硝基、氨基、单(C
1-C
6烷基)氨基、二(C
1-C
6烷基)氨基和巯基。
R 7 and R 7 'are the same or different, and independently represent C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkyl alkyl, C 4 -C 10 alkyl Cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl or C 7 -C 20 alkyl aryl, wherein the aforementioned C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkylalkyl, C 4 -C 10 alkylcycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkyl aryl are optional Ground is substituted by one or more groups independently selected from the following group: C 1 -C 6 alkyl, C 1 -C 6 alkylthio, C 1 -C 6 alkoxy, halogen, nitro, amino, Mono(C 1 -C 6 alkyl)amino, di(C 1 -C 6 alkyl)amino and mercapto groups.
2.根据第1项的化合物，其中m为0-4的整数，优选为0、1或2。2. The compound according to item 1, wherein m is an integer of 0-4, preferably 0, 1, or 2.
3.根据第1或2项的化合物，其中R
a为H或C
1-C
4烷基；优选的是，m个A
1以及A
2彼此相同，并且表示O、S或NR
a，其中R
a为H或C
1-C
4烷基，优选H、甲基或乙基。
3. A compound of Item 1 or 2, wherein R a is H or C 1 -C 4 alkyl; preferably is, m of A 1 and A 2 identical to each other, and represent O, S or NR a, wherein R a is H or C 1 -C 4 alkyl, preferably H, methyl or ethyl.
4.根据第1-3项中任一项的化合物，其中4. The compound according to any one of items 1-3, wherein
R
1、R
2、R
3、R
4相同或不同，并且相互独立地表示氢、卤素、硝基、氨基、氰基、C
1-C
6烷基、C
1-C
6烷氧基、C
1-C
6烷硫基、单C
1-C
6烷基氨基、二C
1-C
6烷基氨基、C
6-C
10芳氧基 或C
6-C
10芳硫基，其中前述C
6-C
10芳氧基和C
6-C
10芳硫基基团中的芳基可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、NH
2、氰基、C
1-C
4烷基、C
1-C
4烷氧基和C
1-C
4烷硫基；
R 1 , R 2 , R 3 , R 4 are the same or different, and independently represent hydrogen, halogen, nitro, amino, cyano, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, mono C 1 -C 6 alkylamino, di C 1 -C 6 alkylamino, C 6 -C 10 aryloxy or C 6 -C 10 arylthio, wherein the aforementioned C 6 The aryl groups in the -C 10 aryloxy and C 6 -C 10 arylthio groups may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, NH 2 , cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1 -C 4 alkylthio;
优选的是，R
1、R
2、R
3、R
4相同或不同，并且相互独立地表示氢、卤素、硝基、氨基、氰基、C
1-C
4烷基、C
1-C
4烷氧基、C
1-C
4烷硫基、单C
1-C
4烷基氨基、二C
1-C
4烷基氨基、苯氧基或苯硫基，其中前述苯氧基和苯硫基基团中的苯基可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、NH
2、氰基、C
1-C
4烷基、C
1-C
4烷氧基和C
1-C
4烷硫基。
Preferably, R 1 , R 2 , R 3 , and R 4 are the same or different, and independently represent hydrogen, halogen, nitro, amino, cyano, C 1 -C 4 alkyl, C 1 -C 4 alkane Oxy, C 1 -C 4 alkylthio, mono C 1 -C 4 alkylamino, di C 1 -C 4 alkylamino, phenoxy or phenylthio, wherein the aforementioned phenoxy and phenylthio The phenyl group in the group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, NH 2 , cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1 -C 4 alkylthio.
5.根据第1-4项中任一项的化合物，其中5. The compound according to any one of items 1 to 4, wherein
R
5表示氢、卤素、硝基、氰基、C
1-C
6烷基、C
1-C
6烷氧基、C
1-C
6烷硫基、C
6-C
13芳基、C
6-C
13芳基C
1-C
4烷基、C
6-C
13芳基C
1-C
4亚烷基、C
6-C
13芳氧基、C
6-C
13芳硫基、9H-咔唑-9基-C
1-C
4烷基、9H-咔唑-9基-C
1-C
4亚烷基、9H-芴-9基-C
1-C
4烷基或9H-芴-9基-C
1-C
4亚烷基，其中前述C
6-C
13芳基、C
6-C
13芳基C
1-C
4烷基、C
6-C
13芳基C
1-C
4亚烷基、C
6-C
13芳氧基、C
6-C
13芳硫基、9H-咔唑-9基-C
1-C
4烷基、9H-咔唑-9基-C
1-C
4亚烷基、9H-芴-9基-C
1-C
4烷基和9H-芴-9基-C
1-C
4亚烷基基团中的芳基可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、NH
2、氰基、C
1-C
4烷基、C
1-C
4烷氧基、C
1-C
4烷硫基和二苯基氨基，其中二苯基氨基中的苯基各自独立地任选包含一个或多个选自卤素、C
1-C
4烷基、C
1-C
4烷氧基和C
1-C
4烷硫基的取代基取代；
R 5 represents hydrogen, halogen, nitro, cyano, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 6 -C 13 aryl, C 6- C 13 aryl, C 1 -C 4 alkyl, C 6 -C 13 aryl, C 1 -C 4 alkylene, C 6 -C 13 aryloxy, C 6 -C 13 arylthio, 9H-carbazole -9 group-C 1 -C 4 alkyl group, 9H-carbazol-9 group-C 1 -C 4 alkylene group, 9H-fluoren-9 group-C 1 -C 4 alkyl group or 9H-fluoren-9 group -C 1 -C 4 alkylene, wherein the aforementioned C 6 -C 13 aryl, C 6 -C 13 aryl C 1 -C 4 alkyl, C 6 -C 13 aryl C 1 -C 4 alkylene , C 6 -C 13 aryloxy group, C 6 -C 13 arylthio group, 9H-carbazol-9 group-C 1 -C 4 alkyl group, 9H-carbazol-9 group-C 1 -C 4 alkylene Group, 9H-fluoren-9 group-C 1 -C 4 alkyl group and 9H-fluoren-9 group-C 1 -C 4 alkylene group in the aryl group can be optionally selected by one or more independently Substitution from the following group: halogen, nitro, hydroxyl, mercapto, NH 2 , cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio and two Phenylamino, wherein each of the phenyl groups in the diphenylamino group independently optionally contains one or more selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1 -C 4 alkane Substituent substitution of thio group;
优选的是，R
5表示氢、卤素、硝基、氰基、C
1-C
4烷基、C
1-C
4烷氧基、C
1-C
4烷硫基、苯基、C
6-C
13芳基C
1-C
2烷基、C
6-C
13芳基C
1-C
2亚烷基、C
6-C
10芳氧基、C
6-C
10芳硫基、9H-咔唑-9基-C
1-C
2烷基、9H-咔唑-9基-C
1-C
2亚烷基、9H-芴-9基-C
1-C
2烷基或9H-芴-9基-C
1-C
2亚烷基，其中前述苯基、C
6-C
13芳基C
1-C
2烷基、C
6-C
13芳基C
1-C
2亚烷基、C
6-C
10芳氧基、C
6-C
10芳硫基、9H-咔唑-9基-C
1-C
2烷基、9H-咔唑-9基-C
1-C
2亚烷基、9H-芴-9基-C
1-C
2烷基和9H-芴-9基-C
1-C
2亚烷基基团中的芳基可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、NH
2、氰基、C
1-C
4烷基、C
1-C
4烷氧基、C
1-C
4烷硫基和二苯基氨基，其中二苯基氨基中的苯基各自独立地任选包含一个或多个选自卤素、C
1-C
4烷基、C
1-C
4烷氧基和C
1-C
4烷硫基的取代基。
Preferably, R 5 represents hydrogen, halogen, nitro, cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, phenyl, C 6 -C 13 aryl C 1 -C 2 alkyl, C 6 -C 13 aryl C 1 -C 2 alkylene, C 6 -C 10 aryloxy, C 6 -C 10 arylthio, 9H-carbazole- 9 group-C 1 -C 2 alkyl group, 9H-carbazol-9 group-C 1 -C 2 alkylene group, 9H-fluoren-9 group-C 1 -C 2 alkyl group or 9H-fluoren-9 group- C 1 -C 2 alkylene group, wherein the aforementioned phenyl group, C 6 -C 13 aryl group C 1 -C 2 alkyl group, C 6 -C 13 aryl group C 1 -C 2 alkylene group, C 6 -C 10 Aryloxy group, C 6 -C 10 arylthio group, 9H-carbazol-9 group-C 1 -C 2 alkyl group, 9H-carbazol-9 group-C 1 -C 2 alkylene group, 9H-fluorene- The aryl group in the 9 group-C 1 -C 2 alkyl group and the 9H-fluoren-9 group-C 1 -C 2 alkylene group may optionally be one or more groups independently selected from the following group Substitution: halogen, nitro, hydroxyl, mercapto, NH 2 , cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio and diphenylamino, two of which The phenyl groups in the phenylamino group each independently optionally include one or more substituents selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, and C 1 -C 4 alkylthio.
6.根据第1-5项中任一项的方法，其中6. The method according to any one of items 1-5, wherein
R
6与R
6’相同或不同，并且相互独立地表示H、氰基、C
1-C
6烷基、C
3-C
8环烷基、C
4-C
8环烷基烷基、C
4-C
8烷基环烷基、C
6-C
10芳基、C
7-C
11芳烷基或C
7-C
11烷基芳基，其中前述C
1-C
6烷基、C
3-C
8环烷基、C
4-C
8环烷基烷基、C
4-C
8烷基环烷基、C
6-C
10芳基、C
7-C
11芳烷基和C
7-C
11烷基芳基任选地被一个或多个独立地选自下组的基团取代：C
1-C
4烷基、C
1-C
4烷硫基、C
1-C
4烷氧基、卤素、硝基、氨基、单(C
1-C
4烷基)氨基、二(C
1-C
4烷基)氨基和巯基；
R 6 and R 6 ′ are the same or different, and independently represent H, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkyl alkyl, C 4 -C 8 alkyl cycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl or C 7 -C 11 alkyl aryl, wherein the aforementioned C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl, and C 7 -C 11 alkane Alkylaryl is optionally substituted with one or more groups independently selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkylthio, C 1 -C 4 alkoxy, halogen, Nitro, amino, mono(C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkyl)amino, and mercapto;
优选的是，R
6与R
6’相同或不同，并且相互独立地表示H、氰基、C
1-C
6烷基、C
3-C
6环烷基或C
3-C
6环烷基C
1-C
2烷基，其中前述C
1-C
6烷基、C
3-C
6环烷基和C
3-C
6环烷基C
1-C
2烷基任选地被一个或多个独立地选自下组的基团取代：C
1-C
4烷基、C
1-C
4烷硫基、C
1-C
4烷氧 基、卤素、硝基、氨基、单(C
1-C
4烷基)氨基、二(C
1-C
4烷基)氨基和巯基。
Preferably, R 6 and R 6 ′ are the same or different and independently represent H, cyano, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl or C 3 -C 6 cycloalkyl C 1 -C 2 alkyl, wherein the aforementioned C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl and C 3 -C 6 cycloalkyl C 1 -C 2 alkyl are optionally separated by one or more Substitution by a group selected from the following group: C 1 -C 4 alkyl, C 1 -C 4 alkylthio, C 1 -C 4 alkoxy, halogen, nitro, amino, mono (C 1 -C 4 Alkyl)amino, di(C 1 -C 4 alkyl)amino and mercapto.
7.根据第1-6项中任一项的化合物，其中7. The compound according to any one of items 1-6, wherein
R
7与R
7’相同或不同，并且相互独立地表示C
1-C
6烷基、C
3-C
8环烷基、C
4-C
8环烷基烷基、C
4-C
8烷基环烷基、C
6-C
10芳基、C
7-C
11芳烷基或C
7-C
11烷基芳基，其中前述C
1-C
6烷基、C
3-C
8环烷基、C
4-C
8环烷基烷基、C
4-C
8烷基环烷基、C
6-C
10芳基、C
7-C
11芳烷基和C
7-C
11烷基芳基任选地被一个或多个独立地选自下组的基团取代：C
1-C
4烷基、C
1-C
4烷硫基、C
1-C
4烷氧基、卤素、硝基、氨基、单(C
1-C
4烷基)氨基、二(C
1-C
4烷基)氨基和巯基；
R 7 and R 7 'are the same or different, and independently represent C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkyl alkyl, C 4 -C 8 alkyl Cycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl or C 7 -C 11 alkyl aryl, wherein the aforementioned C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl and C 7 -C 11 alkyl aryl optionally Ground is substituted by one or more groups independently selected from the following group: C 1 -C 4 alkyl, C 1 -C 4 alkylthio, C 1 -C 4 alkoxy, halogen, nitro, amino, Mono(C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkyl)amino and mercapto;
优选的是，R
7与R
7’相同或不同，并且相互独立地表示C
1-C
4烷基或苯基，其中前述C
1-C
4烷基和苯基任选地被一个或多个独立地选自下组的基团取代：C
1-C
4烷基、C
1-C
4烷硫基、C
1-C
4烷氧基、卤素、硝基、氨基、单(C
1-C
4烷基)氨基、二(C
1-C
4烷基)氨基和巯基。
Preferably, R 7 and R 7 ′ are the same or different, and independently represent C 1 -C 4 alkyl or phenyl, wherein the aforementioned C 1 -C 4 alkyl and phenyl are optionally substituted by one or more Substitution groups independently selected from the following group: C 1 -C 4 alkyl, C 1 -C 4 alkylthio, C 1 -C 4 alkoxy, halogen, nitro, amino, mono (C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkyl)amino and mercapto.
8.根据第1项的化合物，其中式(I)和(II)化合物选自下文的化合物1-65。8. The compound according to item 1, wherein the compounds of formula (I) and (II) are selected from compounds 1-65 below.
9.一种制备如第1-8项中任一项所要求的化合物的方法，包括以下步骤：9. A method for preparing the compound as claimed in any one of items 1-8, comprising the following steps:
(1)肟化反应：当n和n’为0时，使式(III)和(IV)化合物各自与羟胺和/或盐酸羟胺进行肟化反应，分别得到式(IIIa)和(IVa)化合物，(1) Oximation reaction: when n and n'are 0, the compounds of formula (III) and (IV) are oximated with hydroxylamine and/or hydroxylamine hydrochloride to obtain compounds of formula (IIIa) and (IVa) respectively ,
当n和n’为1时，使式(III)和(IV)化合物各自与选自亚硝酸、亚硝酸盐和亚硝酸烷基酯中的试剂进行肟化反应，分别得到式(IIIb)和(IVb)化合物，When n and n'are 1, the compounds of formula (III) and (IV) are each reacted with a reagent selected from the group consisting of nitrous acid, nitrite and alkyl nitrite to obtain formula (IIIb) and (IVb) compound,
其中式(III)、(IV)、(IIIa)、(IVa)、(IIIb)和(IVb)中的m、A
1、A
2、R
1-R
4和R
6，式(III)、(IIIa)和(IIIb)中的R
5以及式(IV)、(IVa)和(IVb)中的R
6’如第1-8项中任一项所定义；以及
Where m, A 1 , A 2 , R 1 -R 4 and R 6 in formulas (III), (IV), (IIIa), (IVa), (IIIb) and (IVb), formulas (III), ( R 5 in IIIa) and (IIIb) and R 6 ′ in formulas (IV), (IVa) and (IVb) are as defined in any one of items 1-8; and
(2)将式(IIIa)和(IIIb)酯化，将式(IVa)和(IVb)化合物酯化，分别得到式(I)和(II)化合物。(2) Esterification of formula (IIIa) and (IIIb), and esterification of compounds of formula (IVa) and (IVb) to obtain compounds of formula (I) and (II), respectively.
10.根据第9项的方法，其中10. The method according to item 9, where
当n和n’为0时：肟化反应在乙酸钠、吡啶、哌啶、三乙胺、四甲基氢氧化铵或其混合物存在下进行；和/或，肟化反应在乙醇或含水的乙醇作为溶剂存在下进行；和/或，肟化反应的温度为60-120℃；和/或，肟化反应时间为0.1-20小时，优选0.5-10小时；和/或，式(III)和(IV)化合物各自与选自羟胺和/或盐酸羟胺的化合物的摩尔比为1:1.5-1.5:1，优选为1:1.2-1.2:1；When n and n'are 0: the oximation reaction is carried out in the presence of sodium acetate, pyridine, piperidine, triethylamine, tetramethylammonium hydroxide or a mixture thereof; and/or, the oximation reaction is carried out in ethanol or water It is carried out in the presence of ethanol as a solvent; and/or, the temperature of the oximation reaction is 60-120°C; and/or, the oximation reaction time is 0.1-20 hours, preferably 0.5-10 hours; and/or, formula (III) The molar ratio of each of and (IV) compound to a compound selected from hydroxylamine and/or hydroxylamine hydrochloride is 1:1.5-1.5:1, preferably 1:1.2-1.2:1;
当n和n’为1时，肟化反应在20-40％的浓盐酸存在下进行；和/或，肟化反应在四氢呋喃、乙醇或含水的乙醇作为溶剂存在下进行；和/或，肟化反应的温度为-30至20℃，优选5-20℃；和/或，肟化反应时间为0.1-20小时，优选0.5-10小时；和/或，式(III)和(IV)化合物各自与选自亚硝酸、亚硝酸盐和/或亚硝酸烷基酯的化合物的摩尔比为1:1.5-1.5:1，优选为1:1.2-1.2:1。When n and n'are 1, the oximation reaction is carried out in the presence of 20-40% concentrated hydrochloric acid; and/or, the oximation reaction is carried out in the presence of tetrahydrofuran, ethanol or water-containing ethanol as a solvent; and/or, oxime The temperature of the reaction is -30 to 20°C, preferably 5-20°C; and/or, the oximation reaction time is 0.1-20 hours, preferably 0.5-10 hours; and/or, compounds of formula (III) and (IV) The molar ratio of each to the compound selected from nitrous acid, nitrite and/or alkyl nitrite is 1:1.5-1.5:1, preferably 1:1.2-1.2:1.
11.根据第9或10项的方法，其中亚硝酸烷基酯为亚硝酸C
1-C
6烷基酯，例如亚硝酸甲酯、亚硝酸乙酯、亚硝酸异丙酯、亚硝酸丁酯、亚硝酸异戊酯；和/或，步骤(2)的酯化采用选自下式(Va)、IVb)和(Vc)化合物的酯化试剂进行：
11. The method according to item 9 or 10, wherein the alkyl nitrite is a C 1 -C 6 alkyl nitrite, such as methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite , Isoamyl nitrite; and/or, the esterification of step (2) is carried out using an esterification reagent selected from the following formulas (Va), IVb) and (Vc):
其中X为卤素，尤其是氯，和R
7如第项1-8中任一项的R
7和R
7’所定义。
Wherein X is halogen, especially chlorine, and R 7 is as defined by R 7 and R 7 ′ in any one of items 1-8.
12.根据第9-11项中任一项的方法，其中酯化反应在选自下组的一种或多种催化剂存在下进行：硫酸、高氯酸、氯化锌、三氯化铁、吡啶、对甲基苯磺酸、氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、叔丁醇钠、乙醇钠、氢化钠、氢化钾、氢化钙和叔胺，例如三烷基胺，如三甲基胺和三乙胺。12. The method according to any one of items 9-11, wherein the esterification reaction is carried out in the presence of one or more catalysts selected from the group consisting of sulfuric acid, perchloric acid, zinc chloride, ferric chloride, Pyridine, p-toluenesulfonic acid, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium tert-butoxide, sodium ethoxide, sodium hydride, potassium hydride, calcium hydride and tertiary amines, such as trialkylamines, Such as trimethylamine and triethylamine.
13.根据第9-12项中任一项的方法，其中酯化反应在选自四氢呋喃、苯、甲苯、N，N-二甲基甲酰胺、二氯甲烷和丙酮的溶剂中进行；和/或，式(IIIa)、(IIIb)、(IVa)和(IVb)化合物各自与选自(Va)、(Vb)和(Vc)化合物的酯化试剂的摩尔比为1:1.5-1.5:1，优选为1:1.2-1.2:1。13. The method according to any one of items 9-12, wherein the esterification reaction is carried out in a solvent selected from the group consisting of tetrahydrofuran, benzene, toluene, N,N-dimethylformamide, dichloromethane and acetone; and/ Or, the molar ratio of each compound of formula (IIIa), (IIIb), (IVa) and (IVb) to the esterification agent selected from the group consisting of (Va), (Vb) and (Vc) compounds is 1:1.5-1.5:1 , Preferably 1:1.2-1.2:1.
14.如第1-8项中任一项所要求的式(I)和(II)化合物各自作为光引发剂的用途，尤其是在UV-LED光固化体系中作为光引发剂的用途，特别是在辐射波长为350-450nm、尤其365-420nm的光固化体系中作为光引发剂的用途。14. The use of each of the compounds of formula (I) and (II) as required by any one of items 1-8 as photoinitiators, especially the use as photoinitiators in UV-LED light curing systems, especially It is used as a photoinitiator in a light curing system with a radiation wavelength of 350-450nm, especially 365-420nm.
图1是乌格拉(Ugra)晒版测试条的示意图，其中Figure 1 is a schematic diagram of Ugra printing test strips, where
1——连续密度梯尺段，1——Continuous density ladder section,
2——阴阳微米等线同心圆线圈段，2——Yin-Yang micron contour concentric circle segment,
3——全阶调网点段，3——Full-level adjustment network point segment,
4——重影控制段，和4-Ghost control segment, and
5——高光、暗调控制段。5——High light and dark tone control section.
图2是化合物1的紫外吸收光谱图。Figure 2 is the UV absorption spectrum of Compound 1.
图3是化合物1与市售光引发剂OXE-02在TPGDA中的差热分析结果谱图。Fig. 3 is a differential thermal analysis result spectrum of compound 1 and the commercially available photoinitiator OXE-02 in TPGDA.
图4是在365nmLED光源下TPGDA在不同浓度光引发剂下的转化率与辐照时间关系图谱。Figure 4 is a graph showing the relationship between the conversion rate of TPGDA under different concentrations of photoinitiator and the irradiation time under a 365nm LED light source.
图5是在395nmLED光源下TPGDA在不同浓度光引发剂下的转化率与辐照时间关系图谱。Figure 5 is a graph showing the relationship between the conversion rate of TPGDA under different concentrations of photoinitiator and the irradiation time under a 395nm LED light source.
图6是在405nmLED光源下TPGDA在不同浓度光引发剂下的转化率与辐照时间关系图谱。Figure 6 is a graph showing the relationship between the conversion rate of TPGDA under different concentrations of photoinitiator and the irradiation time under a 405nm LED light source.
根据本发明的第一个方面，提供了式(I)和(II)的含有不饱和五元芳杂环结构的肟酯类化合物：According to the first aspect of the present invention, an oxime ester compound containing an unsaturated five-membered aromatic heterocyclic structure of formula (I) and (II) is provided:
其中：among them:
m为0-8的整数；m is an integer of 0-8;
n和n’相同并且为0或1；n and n’ are the same and are 0 or 1;
m个A
1以及A
2相同或不同，并且相互独立地表示O、S和NR
a，其中R
a为H或C
1-C
6烷基；
m of A 1 and A 2 are the same or different, and each independently represents O, S and NR a, wherein R a is H or C 1 -C 6 alkyl;
R
1、R
2、R
3、R
4相同或不同，并且相互独立地表示氢、卤素、硝基、氨基、氰基、C
1-C
20烷基、C
1-C
20烷氧基、C
1-C
20烷硫基、单C
1-C
12烷基氨基、二C
1-C
12烷基氨基、C
6-C
18芳氧基或C
6-C
18芳硫基，其中前述C
6-C
18芳氧基和C
6-C
18芳硫基基团中的芳基可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、NH
2、氰基、C
1-C
6烷基、C
1-C
6烷氧基和C
1-C
6烷硫基；
R 1 , R 2 , R 3 , and R 4 are the same or different, and independently represent hydrogen, halogen, nitro, amino, cyano, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, mono C 1 -C 12 alkylamino, di C 1 -C 12 alkylamino, C 6 -C 18 aryloxy or C 6 -C 18 arylthio, wherein the aforementioned C 6 The aryl groups in the -C 18 aryloxy and C 6 -C 18 arylthio groups may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, NH 2 , cyano, C 1 -C 6 alkyl, C 1 -C 6 alkoxy and C 1 -C 6 alkylthio;
R
5是氢、卤素、硝基、氰基、C
1-C
20烷基、C
1-C
20烷氧基、C
1-C
20烷硫基、C
6-C
18芳基、C
6-C
18芳基C
1-C
6烷基、C
6-C
18芳基C
1-C
6亚烷基、C
6-C
18芳氧基、C
6-C
18芳硫基、9H-咔唑-9基-C
1-C
6烷基、9H-咔唑-9基-C
1-C
6亚烷基、9H-芴-9基-C
1-C
6烷基或9H-芴-9基-C
1-C
6亚烷基，其中前述C
6-C
18芳基、C
6-C
18芳基C
1-C
6烷基、C
6-C
18芳基C
1-C
6亚烷基、C
6-C
18芳氧基、C
6-C
18芳硫基、9H-咔唑-9基-C
1-C
6烷基、9H-咔唑-9基-C
1-C
6亚烷基、9H-芴-9基-C
1-C
6烷基和9H-芴-9基-C
1-C
6亚烷基基团中的芳基可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、NH
2、氰基、C
1-C
6烷基、C
1-C
6烷氧基、C
1-C
6烷硫基和二苯基氨 基，其中二苯基氨基中的苯基各自独立地任选包含一个或多个选自卤素、C
1-C
6烷基、C
1-C
6烷氧基和C
1-C
6烷硫基的取代基；
R 5 is hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, C 6 -C 18 aryl, C 6- C 18 aryl C 1 -C 6 alkyl, C 6 -C 18 aryl C 1 -C 6 alkylene, C 6 -C 18 aryloxy, C 6 -C 18 arylthio, 9H-carbazole -9 group-C 1 -C 6 alkyl group, 9H-carbazol-9 group-C 1 -C 6 alkylene group, 9H-fluoren-9 group-C 1 -C 6 alkyl group or 9H-fluoren-9 group -C 1 -C 6 alkylene group, wherein the aforementioned C 6 -C 18 aryl group, C 6 -C 18 aryl group, C 1 -C 6 alkyl group, C 6 -C 18 aryl group, C 1 -C 6 alkylene group , C 6 -C 18 aryloxy group, C 6 -C 18 arylthio group, 9H-carbazol-9 group-C 1 -C 6 alkyl group, 9H-carbazol-9 group-C 1 -C 6 alkylene Group, 9H-fluoren-9 group-C 1 -C 6 alkyl group and 9H-fluoren-9 group-C 1 -C 6 alkylene group in the aryl group can be optionally selected by one or more independently Substitution from the following group: halogen, nitro, hydroxyl, mercapto, NH 2 , cyano, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio and two Phenylamino, wherein each of the phenyl groups in the diphenylamino group independently optionally contains one or more selected from halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy and C 1 -C 6 alkane Substituents of thio groups;
R
6与R
6’相同或不同，并且相互独立地表示H、氰基、C
1-C
20烷基、C
3-C
10环烷基、C
4-C
10环烷基烷基、C
4-C
10烷基环烷基、C
6-C
20芳基、C
7-C
20芳烷基或C
7-C
20烷基芳基，其中前述C
1-C
20烷基、C
3-C
10环烷基、C
4-C
10环烷基烷基、C
4-C
10烷基环烷基、C
6-C
20芳基、C
7-C
20芳烷基和C
7-C
20烷基芳基任选地被一个或多个独立地选自下组的基团取代：C
1-C
6烷基、C
1-C
6烷硫基、C
1-C
6烷氧基、卤素、硝基、氨基、单(C
1-C
6烷基)氨基、二(C
1-C
6烷基)氨基和巯基；以及
R 6 and R 6 ′ are the same or different, and independently represent H, cyano, C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkyl alkyl, C 4 -C 10 alkyl cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl or C 7 -C 20 alkyl aryl, wherein the aforementioned C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkyl alkyl, C 4 -C 10 alkyl cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkane Alkylaryl is optionally substituted with one or more groups independently selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 alkylthio, C 1 -C 6 alkoxy, halogen, Nitro, amino, mono(C 1 -C 6 alkyl)amino, di(C 1 -C 6 alkyl)amino, and mercapto; and
R
7与R
7’相同或不同，并且相互独立地表示C
1-C
20烷基、C
3-C
10环烷基、C
4-C
10环烷基烷基、C
4-C
10烷基环烷基、C
6-C
20芳基、C
7-C
20芳烷基或C
7-C
20烷基芳基，其中前述C
1-C
20烷基、C
3-C
10环烷基、C
4-C
10环烷基烷基、C
4-C
10烷基环烷基、C
6-C
20芳基、C
7-C
20芳烷基和C
7-C
20烷基芳基任选地被一个或多个独立地选自下组的基团取代：C
1-C
6烷基、C
1-C
6烷硫基、C
1-C
6烷氧基、卤素、硝基、氨基、单(C
1-C
6烷基)氨基、二(C
1-C
6烷基)氨基和巯基。
R 7 and R 7 'are the same or different, and independently represent C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkyl alkyl, C 4 -C 10 alkyl Cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl or C 7 -C 20 alkyl aryl, wherein the aforementioned C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkylalkyl, C 4 -C 10 alkylcycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkyl aryl are optional Ground is substituted by one or more groups independently selected from the following group: C 1 -C 6 alkyl, C 1 -C 6 alkylthio, C 1 -C 6 alkoxy, halogen, nitro, amino, Mono(C 1 -C 6 alkyl)amino, di(C 1 -C 6 alkyl)amino and mercapto groups.
式(I)和(II)化合物中既包含至少一个五元芳族杂环结构部分，又包含肟酯类结构部分。这些化合物在350-450nm范围内具有很强的光吸收，吸收光能后能够迅速发生能量转移，持续引发聚合，在感光性及图案完整性方面具有明显优势，非常适合于UV-LED光源且其安全无毒可用于食品包装等领域。此外，式(I)和(II)化合物还具有良好的热稳定性。The compounds of formula (I) and (II) contain both at least one five-membered aromatic heterocyclic structure part and an oxime ester structure part. These compounds have strong light absorption in the 350-450nm range. After absorbing light energy, they can quickly transfer energy and continue to initiate polymerization. They have obvious advantages in photosensitivity and pattern integrity, and are very suitable for UV-LED light sources. Safe and non-toxic can be used in food packaging and other fields. In addition, the compounds of formula (I) and (II) also have good thermal stability.
在本发明中，前缀“C
n-C
m”在每种情况下表示该基团中包含的碳原子数为n-m个。
In the present invention, the prefix "C n -C m "in each case indicates that the number of carbon atoms contained in the group is nm.
“卤素”是指氟、氯、溴和碘。在本发明中，优选的是，卤素包括F、Cl或其组合。"Halogen" refers to fluorine, chlorine, bromine and iodine. In the present invention, it is preferable that the halogen includes F, Cl or a combination thereof.
本文所用的术语“C
n-C
m烷基”是指具有n-m个，例如1-20个，优选1-12个，更优选1-8个，特别优选1-6个，尤其优选1-4个碳原子的支化或未支化饱和烃基，例如甲基、乙基、丙基、1-甲基乙基、丁基、1-甲基丙基、2-甲基丙基、1，1-二甲基乙基、戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、2,2-二甲基丙基、1-乙基丙基、己基、1,1-二甲基丙基、1,2-二甲基丙基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1,1-二甲基丁基、1,2-二甲基丁基、1,3-二甲基丁基、2,2-二甲基丁基、2,3-二甲基丁基、3,3-二甲基丁基、1-乙基丁基、2-乙基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基-1-甲基丙基、1-乙基-2-甲基丙基、庚基、辛基、2-乙基己基、壬基、癸基、十一烷基、十二烷基及其异构体。
The term "C n -C m alkyl group" as used herein means having nm number, for example 1-20, preferably 1-12, more preferably 1-8, particularly preferably 1-6, especially preferably 1-4 Branched or unbranched saturated hydrocarbon groups with three carbon atoms, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1 -Dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl -1-methylpropyl, 1-ethyl-2-methylpropyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl and isopropyl Construct.
本文所用术语“C
3-C
m环烷基”是指具有3-m个，例如3-20个，优选3-8个，更优选5-6个环碳原子的饱和脂环族单环基团，例如环丙基、环丁基、环戊基、环己基、环庚基、环辛基和环癸基。
The term "C 3 -C m cycloalkyl" as used herein refers to a saturated alicyclic monocyclic group having 3 to m, such as 3 to 20, preferably 3 to 8, and more preferably 5 to 6 carbon atoms. Groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.
术语“C
4-C
m环烷基烷基”表示被环烷基取代的烷基并且总共含有4-m个碳原子，例如4-20个碳原子，优选4-10个碳原子，更优选4-6个碳原子，其中烷基和环烷基适用本文所定义，例如环丙基甲基、环丙基乙基、环丙基丙基、环丙基丁基、环丁基甲基、环丁基乙基、环丁基丙基、环丁基丁基、环戊基甲基、环戊基乙基、环戊基丙基、环戊基丁基、环己基甲基、环己基乙基、环己基丙基、环己基丁基等。
The term "C 4 -C m cycloalkylalkyl" means an alkyl group substituted by a cycloalkyl group and contains a total of 4 to m carbon atoms, for example 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms, more preferably 4-6 carbon atoms, of which alkyl and cycloalkyl apply as defined herein, such as cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopropylbutyl, cyclobutylmethyl, cyclobutyl Cycloethyl, cyclobutylpropyl, cyclobutylbutyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, Cyclohexylpropyl, cyclohexylbutyl, etc.
术语“C
4-C
10烷基环烷基”表示被烷基取代的环烷基并且总共含有4-m个碳原子，例如4-10 个碳原子，优选4-8个碳原子，更优选4-6个碳原子，其中烷基和环烷基适用本文所定义，例如甲基环丙基、乙基环丙基、丙基环丙基、丁基环丙基、甲基环丁基、乙基环丁基、丙基环丁基、丁基环丁基、甲基环戊基、乙基环戊基、丙基环戊基、丁基环戊基、甲基环己基、乙基环己基、丙基环己基、丁基环己基等。
The term "C 4 -C 10 alkylcycloalkyl" means a cycloalkyl substituted by an alkyl group and contains a total of 4 to m carbon atoms, for example 4 to 10 carbon atoms, preferably 4 to 8 carbon atoms, more preferably 4-6 carbon atoms, of which alkyl and cycloalkyl apply as defined herein, such as methylcyclopropyl, ethylcyclopropyl, propylcyclopropyl, butylcyclopropyl, methylcyclobutyl, ethyl Cyclobutyl, propylcyclobutyl, butylcyclobutyl, methylcyclopentyl, ethylcyclopentyl, propylcyclopentyl, butylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl , Butylcyclohexyl, etc.
本文所用术语“C
6-C
m芳基”是指含有6-m个碳原子，例如6-18或6-15个，优选6-10个碳原子的单环、双环、三环或更多环芳族烃基。作为C
6-C
m芳基的实例，可提及苯基、甲苯基、乙苯基、丙苯基、丁苯基、二甲苯基、甲基乙基苯基、二乙基苯基、甲基.丙基苯基、萘基、咔唑基、芴基等；优选苯基或萘基，尤其是苯基。
As used herein, the term "C 6 -C m aryl" refers to a monocyclic, bicyclic, tricyclic or more containing 6-m carbon atoms, such as 6-18 or 6-15, preferably 6-10 carbon atoms Ring aromatic hydrocarbon group. As examples of C 6 -C m aryl groups, mention may be made of phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, xylyl, methylethylphenyl, diethylphenyl, methyl Group. Propylphenyl, naphthyl, carbazolyl, fluorenyl, etc.; preferably phenyl or naphthyl, especially phenyl.
术语“C
7-C
20芳烷基”表示被芳基取代的烷基并且总共含有7-20个碳原子，例如7-15个或7-12个，优选7-10个碳原子，更优选7-8个碳原子，其中烷基和芳基适用本文所定义，例如苯甲基、苯乙基、萘甲基、萘乙基、芴甲基、芴乙基等。
The term "C 7 -C 20 aralkyl" means an alkyl group substituted by an aryl group and contains 7-20 carbon atoms in total, for example 7-15 or 7-12, preferably 7-10 carbon atoms, more preferably 7-8 carbon atoms, of which alkyl and aryl are defined herein, such as benzyl, phenethyl, naphthylmethyl, naphthylethyl, fluorenylmethyl, fluorenylethyl and the like.
术语“C
7-C
20烷基芳基”表示被烷基取代的芳基并且总共含有7-20个碳原子，例如7-12个，优选7-10个碳原子，更优选7-8个碳原子，其中烷基和芳基适用本文所定义，例如甲基苯基、二甲基苯基、三甲基苯基、乙基苯基、二乙基苯基、三乙基苯基、甲基萘基、乙基萘基等。
The term "C 7 -C 20 alkylaryl" means an aryl group substituted by an alkyl group and contains a total of 7-20 carbon atoms, for example 7-12, preferably 7-10 carbon atoms, more preferably 7-8 Carbon atoms, in which alkyl and aryl groups are defined herein, such as methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, methyl Naphthyl, ethylnaphthyl, etc.
术语“C
n-C
m烷氧基”和“C
n-C
m烷硫基”是指在C
n-C
m烷基对应的开链C
n-C
m烷烃的任何碳原子上键合有一个氧原子或一个硫原子作为连接基团的C
n-C
m烷基，例如C
1-C
20烷氧(或硫)基，优选C
1-C
12烷氧(或硫)基，更优选C
1-C
8烷氧(或硫)基，特别优选C
1-C
6烷氧(或硫)基，尤其优选C
1-C
4烷氧(或硫)基。C
1-C
8烷氧基可以是甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、2-丁氧基、叔丁氧基、戊氧基、异戊氧基、己氧基、庚氧基、辛氧基、异辛氧基及其异构体。C
1-C
8烷硫基可以是甲硫基、乙硫基、丙硫基、异丙硫基、正丁硫基、2-丁硫基、叔丁硫基、戊硫基、异戊硫基、己硫基、庚硫基、辛硫基、异辛硫基及其异构体。
The terms "C n -C m alkoxy" and "C n -C m alkylthio" mean that any carbon atom of the open chain C n -C m alkane corresponding to the C n -C m alkyl group is bonded to any carbon atom A C n -C m alkyl group with an oxygen atom or a sulfur atom as the linking group, for example, a C 1 -C 20 alkoxy (or thio) group, preferably a C 1 -C 12 alkoxy (or thio) group, more preferably A C 1 -C 8 alkoxy (or thio) group, particularly preferably a C 1 -C 6 alkoxy (or thio) group, and particularly preferably a C 1 -C 4 alkoxy (or thio) group. C 1 -C 8 alkoxy can be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, pentoxy, isopentoxy Group, hexyloxy, heptyloxy, octyloxy, isooctyloxy and its isomers. The C 1 -C 8 alkylthio group can be methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, 2-butylthio, tert-butylthio, pentylthio, isoamylthio Group, hexylthio, heptylthio, octylthio, isooctylthio and its isomers.
本文所用术语“C
6-C
m芳氧基”和“C
6-C
m芳硫基”是指在C
6-C
m芳基对应的C
6-C
m芳烃中的任何芳族碳原子上键合有一个氧原子或一个硫原子作为连接基团的C
6-C
m芳基，例如苯硫基、苯氧基、甲苯氧基、甲苯硫基、萘硫基、萘氧基等。
The term "C 6 -C m aryloxy" and "arylthio C 6 -C m" refers to the -C m any aromatic carbon atoms in the aromatic C 6 -C aryl group m corresponding to C 6 The C 6 -C m aryl group to which an oxygen atom or a sulfur atom is bonded as a linking group, such as phenylthio, phenoxy, tolyloxy, tolylthio, naphthylthio, naphthyloxy and the like.
在本发明中，m为0-8的整数，优选为0-4的整数，更优选为0、1或2。In the present invention, m is an integer of 0-8, preferably an integer of 0-4, and more preferably 0, 1, or 2.
在本发明中，m个A
1彼此可以相同或不同。当m不为0时，A
1与A
2可相同或不同。通常而言，m个A
1以及A
2相同或不同，并且相互独立地表示O、S和NR
a，其中R
a为H或C
1-C
6烷基。优选的是，m个A
1以及A
2相同或不同，并且相互独立地表示O、S和NR
a，其中R
a为H或C
1-C
4烷基。更优选的是，m个A
1以及A
2彼此相同，并且表示O、S或NR
a，其中R
a为H或C
1-C
4烷基，例如H、甲基或乙基。
In the present invention, m A 1 s may be the same or different. When m is not 0, A 1 and A 2 may be the same or different. Generally, m of A 1 and A 2 are the same or different, and each independently represents O, S and NR a, wherein R a is H or C 1 -C 6 alkyl. Is preferably, m of A 1 and A 2 are the same or different, and each independently represents O, S and NR a, wherein R a is H or C 1 -C 4 alkyl. And more preferably, m of A 1 and A 2 identical to each other, and represent O, S or NR a, wherein R a is H or C 1 -C 4 alkyl, for example H, methyl or ethyl.
在本发明中，R
1、R
2、R
3、R
4相互独立地表示氢、卤素、硝基、氨基、氰基、C
1-C
20烷基、C
1-C
20烷氧基、C
1-C
20烷硫基、单C
1-C
12烷基氨基、二C
1-C
12烷基氨基、C
6-C
18芳氧基或C
6-C
18芳硫基，其中前述C
6-C
18芳氧基和C
6-C
18芳硫基基团中的芳基可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、NH
2、氰基、C
1-C
6烷基、C
1-C
6烷氧基和C
1-C
6烷硫基。
In the present invention, R 1 , R 2 , R 3 , and R 4 independently represent hydrogen, halogen, nitro, amino, cyano, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, mono C 1 -C 12 alkylamino, di C 1 -C 12 alkylamino, C 6 -C 18 aryloxy or C 6 -C 18 arylthio, wherein the aforementioned C 6 The aryl groups in the -C 18 aryloxy and C 6 -C 18 arylthio groups may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, NH 2 , cyano, C 1 -C 6 alkyl, C 1 -C 6 alkoxy and C 1 -C 6 alkylthio.
优选的是，R
1、R
2、R
3、R
4相互独立地表示氢、卤素、硝基、氨基、氰基、C
1-C
6烷基、 C
1-C
6烷氧基、C
1-C
6烷硫基、单C
1-C
6烷基氨基、二C
1-C
6烷基氨基、C
6-C
10芳氧基或C
6-C
10芳硫基，其中前述C
6-C
10芳氧基和C
6-C
10芳硫基基团中的芳基可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、NH
2、氰基、C
1-C
4烷基、C
1-C
4烷氧基和C
1-C
4烷硫基。
Preferably, R 1 , R 2 , R 3 , and R 4 independently represent hydrogen, halogen, nitro, amino, cyano, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, mono-C 1 -C 6 alkylamino, di-C 1 -C 6 alkylamino, C 6 -C 10 aryloxy or C 6 -C 10 arylthio, wherein the aforementioned C 6- The aryl groups in the C 10 aryloxy and C 6 -C 10 arylthio groups may be optionally substituted with one or more groups independently selected from the following group: halogen, nitro, hydroxyl, mercapto, NH 2. Cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1 -C 4 alkylthio.
特别优选的是，R
1、R
2、R
3、R
4相互独立地表示氢、卤素、硝基、氨基、氰基、C
1-C
4烷基、C
1-C
4烷氧基、C
1-C
4烷硫基、单C
1-C
4烷基氨基、二C
1-C
4烷基氨基、苯氧基或苯硫基，其中前述苯氧基和苯硫基基团中的苯基可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、NH
2、氰基、C
1-C
4烷基、C
1-C
4烷氧基和C
1-C
4烷硫基。
Particularly preferably, R 1 , R 2 , R 3 , and R 4 independently represent hydrogen, halogen, nitro, amino, cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1- C 4 alkylthio, mono C 1 -C 4 alkylamino, di C 1 -C 4 alkylamino, phenoxy or phenylthio, wherein the benzene in the aforementioned phenoxy and phenylthio groups The group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, NH 2 , cyano, C 1 -C 4 alkyl, C 1 -C 4 alkane Oxy and C 1 -C 4 alkylthio.
在本发明中，R
5表示氢、卤素、硝基、氰基、C
1-C
20烷基、C
1-C
20烷氧基、C
1-C
20烷硫基、C
6-C
18芳基、C
6-C
18芳基C
1-C
6烷基、C
6-C
18芳基C
1-C
6亚烷基、C
6-C
18芳氧基、C
6-C
18芳硫基、9H-咔唑-9基-C
1-C
6烷基、9H-咔唑-9基-C
1-C
6亚烷基、9H-芴-9基-C
1-C
6烷基或9H-芴-9基-C
1-C
6亚烷基，其中前述C
6-C
18芳基、C
6-C
18芳基C
1-C
6烷基、C
6-C
18芳基C
1-C
6亚烷基、C
6-C
18芳氧基、C
6-C
18芳硫基、9H-咔唑-9基-C
1-C
6烷基、9H-咔唑-9基-C
1-C
6亚烷基、9H-芴-9基-C
1-C
6烷基和9H-芴-9基-C
1-C
6亚烷基基团中的芳基可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、NH
2、氰基、C
1-C
6烷基、C
1-C
6烷氧基、C
1-C
6烷硫基和二苯基氨基，其中二苯基氨基中的苯基各自独立地任选包含一个或多个选自卤素、C
1-C
6烷基、C
1-C
6烷氧基和C
1-C
6烷硫基的取代基取代。
In the present invention, R 5 represents hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, C 6 -C 18 aryl Group, C 6 -C 18 aryl, C 1 -C 6 alkyl, C 6 -C 18 aryl, C 1 -C 6 alkylene, C 6 -C 18 aryloxy, C 6 -C 18 arylthio , 9H-carbazol-9yl-C 1 -C 6 alkyl, 9H-carbazol-9yl-C 1 -C 6 alkylene, 9H-fluoren-9yl-C 1 -C 6 alkyl or 9H -Fluoren-9 group-C 1 -C 6 alkylene group, wherein the aforementioned C 6 -C 18 aryl group, C 6 -C 18 aryl group C 1 -C 6 alkyl group, C 6 -C 18 aryl group C 1- C 6 alkylene, C 6 -C 18 aryloxy, C 6 -C 18 arylthio, 9H-carbazol-9yl-C 1 -C 6 alkyl, 9H-carbazol-9yl-C 1 -C 6 alkylene group, 9H-fluoren-9 group-C 1 -C 6 alkyl group and 9H-fluoren-9 group-C 1 -C 6 alkylene group may optionally be one or Substitution with multiple groups independently selected from the following group: halogen, nitro, hydroxy, mercapto, NH 2 , cyano, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 Alkylthio and diphenylamino, wherein the phenyl in the diphenylamino each independently optionally contains one or more selected from halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy and C The 1- C 6 alkylthio group is substituted by the substituent.
优选的是，R
5表示氢、卤素、硝基、氰基、C
1-C
6烷基、C
1-C
6烷氧基、C
1-C
6烷硫基、C
6-C
13芳基、C
6-C
13芳基C
1-C
4烷基、C
6-C
13芳基C
1-C
4亚烷基、C
6-C
13芳氧基、C
6-C
13芳硫基、9H-咔唑-9基-C
1-C
4烷基、9H-咔唑-9基-C
1-C
4亚烷基、9H-芴-9基-C
1-C
4烷基或9H-芴-9基-C
1-C
4亚烷基，其中前述C
6-C
13芳基、C
6-C
13芳基C
1-C
4烷基、C
6-C
13芳基C
1-C
4亚烷基、C
6-C
13芳氧基、C
6-C
13芳硫基、9H-咔唑-9基-C
1-C
4烷基、9H-咔唑-9基-C
1-C
4亚烷基、9H-芴-9基-C
1-C
4烷基和9H-芴-9基-C
1-C
4亚烷基基团中的芳基可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、NH
2、氰基、C
1-C
4烷基、C
1-C
4烷氧基、C
1-C
4烷硫基和二苯基氨基，其中二苯基氨基中的苯基各自独立地任选包含一个或多个选自卤素、C
1-C
4烷基、C
1-C
4烷氧基和C
1-C
4烷硫基的取代基。
Preferably, R 5 represents hydrogen, halogen, nitro, cyano, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 6 -C 13 aryl , C 6 -C 13 aryl C 1 -C 4 alkyl, C 6 -C 13 aryl, C 1 -C 4 alkylene, C 6 -C 13 aryloxy, C 6 -C 13 arylthio, 9H-carbazol-9 group-C 1 -C 4 alkyl group, 9H-carbazol-9 group-C 1 -C 4 alkylene group, 9H-fluoren-9 group-C 1 -C 4 alkyl group or 9H- Fluoren-9yl-C 1 -C 4 alkylene group, wherein the aforementioned C 6 -C 13 aryl group, C 6 -C 13 aryl group C 1 -C 4 alkyl group, C 6 -C 13 aryl group C 1 -C 4 alkylene, C 6 -C 13 aryloxy, C 6 -C 13 aryl group, 9H- carbazol-9-yl -C 1 -C 4 alkyl, 9H- carbazol-9-yl -C 1 - The aryl group in the C 4 alkylene group, 9H-fluoren-9 group-C 1 -C 4 alkyl group and 9H-fluoren-9 group-C 1 -C 4 alkylene group may be optionally substituted by one or more Substitution by a group independently selected from the following group: halogen, nitro, hydroxyl, mercapto, NH 2 , cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkane Thio and diphenylamino, wherein the phenyl in the diphenylamino each independently optionally contains one or more selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1 -Substituents of C 4 alkylthio.
特别优选的是，R
5表示氢、卤素、硝基、氰基、C
1-C
4烷基、C
1-C
4烷氧基、C
1-C
4烷硫基、苯基、C
6-C
13芳基C
1-C
2烷基、C
6-C
13芳基C
1-C
2亚烷基、C
6-C
10芳氧基、C
6-C
10芳硫基、9H-咔唑-9基-C
1-C
2烷基、9H-咔唑-9基-C
1-C
2亚烷基、9H-芴-9基-C
1-C
2烷基或9H-芴-9基-C
1-C
2亚烷基，其中前述苯基、C
6-C
13芳基C
1-C
2烷基、C
6-C
13芳基C
1-C
2亚烷基、C
6-C
10芳氧基、C
6-C
10芳硫基、9H-咔唑-9基-C
1-C
2烷基、9H-咔唑-9基-C
1-C
2亚烷基、9H-芴-9基-C
1-C
2烷基和9H-芴-9基-C
1-C
2亚烷基基团中的芳基可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、NH
2、氰基、C
1-C
4烷基、C
1-C
4烷氧基、C
1-C
4烷硫基和二苯基氨基，其中二苯基氨基中的苯基各自独立地任选包含一个或多个选自卤素、C
1-C
4烷基、C
1-C
4烷氧基和C
1-C
4烷硫基的取代基。
Particularly preferably, R 5 represents hydrogen, halogen, nitro, cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, phenyl, C 6- C 13 aryl C 1 -C 2 alkyl, C 6 -C 13 aryl C 1 -C 2 alkylene, C 6 -C 10 aryloxy, C 6 -C 10 arylthio, 9H-carbazole -9 group-C 1 -C 2 alkyl group, 9H-carbazol-9 group-C 1 -C 2 alkylene group, 9H-fluoren-9 group-C 1 -C 2 alkyl group or 9H-fluoren-9 group -C 1 -C 2 alkylene, wherein the aforementioned phenyl, C 6 -C 13 aryl C 1 -C 2 alkyl, C 6 -C 13 aryl C 1 -C 2 alkylene, C 6 -C 10 aryloxy group, C 6 -C 10 arylthio group, 9H-carbazol-9 group-C 1 -C 2 alkyl group, 9H-carbazol-9 group-C 1 -C 2 alkylene group, 9H-fluorene The aryl group in the -9 group-C 1 -C 2 alkyl group and the 9H-fluoren-9 group-C 1 -C 2 alkylene group may be optionally selected by one or more groups independently selected from the following group Group substitution: halogen, nitro, hydroxyl, mercapto, NH 2 , cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio and diphenylamino, where The phenyl groups in the diphenylamino group each independently optionally contain one or more substituents selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, and C 1 -C 4 alkylthio .
在本发明中，R
6与R
6’相同或不同，并且相互独立地表示H、氰基、C
1-C
20烷基、C
3- C
10环烷基、C
4-C
10环烷基烷基、C
4-C
10烷基环烷基、C
6-C
20芳基、C
7-C
20芳烷基或C
7-C
20烷基芳基，其中前述C
1-C
20烷基、C
3-C
10环烷基、C
4-C
10环烷基烷基、C
4-C
10烷基环烷基、C
6-C
20芳基、C
7-C
20芳烷基和C
7-C
20烷基芳基任选地被一个或多个独立地选自下组的基团取代：C
1-C
6烷基、C
1-C
6烷硫基、C
1-C
6烷氧基、卤素、硝基、氨基、单(C
1-C
6烷基)氨基、二(C
1-C
6烷基)氨基和巯基。
In the present invention, R 6 and R '6 are identical or different and each independently represents H, cyano, C 1 -C 20 alkyl, C 3 - C 10 cycloalkyl, C 4 -C 10 cycloalkyl Alkyl group, C 4 -C 10 alkyl cycloalkyl group, C 6 -C 20 aryl group, C 7 -C 20 aralkyl group or C 7 -C 20 alkyl aryl group, wherein the aforementioned C 1 -C 20 alkyl group , C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkyl alkyl, C 4 -C 10 alkyl cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C The 7 -C 20 alkyl aryl group is optionally substituted with one or more groups independently selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 alkylthio, C 1 -C 6 alkane Oxy, halogen, nitro, amino, mono(C 1 -C 6 alkyl)amino, di(C 1 -C 6 alkyl)amino, and mercapto.
优选的是，R
6与R
6’相同或不同，并且相互独立地表示H、氰基、C
1-C
6烷基、C
3-C
8环烷基、C
4-C
8环烷基烷基、C
4-C
8烷基环烷基、C
6-C
10芳基、C
7-C
11芳烷基或C
7-C
11烷基芳基，其中前述C
1-C
6烷基、C
3-C
8环烷基、C
4-C
8环烷基烷基、C
4-C
8烷基环烷基、C
6-C
10芳基、C
7-C
11芳烷基和C
7-C
11烷基芳基任选地被一个或多个独立地选自下组的基团取代：C
1-C
4烷基、C
1-C
4烷硫基、C
1-C
4烷氧基、卤素、硝基、氨基、单(C
1-C
4烷基)氨基、二(C
1-C
4烷基)氨基和巯基。
Preferably, R 6 and R 6 'are the same or different, and independently represent H, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkyl alkane Group, C 4 -C 8 alkylcycloalkyl group, C 6 -C 10 aryl group, C 7 -C 11 aralkyl group or C 7 -C 11 alkyl aryl group, wherein the aforementioned C 1 -C 6 alkyl group, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl and C 7 -C 11 alkylaryl is optionally substituted with one or more groups independently selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkylthio, C 1 -C 4 alkoxy Group, halogen, nitro, amino, mono(C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkyl)amino and mercapto.
特别优选的是，R
6与R
6’相同或不同，并且相互独立地表示H、氰基、C
1-C
6烷基、C
3-C
6环烷基或C
3-C
6环烷基C
1-C
2烷基，其中前述C
1-C
6烷基、C
3-C
6环烷基和C
3-C
6环烷基C
1-C
2烷基任选地被一个或多个独立地选自下组的基团取代：C
1-C
4烷基、C
1-C
4烷硫基、C
1-C
4烷氧基、卤素、硝基、氨基、单(C
1-C
4烷基)氨基、二(C
1-C
4烷基)氨基和巯基。
It is particularly preferred that R 6 and R 6 ′ are the same or different, and independently represent H, cyano, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl or C 3 -C 6 cycloalkyl. C 1 -C 2 alkyl, wherein the aforementioned C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl and C 3 -C 6 cycloalkyl C 1 -C 2 alkyl are optionally substituted by one or more Substitution groups independently selected from the following group: C 1 -C 4 alkyl, C 1 -C 4 alkylthio, C 1 -C 4 alkoxy, halogen, nitro, amino, mono (C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkyl)amino and mercapto.
在本发明中，R
7与R
7’相同或不同，并且相互独立地表示C
1-C
20烷基、C
3-C
10环烷基、C
4-C
10环烷基烷基、C
4-C
10烷基环烷基、C
6-C
20芳基、C
7-C
20芳烷基或C
7-C
20烷基芳基，其中前述C
1-C
20烷基、C
3-C
10环烷基、C
4-C
10环烷基烷基、C
4-C
10烷基环烷基、C
6-C
20芳基、C
7-C
20芳烷基和C
7-C
20烷基芳基任选地被一个或多个独立地选自下组的基团取代：C
1-C
6烷基、C
1-C
6烷硫基、C
1-C
6烷氧基、卤素、硝基、氨基、单(C
1-C
6烷基)氨基、二(C
1-C
6烷基)氨基和巯基。
In the present invention, R 7 and R 7 ′ are the same or different, and independently represent C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkyl alkyl, C 4 -C 10 alkyl cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl or C 7 -C 20 alkyl aryl, wherein the aforementioned C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkyl alkyl, C 4 -C 10 alkyl cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkane Alkylaryl is optionally substituted with one or more groups independently selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 alkylthio, C 1 -C 6 alkoxy, halogen, Nitro, amino, mono(C 1 -C 6 alkyl)amino, di(C 1 -C 6 alkyl)amino, and mercapto.
优选的是，R
7与R
7’相同或不同，并且相互独立地表示C
1-C
6烷基、C
3-C
8环烷基、C
4-C
8环烷基烷基、C
4-C
8烷基环烷基、C
6-C
10芳基、C
7-C
11芳烷基或C
7-C
11烷基芳基，其中前述C
1-C
6烷基、C
3-C
8环烷基、C
4-C
8环烷基烷基、C
4-C
8烷基环烷基、C
6-C
10芳基、C
7-C
11芳烷基和C
7-C
11烷基芳基任选地被一个或多个独立地选自下组的基团取代：C
1-C
4烷基、C
1-C
4烷硫基、C
1-C
4烷氧基、卤素、硝基、氨基、单(C
1-C
4烷基)氨基、二(C
1-C
4烷基)氨基和巯基。
Preferably, R 7 and R 7 ′ are the same or different, and independently represent C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkyl alkyl, C 4- C 8 alkyl cycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl or C 7 -C 11 alkyl aryl, wherein the aforementioned C 1 -C 6 alkyl, C 3 -C 8 Cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl, and C 7 -C 11 alkyl The aryl group is optionally substituted by one or more groups independently selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkylthio, C 1 -C 4 alkoxy, halogen, nitro Group, amino group, mono(C 1 -C 4 alkyl)amino group, di(C 1 -C 4 alkyl)amino group and mercapto group.
特别优选的是，R
7与R
7’相同或不同，并且相互独立地表示C
1-C
4烷基或苯基，其中前述C
1-C
4烷基和苯基任选地被一个或多个独立地选自下组的基团取代：C
1-C
4烷基、C
1-C
4烷硫基、C
1-C
4烷氧基、卤素、硝基、氨基、单(C
1-C
4烷基)氨基、二(C
1-C
4烷基)氨基和巯基。
It is particularly preferred that R 7 and R 7 'are the same or different, and independently represent C 1 -C 4 alkyl or phenyl, wherein the aforementioned C 1 -C 4 alkyl and phenyl are optionally substituted by one or more Substitution by a group independently selected from the following group: C 1 -C 4 alkyl, C 1 -C 4 alkylthio, C 1 -C 4 alkoxy, halogen, nitro, amino, mono (C 1- C 4 alkyl) amino, di(C 1 -C 4 alkyl) amino and mercapto.
在本发明的一个特别优选的实施方案中，式(I)和式(II)化合物选自下文列出的化合物1-65。In a particularly preferred embodiment of the present invention, the compounds of formula (I) and (II) are selected from compounds 1-65 listed below.
根据本发明的第二个方面，提供了一种制备本发明式(I)和(II)化合物的方法，包括以下步骤：According to the second aspect of the present invention, there is provided a method for preparing the compounds of formula (I) and (II) of the present invention, which comprises the following steps:
(1)肟化反应：当n和n’为0时，使式(III)和(IV)化合物各自与羟胺和/或盐酸羟胺进行肟化反应，分别得到式(IIIa)和(IVa)化合物(1) Oximation reaction: when n and n'are 0, the compounds of formula (III) and (IV) are oximated with hydroxylamine and/or hydroxylamine hydrochloride to obtain compounds of formula (IIIa) and (IVa), respectively
当n和n’为1时，使式(III)和(IV)化合物各自与选自亚硝酸、亚硝酸盐和亚硝酸烷基酯中的试剂进行肟化反应，分别得到式(IIIb)和(IVb)化合物:When n and n'are 1, the compounds of formula (III) and (IV) are each reacted with a reagent selected from the group consisting of nitrous acid, nitrite and alkyl nitrite to obtain formula (IIIb) and (IVb) Compound:
其中，式(III)、(IV)、(IIIa)、(IVa)、(IIIb)和(IVb)中的m、A
1、A
2、R
1-R
4和R
6，式(III)、(IIIa)和(IIIb)中的R
5以及式(IV)、(IVa)和(IVb)中的R
6’如对式(I)和式(II)化合物所定义；以及
Wherein, m, A 1 , A 2 , R 1 -R 4 and R 6 in formula (III), (IV), (IIIa), (IVa), (IIIb) and (IVb), formula (III), R 5 in (IIIa) and (IIIb) and R 6 ′ in formulas (IV), (IVa) and (IVb) are as defined for the compounds of formula (I) and formula (II); and
(2)将式(IIIa)和(IIIb)酯化，将式(IVa)和(IVb)化合物酯化，分别得到式(I)和(II)化合物。(2) Esterification of formula (IIIa) and (IIIb), and esterification of compounds of formula (IVa) and (IVb) to obtain compounds of formula (I) and (II), respectively.
为了制备本发明的式(I)和(II)化合物，需要先进行肟化反应，以引入肟基，然后使肟基中的羟基经酯化反应转变成相应的酯基，从而获得本发明的肟酯化合物。In order to prepare the compounds of formula (I) and (II) of the present invention, an oximation reaction is required to introduce an oxime group, and then the hydroxyl group in the oxime group is converted into the corresponding ester group through an esterification reaction to obtain the compound of the present invention. Oxime ester compound.
肟化反应Oximation reaction
肟化反应通常从羰基化合物开始。为此，当n和n’为0时，使式(III)和(IV)化合物各自与羟胺和/或盐酸羟胺进行肟化反应，分别得到式(IIIa)和(IVa)化合物：The oximation reaction usually starts from the carbonyl compound. For this reason, when n and n'are 0, the compounds of formula (III) and (IV) are respectively subjected to oximation reaction with hydroxylamine and/or hydroxylamine hydrochloride to obtain compounds of formula (IIIa) and (IVa) respectively:
式(III)、(IV)、(IIIa)和(IVa)中的m、A
1、A
2、R
1-R
4和R
6，式(III)和(IIIa)中的R
5以及式(IV)和(IVa)中的R
6’如对式(I)和(II)化合物所定义。为了将式(III)和(IV)化合物中的非环羰基转变为肟基，通常需要使用盐酸羟胺(NH
2OH.HCl)、羟胺(NH
2OH)或其混合物作为肟化试剂。该肟化反应通常在有机溶剂中进行，优选在有机极性溶剂中进行。可采用的溶剂例如有乙醇或含水的乙醇。为了促进肟化反应进行完全，一般需加入乙酸钠、吡啶、哌啶、三乙胺、四甲基氢氧化铵之类的碱或其混合物。这当中，吡啶、哌啶、三乙胺也可用作碱和/或溶剂或助溶剂。肟化反应的温度一般为溶剂的回流温度，温度范围通常在60-120℃。肟化反应时间也没有特别的限制，通常进行0.1-20小时，优选0.5-10小时。式(III)和(IV)化合物各自与选自羟胺和/或盐酸羟胺的化合物的相对用量没有特别的限制，通常而言它们以大致等摩尔量使用，例如二者的摩尔比为1:1.5-1.5:1，优选为1:1.2-1.2:1。
Of formula (III), (IV), (IIIa) and (IVa) in m, A 1, A 2, R 1 -R 4 and R 6, of formula (III) and (IIIa) and R 5 in formula ( R 6 ′ in IV) and (IVa) is as defined for the compounds of formula (I) and (II). In order to convert the acyclic carbonyl group in the compounds of formula (III) and (IV) into an oxime group, it is usually necessary to use hydroxylamine hydrochloride (NH 2 OH.HCl), hydroxylamine (NH 2 OH) or a mixture thereof as an oximation reagent. The oximation reaction is usually carried out in an organic solvent, preferably in an organic polar solvent. Examples of usable solvents include ethanol or water-containing ethanol. In order to promote the completion of the oximation reaction, it is generally necessary to add a base such as sodium acetate, pyridine, piperidine, triethylamine, tetramethylammonium hydroxide, or a mixture thereof. Among them, pyridine, piperidine, and triethylamine can also be used as bases and/or solvents or co-solvents. The temperature of the oximation reaction is generally the reflux temperature of the solvent, and the temperature range is usually 60-120°C. The oximation reaction time is also not particularly limited, and it is usually carried out for 0.1-20 hours, preferably 0.5-10 hours. The relative amount of each compound of formula (III) and (IV) and the compound selected from hydroxylamine and/or hydroxylamine hydrochloride is not particularly limited. Generally speaking, they are used in approximately equimolar amounts, for example, the molar ratio of the two is 1:1.5 -1.5:1, preferably 1:1.2-1.2:1.
当n和n’为1时，使上述式(III)和(IV)化合物各自与选自亚硝酸、亚硝酸盐和亚硝酸烷基酯中的试剂进行肟化反应，分别得到式(IIIb)和(IVb)化合物:When n and n'are 1, the compounds of the above formula (III) and (IV) are reacted with a reagent selected from the group consisting of nitrous acid, nitrite and alkyl nitrite, respectively, to obtain formula (IIIb) And (IVb) compound:
其中，式(IIIb)和(IVb)中的m、A
1、A
2、R
1-R
4和R
6，式(IIIb)中的R
5以及式(IVb)中的R
6’如对式(I)和(II)化合物所定义。为了将式(III)和(IV)化合物中的非环羰基转变为酮肟基，通常需要使用亚硝酸、亚硝酸盐和/或亚硝酸烷基酯作为肟化试剂。该试剂将“活性”(亚)甲基(α-(亚)甲基，即紧挨着非环羰基的(亚)甲基)进行亚硝化。作为亚硝酸盐，通常使用亚硝酸钠。亚硝酸烷基酯可以是亚硝酸C
1-C
6烷基酯，例如亚硝酸甲酯、亚硝酸乙酯、亚硝酸异丙酯、亚硝酸丁酯、亚硝酸异戊酯。该肟化反应通常在有机溶剂中进行，优选在有机极性溶剂中进行。可采用的溶剂例如有四氢呋喃、乙醇或含水的乙醇。为了促进肟化反应进行完全，一般需加入浓盐酸，其浓度通常为20-40％。浓盐酸也可用作酸和/或溶剂或助溶剂。肟化反应的温度为低温，温度范围通常在-30至20℃，优选5-20℃。肟化反应时间也没有特别的限制，通常进行0.1-20小时，优选0.5-10小时。式(III)和(IV)化合物各自与选自亚硝酸、亚硝酸盐和/或亚硝酸烷基酯的化合物的相对用量没有特别的限制，通常而言它们以大致等摩尔量使用，例如二者的摩尔比为1:1.5-1.5:1，优选为1:1.2-1.2:1。
Wherein, m, A 1 , A 2 , R 1 -R 4 and R 6 in formulas (IIIb) and (IVb), R 5 in formula (IIIb) and R 6 'in formula (IVb) are the same as (I) and (II) as defined by compounds. In order to convert the acyclic carbonyl group in the compound of formula (III) and (IV) into a ketoxime group, it is usually necessary to use nitrous acid, nitrite and/or alkyl nitrite as an oximation reagent. This reagent nitrosates the "active" (methylene) methyl group (α-(methylene) methyl group, that is, the (methylene) group next to the non-cyclic carbonyl group). As the nitrite, sodium nitrite is usually used. The alkyl nitrite may be a C 1 -C 6 alkyl nitrite, such as methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, and isoamyl nitrite. The oximation reaction is usually carried out in an organic solvent, preferably in an organic polar solvent. Examples of usable solvents include tetrahydrofuran, ethanol, or water-containing ethanol. In order to promote the completion of the oximation reaction, it is generally necessary to add concentrated hydrochloric acid, the concentration of which is usually 20-40%. Concentrated hydrochloric acid can also be used as acid and/or solvent or co-solvent. The temperature of the oximation reaction is a low temperature, and the temperature range is usually -30 to 20°C, preferably 5-20°C. The oximation reaction time is also not particularly limited, and it is usually carried out for 0.1-20 hours, preferably 0.5-10 hours. The relative amounts of the compounds of formula (III) and (IV) and the compound selected from the group consisting of nitrous acid, nitrite and/or alkyl nitrite are not particularly limited. Generally speaking, they are used in approximately equimolar amounts, such as two The molar ratio of these is 1:1.5-1.5:1, preferably 1:1.2-1.2:1.
每个肟酯基可能存在两种构型，(Z)型或(E)型。可通过常规方法分离异构体，但也可使 用异构体混合物作为光引发物质。因此，本发明还涉及式(I)和(II)化合物各自的构型异构体的混合物。Each oxime ester group may have two configurations, (Z) type or (E) type. The isomers can be separated by conventional methods, but a mixture of isomers can also be used as the photoinitiating substance. Therefore, the present invention also relates to a mixture of respective configurational isomers of the compounds of formula (I) and (II).
酯化反应Esterification reaction
式(IIIa)、(IIIb)、(IVa)和(IVb)化合物的酯化是常规的，通过该反应，肟基中的羟基转变为酯基，从而获得式(I)和(II)化合物。作为酯化试剂，没有特别的限制，只要能将式(IIIa)、(IIIb)、(IVa)和(IVb)化合物肟基中的羟基转变为酯基即可。作为酯化试剂，可以使用相应的酰卤，如酰氯，也可使用相应的羧酸，还可使用相应的酸酐。这些化合物可分别表示为式(Va)、(Vb)和(Vc):The esterification of compounds of formula (IIIa), (IIIb), (IVa) and (IVb) is conventional. Through this reaction, the hydroxyl group in the oxime group is converted into an ester group, thereby obtaining the compounds of formula (I) and (II). As the esterification agent, there is no particular limitation, as long as it can convert the hydroxyl group in the oxime group of the compounds of formula (IIIa), (IIIb), (IVa) and (IVb) into an ester group. As the esterification reagent, the corresponding acid halide, such as acid chloride, the corresponding carboxylic acid, and the corresponding acid anhydride can also be used. These compounds can be represented as formula (Va), (Vb) and (Vc) respectively:
其中X为卤素，尤其是氯，和R
7如对式(I)和(II)化合物中的R
7和(II)化合物中的R
7’所定义。
Wherein X is halogen, in particular chlorine, and R 7 are as defined for formula (I) and (II) compound R (II) R compound 7 and 7 'are defined.
为了加速酯化反应，上述酯化反应通常在适于酯化反应的催化剂存在下进行。作为催化剂，既可以使用酸性催化剂，也可以使用碱性催化剂。作为催化剂，可以使用选自下组的一种或多种：硫酸、高氯酸、氯化锌、三氯化铁、吡啶、对甲基苯磺酸、氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、叔丁醇钠、乙醇钠、氢化钠、氢化钾、氢化钙和叔胺，例如三烷基胺，如三甲基胺和三乙胺。催化剂的用量是常规的，可以通过本领域的常识确定，或者通过几个例行的预备实验来确定。In order to accelerate the esterification reaction, the above-mentioned esterification reaction is usually carried out in the presence of a catalyst suitable for the esterification reaction. As the catalyst, either an acid catalyst or a basic catalyst may be used. As the catalyst, one or more selected from the group consisting of sulfuric acid, perchloric acid, zinc chloride, ferric chloride, pyridine, p-toluenesulfonic acid, sodium hydroxide, potassium hydroxide, sodium carbonate can be used , Sodium bicarbonate, sodium tert-butoxide, sodium ethoxide, sodium hydride, potassium hydride, calcium hydride and tertiary amines such as trialkylamines such as trimethylamine and triethylamine. The amount of catalyst used is conventional and can be determined by common sense in the field or through several routine preliminary experiments.
为了提高式(I)和(II)化合物的产率，有利的是，在酯化反应过程中移除酯化反应产生的水。这例如可以通过蒸馏冷凝来进行。In order to increase the yield of the compounds of formula (I) and (II), it is advantageous to remove water produced by the esterification reaction during the esterification reaction. This can be done, for example, by distillation and condensation.
上述酯化反应通常在溶剂中，优选在有机溶剂中进行。作为溶剂的类型的选择，没有特别的限制，只要能够将式(IIIa)、(IIIb)、(IVa)或(IVb)化合物和酯化试剂溶解并且对酯化反应呈化学惰性即可，即不参与该酯化反应即可。作为溶剂的实例，可以提及四氢呋喃、苯、甲苯、N，N-二甲基甲酰胺、二氯甲烷和丙酮。溶剂可以使用单一种，也可以使用两种或更多种溶剂的混合物。The above-mentioned esterification reaction is usually carried out in a solvent, preferably in an organic solvent. There is no particular restriction on the choice of the type of solvent, as long as it can dissolve the compound of formula (IIIa), (IIIb), (IVa) or (IVb) and the esterification reagent and is chemically inert to the esterification reaction, that is, it is not Just participate in the esterification reaction. As examples of the solvent, tetrahydrofuran, benzene, toluene, N,N-dimethylformamide, dichloromethane and acetone can be mentioned. A single solvent may be used, or a mixture of two or more solvents may be used.
式(IIIa)、(IIIb)、(IVa)或(IVb)化合物各自与选自(Va)、(Vb)和(Vc)化合物的酯化试剂的相对用量没有特别的限制，通常而言它们以大致等摩尔量使用，例如二者的摩尔比为1:1.5-1.5:1，优选为1:1.2-1.2:1。The relative amount of the compound of formula (IIIa), (IIIb), (IVa) or (IVb) and the esterification agent selected from the group consisting of (Va), (Vb) and (Vc) is not particularly limited. Generally speaking, they are It is used in approximately equimolar amounts, for example, the molar ratio of the two is 1:1.5-1.5:1, preferably 1:1.2-1.2:1.
酯化反应可以在非常宽的温度范围内进行。根据本发明有利的是，酯化反应在-10℃至150℃，优选0℃至100℃的温度下进行，优选常温下进行。酯化反应时间也没有特别的限制，通常进行1-24小时，优选1-12小时。The esterification reaction can be carried out in a very wide temperature range. According to the present invention, it is advantageous that the esterification reaction is carried out at a temperature of -10°C to 150°C, preferably 0°C to 100°C, preferably at room temperature. The esterification reaction time is also not particularly limited, and it is usually carried out for 1-24 hours, preferably 1-12 hours.
在酯化反应完成之后，获得包含式(I)或式(II)化合物的反应混合物。因此，需要对该反应混合物进行后处理，以得到提纯的式(I)或式(II)化合物。通常而言，首先过滤酯化反应得到的反应混合物，取出滤液部分。然后，将滤液进行洗涤，以除去催化剂和未反应的原料。 作为洗液，没有特别的限制，只要能除去催化剂和未反应的原料即可。作为洗液的实例，可以提及稀盐酸(水溶液)、饱和碳酸氢钠水溶液和水。稀盐酸的浓度没有特别的限制，通常而言使用浓度为5-12％的稀盐酸。用洗液洗涤可以进行一次，也可进行多次；在进行多次的情况下，可使用单一种洗液，也可依次使用不同的洗液。根据本发明有利的是，将对酯化反应得到的反应混合物过滤得到的滤液依次用稀盐酸、饱和碳酸氢钠水溶液和水进行洗涤。当然，每一次用洗液洗涤后，都需要倒掉水相之后再用下一种洗液对有机相进行洗涤。洗涤之后，需要干燥以除去残留的水。为此，通常可使用无水硫酸钠或硫酸镁进行干燥。干燥之后，再除去残留的有机溶剂。作为这里除去有机溶剂的手段，没有特别的限制，通常可通过减压蒸馏来除去有机溶剂。除去残留有机溶剂之后，得到式(I)或(II)化合物的粗产物。如果想要进一步提高式(I)或(II)化合物的纯度，还可对该化合物进行进一步提纯，这例如可通过重结晶的方式来进行。重结晶溶剂的选择是常规的，没有特别的限制。根据本发明，有利的是，采用甲醇对式(I)或(II)化合物的粗产物进行重结晶。After the esterification reaction is completed, a reaction mixture containing the compound of formula (I) or formula (II) is obtained. Therefore, the reaction mixture needs to be post-treated to obtain a purified compound of formula (I) or formula (II). Generally, the reaction mixture obtained by the esterification reaction is filtered first, and the filtrate portion is taken out. Then, the filtrate is washed to remove the catalyst and unreacted raw materials. As the washing liquid, there is no particular limitation, as long as the catalyst and unreacted raw materials can be removed. As examples of the washing liquid, dilute hydrochloric acid (aqueous solution), saturated sodium bicarbonate aqueous solution and water can be mentioned. The concentration of dilute hydrochloric acid is not particularly limited. Generally, dilute hydrochloric acid with a concentration of 5-12% is used. Washing with lotion can be done once or multiple times; in the case of multiple times, a single lotion can be used, or different lotions can be used in sequence. According to the present invention, it is advantageous that the filtrate obtained by filtering the reaction mixture obtained by the esterification reaction is washed successively with dilute hydrochloric acid, a saturated sodium bicarbonate aqueous solution and water. Of course, after each washing with a lotion, you need to pour off the water phase and then use the next lotion to wash the organic phase. After washing, it needs to be dried to remove residual water. For this reason, anhydrous sodium sulfate or magnesium sulfate can usually be used for drying. After drying, the remaining organic solvent is removed. The means for removing the organic solvent here is not particularly limited, and the organic solvent can usually be removed by distillation under reduced pressure. After removing the residual organic solvent, a crude product of the compound of formula (I) or (II) is obtained. If it is desired to further improve the purity of the compound of formula (I) or (II), the compound can be further purified, for example, by recrystallization. The selection of the recrystallization solvent is conventional and not particularly limited. According to the present invention, it is advantageous to use methanol to recrystallize the crude product of the compound of formula (I) or (II).
本发明式(I)和(II)化合物吸收波长较长，尤其是在365-420nm的波长范围内有较强吸收，故可应用于UV-LED光固化体系中。The compounds of formula (I) and (II) of the present invention have longer absorption wavelengths, especially strong absorption in the wavelength range of 365-420 nm, so they can be applied to UV-LED light curing systems.
因此，根据本发明的第三个方面，提供了本发明式(I)和(II)化合物各自作为光引发剂的用途。本发明式(I)和(II)化合物各自有利地在UV-LED光固化体系中作为光引发剂，可以有效地引发固化反应。特别优选的是，本发明式(I)和(II)化合物各自在辐射波长为350-450nm、尤其365-420nm的光固化体系中作为光引发剂的用途。当式(I)和(II)化合物各自用作光引发剂时，其用量是常规的，或者通过例行的预备试验即可确定。Therefore, according to the third aspect of the present invention, the use of each of the compounds of formula (I) and (II) of the present invention as a photoinitiator is provided. The compounds of formula (I) and (II) of the present invention are each advantageously used as a photoinitiator in a UV-LED light curing system and can effectively initiate a curing reaction. Particularly preferred is the use of each of the compounds of formula (I) and (II) of the present invention as photoinitiators in photocuring systems with radiation wavelengths of 350-450 nm, especially 365-420 nm. When the compounds of formula (I) and (II) are each used as a photoinitiator, the dosage is conventional or can be determined by routine preliminary tests.
实施例Example
以下将结合具体实施例对本发明作进一步说明，但不应将其理解为对本发明保护范围的限制。The present invention will be further described below in conjunction with specific examples, but it should not be understood as a limitation on the protection scope of the present invention.
制备实施例1：化合物1的制备Preparation Example 1: Preparation of Compound 1
化合物1的合成路线如下：The synthetic route of compound 1 is as follows:
中间化合物1a的合成Synthesis of Intermediate Compound 1a
将2,2’-二噻吩(0.08mol，13.6g)溶于50ml二氯乙烷中，然后加入三氟乙酸酐(0.7mol，145g)和Mg(ClO
4)
2(0.08mol，17.87g)，将所得混合液加热至80℃反应4h。然后停止反应，加入200g冰，搅拌至冰溶解，加入饱和碳酸氢钠水溶液中和反应液至中性。然后用二氯甲烷 萃取有机相，并用无水硫酸镁干燥。干燥完毕后，过滤，减压蒸馏除去有机相得粗产物，用石油醚重结晶，得到最终产品17g，产率80％，经鉴定为中间化合物1a。1HNMR(400MHz,CDCl
3,ppm)δ7.11(t,1H),7.26(d,1H),7.43-7.41(m,2H),7.87-7.85(m,1H)。
Dissolve 2,2'-dithiophene (0.08mol, 13.6g) in 50ml dichloroethane, then add trifluoroacetic anhydride (0.7mol, 145g) and Mg(ClO 4 ) 2 (0.08mol, 17.87g) , The resulting mixed solution was heated to 80°C for 4h. Then stop the reaction, add 200 g of ice, stir until the ice dissolves, and add a saturated sodium bicarbonate aqueous solution to neutralize the reaction solution to neutrality. Then the organic phase was extracted with dichloromethane and dried with anhydrous magnesium sulfate. After drying, it was filtered, and the organic phase was removed by distillation under reduced pressure to obtain a crude product, which was recrystallized with petroleum ether to obtain 17 g of the final product with a yield of 80%, which was identified as the intermediate compound 1a. 1HNMR (400MHz, CDCl 3 , ppm) δ 7.11 (t, 1H), 7.26 (d, 1H), 7.43-7.41 (m, 2H), 7.87-7.85 (m, 1H).
中间化合物1b的合成Synthesis of intermediate compound 1b
将所得中间化合物1a(5.5g，0.021mol)和50mL乙醇与水的混合溶液(V
乙醇：V
水＝2:1)倒入100mL三口圆底烧瓶中，再加入盐酸羟胺(1.45g，0.021mol)和醋酸钠(1.72g，0.021mol)。70℃下搅拌反应0.5h后，过滤反应液，然后将滤液真空旋蒸后得淡黄色固体，乙醇重结晶，得5.23g产品，产率为90％，经鉴定为中间化合物1b。1HNMR(400MHz,CDCl
3,ppm)δ7.11(t,1H),7.26(d,1H),7.43-7.41(m,2H),7.87-7.85(m,1H 11.5(s,1H)。
Pour the obtained intermediate compound 1a (5.5 g, 0.021 mol) and 50 mL of a mixed solution of ethanol and water (V ethanol : V water = 2:1) into a 100 mL three-necked round bottom flask, and then add hydroxylamine hydrochloride (1.45 g, 0.021 mol) ) And sodium acetate (1.72g, 0.021mol). After stirring and reacting at 70°C for 0.5 h, the reaction solution was filtered, and then the filtrate was vacuum-rotated to obtain a pale yellow solid, which was recrystallized from ethanol to obtain 5.23 g of product with a yield of 90%. It was identified as intermediate compound 1b. 1HNMR (400MHz, CDCl 3 , ppm) δ 7.11 (t, 1H), 7.26 (d, 1H), 7.43-7.41 (m, 2H), 7.87-7.85 (m, 1H 11.5 (s, 1H).
目标化合物1的合成Synthesis of target compound 1
将所得中间化合物1b(5g，0.018mol)和30ml四氢呋喃加入到100mL三口圆底烧瓶中，然后加入乙酰氯(1.4g，0.018mol)和三乙胺(2.32g，0.023mol)，常温搅拌反应1h。终止反应，将反应液过滤后，滤液倒入水中，用乙酸乙酯萃取，收集有机相后依次用5％的稀盐酸水溶液、饱和碳酸钠水溶液、蒸馏水洗涤，然后收集有机相，并用MgSO
4干燥过夜。过滤后减压蒸馏蒸掉有机相后，得浅黄色固体5.45g，产率95.0％，经鉴定为化合物1。该化合物的核磁数据见下表。
Add the obtained intermediate compound 1b (5g, 0.018mol) and 30ml of tetrahydrofuran into a 100mL three-necked round bottom flask, then add acetyl chloride (1.4g, 0.018mol) and triethylamine (2.32g, 0.023mol), stir and react at room temperature for 1h . The reaction was terminated, the reaction liquid was filtered, the filtrate was poured into water, extracted with ethyl acetate, the organic phase was collected and washed with 5% dilute hydrochloric acid aqueous solution, saturated sodium carbonate aqueous solution, and distilled water successively, and then the organic phase was collected and dried with MgSO 4 overnight. After filtration, the organic phase was distilled off under reduced pressure to obtain 5.45 g of a light yellow solid with a yield of 95.0%, which was identified as compound 1. The NMR data of this compound are shown in the table below.
制备实施例2-3Preparation Example 2-3
重复制备实施例1的方法，适当改变反应原料，分别获得下表化合物2-3及其核磁数据。制备实施例4：化合物4的制备Repeat the method of Preparation Example 1 and appropriately change the reaction raw materials to obtain the following compound 2-3 and its nuclear magnetic data respectively. Preparation Example 4: Preparation of Compound 4
中间化合物4a的合成Synthesis of intermediate compound 4a
将2,2’-二噻吩(0.027mol，4.4g)溶于44ml二氯乙烷中，然后加入N,N-二甲基甲酰胺(0.053mol，3.9g),在0-5℃下向所得混合液中滴加POCl
3(0.042mol，6.3g)，然后室温下搅拌反应5h。然后停止反应，加入饱和碳酸氢钠水溶液中和反应液至中性。然后用二氯甲烷萃取有机相，并用无水硫酸镁干燥。干燥完毕后，过滤，减压蒸馏除去有机相得粗产物，用石油醚重结晶，得到最终产品3.9g，产率75％，经鉴定为中间化合物4a：5-(噻吩-2-基)噻吩-2-甲醛。1HNMR(400MHz,CDCl
3,ppm)δ7.11(t,1H),7.26(d,1H),7.43-7.41(m,2H),7.87-7.85(m,1H),8.4(s,1H)。
Dissolve 2,2'-dithiophene (0.027mol, 4.4g) in 44ml of dichloroethane, and then add N,N-dimethylformamide (0.053mol, 3.9g), at 0-5℃ POCl 3 (0.042 mol, 6.3 g) was added dropwise to the resulting mixed solution, and then the reaction was stirred at room temperature for 5 hours. Then the reaction was stopped, and a saturated aqueous sodium bicarbonate solution was added to neutralize the reaction solution to neutrality. Then the organic phase was extracted with dichloromethane and dried with anhydrous magnesium sulfate. After drying, filter and distill under reduced pressure to remove the organic phase to obtain the crude product. Recrystallize with petroleum ether to obtain the final product 3.9g with a yield of 75%. It was identified as intermediate compound 4a: 5-(thiophen-2-yl)thiophene -2-Formaldehyde. 1HNMR (400MHz, CDCl 3 , ppm) δ 7.11 (t, 1H), 7.26 (d, 1H), 7.43-7.41 (m, 2H), 7.87-7.85 (m, 1H), 8.4 (s, 1H).
最终化合物4的合成方法与最终化合物1的方法类似，只是将中间化合物1a替换为4a。化合物4的核磁数据见下表。The synthesis method of the final compound 4 is similar to that of the final compound 1, except that the intermediate compound 1a is replaced with 4a. The NMR data of compound 4 are shown in the table below.
制备实施例5-36：化合物5-36的制备Preparation Example 5-36: Preparation of Compound 5-36
重复制备实施例1或4的方法，适当改变反应原料，分别获得下表化合物5-36及其核磁数据。Repeat the method of Preparation Example 1 or 4, appropriately change the reaction raw materials, and obtain the following compound 5-36 and its nuclear magnetic data respectively.
制备实施例37：化合物37的制备Preparation Example 37: Preparation of Compound 37
化合物37的合成路线如下：The synthetic route of compound 37 is as follows:
中间化合物37a的合成Synthesis of Intermediate Compound 37a
将2,2’-二噻吩(0.03mol，4.98g)溶于75ml乙酸酐中，然后向反应液中滴加12滴85％的磷酸，然后加热回流反应1h。停止反应，将反应液倒入500g冰水中，搅拌至乙酸酐完全水解。过滤得粗产品，然后将粗产品用2,6-二氧六环重结晶，得浅黄色固体5.8g，产率77％，2,2'-Dithiophene (0.03mol, 4.98g) was dissolved in 75ml of acetic anhydride, and then 12 drops of 85% phosphoric acid were added dropwise to the reaction solution, and then heated and refluxed for 1 hour. The reaction was stopped, and the reaction liquid was poured into 500 g of ice water, and stirred until the acetic anhydride was completely hydrolyzed. The crude product was obtained by filtration, and then the crude product was recrystallized with 2,6-dioxane to obtain 5.8 g of light yellow solid with a yield of 77%.
经鉴定为中间化合物37a。1H-NMR(400MHz,CDCl
3),δ2.61(s,6H),7.19(d,2H),7.26(d,2H).
It was identified as the intermediate compound 37a. 1H-NMR (400MHz, CDCl 3 ), δ 2.61 (s, 6H), 7.19 (d, 2H), 7.26 (d, 2H).
中间化合物37b的合成.Synthesis of intermediate compound 37b.
将所得中间化合物37a(5g，0.02mol)和50mL乙醇与水的混合溶液(V
乙醇：V
水＝2:1)倒入100mL三口圆底烧瓶中，再加入盐酸羟胺(1.45g，0.021mol)和醋酸钠(1.72g，0.021mol)。70℃下搅拌反应0.5h后，过滤反应液，然后将滤液真空旋蒸后得淡黄色固体，乙醇重结晶，得 4.76g产品，产率为85％，经鉴定为中间化合物37b。1H-NMR(400MHz,CDCl
3),δ2.61(s,6H),7.20(d,2H),7.30(d,2H),11.5(s,1H).
The resulting intermediate compound 37a (5g, 0.02mol), and a mixed solution of 50mL of ethanol and water (V ethanol: V water = 2: 1) was poured into a 100mL three neck round bottom flask was added hydroxylamine hydrochloride (1.45g, 0.021mol) And sodium acetate (1.72g, 0.021mol). After stirring and reacting at 70°C for 0.5 h, the reaction solution was filtered, and then the filtrate was vacuum-rotated to obtain a pale yellow solid, which was recrystallized from ethanol to obtain 4.76 g of product with a yield of 85%, which was identified as intermediate compound 37b. 1H-NMR (400MHz, CDCl 3 ), δ 2.61 (s, 6H), 7.20 (d, 2H), 7.30 (d, 2H), 11.5 (s, 1H).
目标化合物37的合成Synthesis of target compound 37
将所得中间化合物37b(5.04g，0.018mol)和30ml四氢呋喃加入到100mL三口圆底烧瓶中，然后加入乙酰氯(1.4g，0.018mol)和三乙胺(2.32g，0.023mol)，常温搅拌反应1h。终止反应，将反应液过滤后，滤液倒入水中，用乙酸乙酯萃取，收集有机相后依次用5％的稀盐酸水溶液、饱和碳酸钠水溶液、蒸馏水洗涤，然后收集有机相，并用MgSO
4干燥过夜。过滤后减压蒸馏蒸掉有机相后，得浅黄色固体6.09g，产率93.0％，经鉴定为化合物37。该化合物的核磁数据见下表。
Add the obtained intermediate compound 37b (5.04g, 0.018mol) and 30ml of tetrahydrofuran into a 100mL three-necked round bottom flask, then add acetyl chloride (1.4g, 0.018mol) and triethylamine (2.32g, 0.023mol), stir and react at room temperature 1h. The reaction was terminated, the reaction liquid was filtered, the filtrate was poured into water, extracted with ethyl acetate, the organic phase was collected and washed with 5% dilute hydrochloric acid aqueous solution, saturated sodium carbonate aqueous solution, and distilled water successively, and then the organic phase was collected and dried with MgSO 4 overnight. After filtration, the organic phase was distilled off under reduced pressure to obtain 6.09 g of a light yellow solid with a yield of 93.0%. It was identified as compound 37. The NMR data of this compound are shown in the table below.
制备实施例38-40：化合物38-40的制备Preparation Example 38-40: Preparation of Compound 38-40
重复制备实施例37的方法，适当改变反应原料，分别获得下表化合物38-40及其核磁数据。Repeat the method of Preparation Example 37, appropriately change the reaction raw materials, and obtain the following compound 38-40 and its nuclear magnetic data respectively.
制备实施例41：化合物41的制备Preparation Example 41: Preparation of Compound 41
将2,2’-二噻吩(0.027mol，4.4g)溶于44ml二氯乙烷中，然后加入N,N-二甲基甲酰胺(0.106mol，7.8g),在0-5℃下向所得混合液中滴加POCl
3(0.084mol，12.6g)，然后室温下搅拌反应5h。然后停止反应，加入饱和碳酸氢钠水溶液中和反应液至中性。然后用二氯甲烷萃取有机相，并用无水硫酸镁干燥。干燥完毕后，过滤，减压蒸馏除去有机相得粗产物，用石油醚重结晶，得到最终产品3.9g，产率75％，经鉴定为中间化合物41a。1HNMR(400MHz,CDCl
3,ppm)δ7.43-7.41(d,2H),7.87-7.85(d,2H),9.0(s,2H)。
2,2'-Dithiophene (0.027mol, 4.4g) was dissolved in 44ml of dichloroethane, and then N,N-dimethylformamide (0.106mol, 7.8g) was added, and the temperature was 0-5℃ POCl 3 (0.084 mol, 12.6 g) was added dropwise to the resulting mixed solution, and then the reaction was stirred at room temperature for 5 hours. Then the reaction was stopped, and a saturated aqueous sodium bicarbonate solution was added to neutralize the reaction solution to neutrality. Then the organic phase was extracted with dichloromethane and dried with anhydrous magnesium sulfate. After drying, it was filtered, and the organic phase was removed by distillation under reduced pressure to obtain a crude product, which was recrystallized with petroleum ether to obtain a final product of 3.9 g with a yield of 75%, which was identified as intermediate compound 41a. 1HNMR (400MHz, CDCl 3 , ppm) δ7.43-7.41 (d, 2H), 7.87-7.85 (d, 2H), 9.0 (s, 2H).
最终化合物41的合成方法与最终化合物37的方法类似，只是将中间化合物37a替换为41a。化合物41的核磁数据见下表。The synthesis method of the final compound 41 is similar to that of the final compound 37, except that the intermediate compound 37a is replaced with 41a. The NMR data of compound 41 are shown in the table below.
制备实施例42-53：化合物42-53的制备Preparation Examples 42-53: Preparation of Compound 42-53
重复制备实施例37或41的方法，适当改变反应原料，分别获得下表化合物42-53及其核磁数据。Repeat the method of Preparation Example 37 or 41, appropriately change the reaction raw materials, and obtain the following compounds 42-53 and their nuclear magnetic data respectively.
制备实施例54：化合物54的制备Preparation Example 54: Preparation of Compound 54
化合物54的合成路线如下：The synthetic route of compound 54 is as follows:
中间化合物54a的合成Synthesis of intermediate compound 54a
将2,2’-二噻吩(0.08mol，13.6g)溶于50ml二氯乙烷中，然后加入辛酸酐(0.7mol，189g)和Mg(ClO
4)
2(0.08mol，17.87g)，将所得混合液加热至80℃反应4h。然后停止反应，加入200g冰，搅拌至冰溶解，加入饱和碳酸氢钠水溶液中和反应液至中性。然后用二氯甲烷萃取有机相，并用无水硫酸镁干燥。干燥完毕后，过滤，减压蒸馏除去有机相得粗产物，用石油醚重 结晶，得到最终产品19.6g，产率84％，经鉴定为中间化合物54a。
Dissolve 2,2'-dithiophene (0.08mol, 13.6g) in 50ml dichloroethane, then add caprylic anhydride (0.7mol, 189g) and Mg(ClO 4 ) 2 (0.08mol, 17.87g), The resulting mixture was heated to 80°C for 4h. Then stop the reaction, add 200 g of ice, stir until the ice dissolves, and add a saturated sodium bicarbonate aqueous solution to neutralize the reaction solution to neutrality. Then the organic phase was extracted with dichloromethane and dried with anhydrous magnesium sulfate. After drying, it was filtered, and the organic phase was removed under reduced pressure to obtain a crude product, which was recrystallized with petroleum ether to obtain a final product of 19.6 g with a yield of 84%, which was identified as intermediate compound 54a.
1HNMR(400MHz,CDCl
3)δ0.88(t,3H),1.31-1.47(m,10H),2.20(t,2H),6.87(t,1H),7.51(d,1H),7.60(d,1H),7.62-7.65(m,1H),7.84(d,1H).
1HNMR (400MHz, CDCl 3 ) δ 0.88 (t, 3H), 1.31-1.47 (m, 10H), 2.20 (t, 2H), 6.87 (t, 1H), 7.51 (d, 1H), 7.60 (d, 1H), 7.62-7.65 (m, 1H), 7.84 (d, 1H).
中间化合物54b的合成Synthesis of intermediate compound 54b
将所得中间化合物54a(5.84g，0.02mol)加入盛有30ml四氢呋喃的100ml三口瓶中，加入15g浓盐酸(35％)，搅拌0.5h后，控制温度在5℃下滴加亚硝酸异戊酯(2.36g，0.02mol)，滴加完毕后继续在10℃下反应3h。反应完毕后，将反应液倒入水中，乙酸乙酯萃取，收集有机相，水洗有机相至中性。干燥有机相，旋蒸除去有机溶剂，用10g石油醚重结晶，低温下抽滤，得白色固体3.85g，产率60％，经鉴定为中间化合物54b。Add the obtained intermediate compound 54a (5.84g, 0.02mol) into a 100ml three-necked flask containing 30ml tetrahydrofuran, add 15g concentrated hydrochloric acid (35%), stir for 0.5h, control the temperature and add isoamyl nitrite dropwise at 5℃ (2.36g, 0.02mol), continue to react at 10°C for 3h after the addition is complete. After the completion of the reaction, the reaction solution was poured into water, extracted with ethyl acetate, the organic phase was collected, and the organic phase was washed with water until it became neutral. The organic phase was dried, the organic solvent was removed by rotary evaporation, recrystallized with 10 g of petroleum ether, and suction filtered at low temperature to obtain 3.85 g of a white solid with a yield of 60%, which was identified as the intermediate compound 54b.
1HNMR(400MHz,CDCl
3)δ0.88(t,3H),1.31-1.47(m,10H),6.87(t,1H),7.51(d,1H),7.60(d,1H),7.62-7.65(m,1H),7.84(d,1H),8.20(s,1H).
1HNMR (400MHz, CDCl 3 ) δ 0.88 (t, 3H), 1.31-1.47 (m, 10H), 6.87 (t, 1H), 7.51 (d, 1H), 7.60 (d, 1H), 7.62-7.65 ( m,1H), 7.84(d,1H), 8.20(s,1H).
目标化合物54的合成Synthesis of target compound 54
将所得中间化合产物54b(3.21g，0.01mol)和30ml四氢呋喃加入到100mL三口圆底烧瓶中，然后加入乙酰氯(0.78g，0.01mol)和三乙胺(1.35g，0.013mol)，常温搅拌反应1h。终止反应，将反应液过滤后，滤液倒入水中，用乙酸乙酯萃取，收集有机相后依次用5％的稀盐酸、饱和碳酸钠水溶液、蒸馏水洗涤，然后收集有机相，并用MgSO
4干燥过夜。过滤后减压蒸馏蒸掉有机相后，得白色固体3.45g，产率95.0％，经鉴定为化合物54。该化合物的核磁数据见下表。
Add the obtained intermediate compound 54b (3.21g, 0.01mol) and 30ml of tetrahydrofuran into a 100mL three-necked round bottom flask, then add acetyl chloride (0.78g, 0.01mol) and triethylamine (1.35g, 0.013mol), stir at room temperature Reaction for 1h. The reaction was terminated, the reaction solution was filtered, the filtrate was poured into water, extracted with ethyl acetate, the organic phase was collected and washed with 5% dilute hydrochloric acid, saturated sodium carbonate aqueous solution, and distilled water in turn, and then the organic phase was collected and dried overnight with MgSO 4 . After filtration, the organic phase was distilled off under reduced pressure to obtain 3.45 g of a white solid with a yield of 95.0%, which was identified as compound 54. The NMR data of this compound are shown in the table below.
制备实施例55-65：化合物55-65的制备Preparation Examples 55-65: Preparation of Compounds 55-65
重复制备实施例54的方法，适当改变反应原料，分别获得下表化合物55-65及其核磁数据。Repeat the method of Preparation Example 54 and appropriately change the reaction materials to obtain compounds 55-65 and their nuclear magnetic data in the following table.
紫外吸收性能测试UV absorption performance test
采用乙腈作溶剂，对化合物1及化合物37各自的紫外吸收进行了测试。其吸收谱图见 图2，最大吸收波长及其在365nm、395nm、405nm摩尔消光系数见下表1。Using acetonitrile as solvent, the UV absorption of compound 1 and compound 37 was tested. The absorption spectrum is shown in Figure 2, and the maximum absorption wavelength and its molar extinction coefficients at 365nm, 395nm and 405nm are shown in Table 1 below.
表1Table 1
由图2可见，相对于市售光引发剂OXE-02，化合物1及化合物37各自在350-420nm处具有更好的紫外吸收，而OXE-02在250-350nm处具有较好的紫外吸收。As can be seen from Figure 2, compared to the commercially available photoinitiator OXE-02, Compound 1 and Compound 37 each have better UV absorption at 350-420nm, while OXE-02 has better UV absorption at 250-350nm.
热稳定性测试Thermal stability test
利用差热分析(DSC)法测试光引发剂引发可聚合单体聚合的初始温度是衡量光引发剂热稳定性有效的方法。利用此方法，选用二缩三丙二醇二丙烯酸酯(TPGDA)作为单体，测试了化合物1与市售肟酯光引发剂OXE-02及CN201710620077.2专利中披露的香豆素肟酯化合物COXE-15各自引发TPGDA聚合的初始温度。差热分析测试结果谱图见图3。测试结果表明，化合物1引发TPGDA聚合的初始温度为175℃，OXE-02(其结构见下文)引发TPGDA聚合的初始温度为105℃，COXE-15(其结构见下文)引发TPGDA聚合初始温度为98℃。Using differential thermal analysis (DSC) to test the initial temperature of the photoinitiator to initiate polymerization of the polymerizable monomer is an effective method to measure the thermal stability of the photoinitiator. Using this method, using tripropylene glycol diacrylate (TPGDA) as the monomer, the compound 1 and the commercially available oxime ester photoinitiator OXE-02 and the coumarin oxime ester compound COXE- disclosed in the CN201710620077.2 patent were tested. 15 each initiates the initial temperature of TPGDA polymerization. Figure 3 shows the spectrum of differential thermal analysis test results. The test results show that the initial temperature of compound 1 to initiate TPGDA polymerization is 175°C, the initial temperature of OXE-02 (see below for its structure) to initiate TPGDA polymerization is 105°C, and the initial temperature of COXE-15 (see below for its structure) to initiate TPGDA polymerization is 98°C.
另外，采用化合物2-36和38-65中的每一个重复上述热稳定性实验。结果显示，化合物2-36和38-65各自引发TPGDA聚合的初始温度均高于150℃。In addition, the above-mentioned thermal stability experiment was repeated using each of Compounds 2-36 and 38-65. The results showed that the initial temperature at which compounds 2-36 and 38-65 each initiated TPGDA polymerization were higher than 150°C.
由此可见，根据本发明的化合物1-65在丙烯酸酯单体中的稳定性显著地高于市售商品OXE-02和COXE-15，因而本发明的化合物1-65具有更佳的热稳定性。It can be seen that the stability of the compound 1-65 in the acrylate monomer according to the present invention is significantly higher than that of the commercial products OXE-02 and COXE-15, so the compound 1-65 of the present invention has better thermal stability Sex.
COXE-15化学式如下所示:The chemical formula of COXE-15 is as follows:
感光性能测试Photographic performance test
1.Photo-DSC测试光引发剂的引发性能1. Photo-DSC test the initiation performance of the photoinitiator
利用Photo-DSC测试手段，测定了化合物1和37各自分别在365nm，395nm，405nm LED光源下，辐照光强为100mW/cm
2，辐照5min时引发TPGDA聚合时TPGDA的双键转化率。TPGDA在不同浓度光引发剂(化合物1)下的转化率与辐照时间关系图谱见图4、图5和图6，以及辐照5min时的双键转化率(化合物1和37)具体值汇总于下表2中。
Using the Photo-DSC test method, the double bond conversion rate of TPGDA when the TPGDA polymerization is initiated when the TPGDA polymerization is initiated at the irradiation intensity of 100mW/cm 2 under 365nm, 395nm, and 405nm LED light sources of Compounds 1 and 37, respectively, was measured. The conversion rate of TPGDA under different concentrations of photoinitiator (compound 1) and irradiation time is shown in Fig. 4, Fig. 5 and Fig. 6, and the double bond conversion rate (compound 1 and 37) specific value summary when irradiated for 5 min In Table 2 below.
表2Table 2
Photo-DSC测试结果表明，化合物1及37各自在3种UV-LED光源下均可以引发丙烯酸酯类单体聚合。Photo-DSC test results show that each of Compounds 1 and 37 can initiate the polymerization of acrylic monomers under three UV-LED light sources.
2.采用乌格拉(Ugra)晒版测试条作掩膜来测试光引发剂的感光性能2. Use Ugra as a mask to test the photosensitive performance of the photoinitiator
乌格拉晒版测试条的各段见图1。乌格拉晒版测试条分为5个控制段，从左到右分别是：连续密度梯尺段(1)；阴阳微米等线同心圆段(2)；全阶调网点段(3)；重影控制段(4)；高光、暗调控制段(5)。第一段：连续密度梯尺段共分为13个梯度用来控制曝光量和显影。第二段：阴阳微米等线同心圆段：由12个阴阳微米等线组成的同心圆线图，分别为4、6、8、10、12、15、20、25、30、40、55、70，用于检测晒PS版时的曝光和显影情况。第三段：全阶调网点段：由10％-100％、极差为10％的评网组成，分为上下两行排列，用于测量晒版、打样和印刷的网点转移情况，并可测制出胶片网点与晒版、打样和印刷网店变化曲线图。第四段：重影控制段：由线宽60线/厘米、面积率为60％的细线条组成，它分为4小块，0°、45°、90°三个角度排列线条和有1/4的D小块中以两边90°、中间小方块45°、上下90°的小短线排列。第五段：高光、暗调控制段，精细网点段由高光小网点与暗调深网点对应排列，用于精细控制晒版曝光和显影的准确性。将包含光引发剂的感光组合物涂敷于铝基板上，然后曝光显影，从得到的图像的连续调梯尺评价感度，从微线条测试块区域评价精度，从而评价感光组合物配方的优劣。The sections of the Ugra printed test strip are shown in Figure 1. The test strip of Ugra printing plate is divided into 5 control sections. From left to right, they are: continuous density ladder section (1); Yin and Yang micron contour concentric circle section (2); full-step adjustment dot section (3); heavy Shadow control section (4); highlight and dark control section (5). The first section: The continuous density ladder section is divided into 13 gradients to control the exposure and development. The second section: Concentric circles with yin and yang micrometer contours: Concentric circles with 12 yin and yang micrometer contours, 4, 6, 8, 10, 12, 15, 20, 25, 30, 40, 55, 70, used to detect the exposure and development of the PS plate. The third section: Full-scale adjustment dot section: It is composed of 10%-100% and a range of 10%, and is arranged in two rows. It is used to measure the transfer of printing, proofing and printing. Measure and produce the change curve graph of film dot and printing, proofing and printing online shop. The fourth section: Ghost control section: It is composed of thin lines with a line width of 60 lines/cm and an area rate of 60%. It is divided into 4 small blocks, with lines arranged at three angles of 0°, 45°, and 90°, and there is 1 The D block of /4 is arranged in small short lines with 90° on both sides, 45° in the middle, and 90° up and down. The fifth segment: highlight and dark tone control segment, the fine dot segment is arranged by the small highlight dots and the dark deep dots correspondingly, which is used to finely control the accuracy of exposure and development. A photosensitive composition containing a photoinitiator is coated on an aluminum substrate, and then exposed and developed. The sensitivity is evaluated from the continuous scale of the obtained image, and the accuracy is evaluated from the micro-line test block area, thereby evaluating the advantages and disadvantages of the photosensitive composition formulation .
具体地，按照以下步骤对化合物1-65各自作为光引发剂的感光性能进行测试。Specifically, the photosensitivity of each compound 1-65 as a photoinitiator was tested according to the following steps.
(1)按照如下组成配制含有光引发剂的感光性组合物：(1) Prepare a photosensitive composition containing a photoinitiator according to the following composition:
上述组合物中光引发剂选自本发明的化合物1-65或现有技术已知的光引发剂(作对比)。丙烯酸酯树脂为从上海釜顺国际贸易有限公司购买的商品名为FS2600K的树脂，官能度为2，数均分子量1400。二季戊四醇六丙烯酸酯为从上海釜顺国际贸易有限公司购买的商品名为 GM66G0C的产品。结晶紫染料为从上海国药购买的商品名为六甲基玫苯胺盐酸盐的产品。感光性能测试The photoinitiator in the above composition is selected from compounds 1-65 of the present invention or photoinitiators known in the prior art (for comparison). Acrylic resin is a resin purchased from Shanghai Fushun International Trade Co., Ltd. under the trade name FS2600K, with a functionality of 2, and a number average molecular weight of 1400. Dipentaerythritol hexaacrylate is a product under the trade name GM66G0C purchased from Shanghai Fushun International Trade Co., Ltd. Crystal violet dye is a product purchased from Shanghai Sinopharm under the trade name of hexamethyl rose aniline hydrochloride. Photographic performance test
(2)将上述各组合物在黄光下搅拌混合均匀，利用离心机旋涂在预先处理好的并满足下列条件的PS铝版基上：(2) Stir and mix the above-mentioned compositions uniformly under yellow light, and spin-coat on the PS aluminum plate substrate that has been pre-treated and meets the following conditions by using a centrifuge:
铝板基尺寸：1030mm×800mmAluminum base size: 1030mm×800mm
铝板基厚度：0.28-0.3mmAluminum base thickness: 0.28-0.3mm
砂目规格：Ra＝0.5-0.6μmSand mesh specifications: Ra＝0.5-0.6μm
Rh＝0.3-0.35μmRh＝0.3-0.35μm
阳极氧化膜重量：3-3.5g/m
2
Anodized film weight: 3-3.5g/m 2
控制离心涂布机的转速，使涂在铝版基上的涂布量(以固含量计)为1.0-2.5g/m
2，在离心涂布机上初步干燥后，转移到100℃的鼓风干燥机中干燥3分钟，得紫激光CTP原版。然后，用Ugra测试条做掩膜测试版材的感光性能，曝光一段时间后用1％NaOH水溶液显影。
Control the rotating speed of the centrifugal coater so that the coating amount (in terms of solid content) coated on the aluminum plate base is 1.0-2.5g/m 2 , after preliminary drying on the centrifugal coater, transfer to a blast at 100°C Dry in the dryer for 3 minutes to get the original CTP of the violet laser. Then, use the Ugra test strip as a mask to test the photosensitive performance of the plate, and develop it with 1% NaOH aqueous solution after a period of exposure.
在曝光区，可光聚合化合物在引发剂存在下发生聚合反应，显影液中不溶，而非曝光区是可溶的，于是得到阴图。通过曝光显影，从得到的图像的连续调梯尺评价光引发剂的感度。引发剂体系感光度特征为显影后保留了(即聚合的)最高灰阶数。灰阶数越高，表明测试体系灵敏度越高。结果示于表3中。In the exposed area, the photopolymerizable compound undergoes polymerization reaction in the presence of the initiator, and is insoluble in the developer, while the non-exposed area is soluble, so a negative image is obtained. By exposure and development, the sensitivity of the photoinitiator was evaluated from the continuous scale of the obtained image. The sensitivity of the initiator system is characterized by the highest number of gray levels retained (ie, polymerized) after development. The higher the number of gray levels, the higher the sensitivity of the test system. The results are shown in Table 3.
表3table 3
在本申请中,OXE-01表示1-[4-(苯硫基)苯基]-1,2-辛烷二酮2-(O-苯甲酰肟)，OXE-02表示1-(6-邻甲基苯甲酰基-9-乙基咔唑-3-基)-(3-乙酮)-1-肟乙酸酯，结构式分别如下：In this application, OXE-01 means 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime), OXE-02 means 1-(6 -O-methylbenzoyl-9-ethylcarbazol-3-yl)-(3-ethanone)-1-oxime acetate, the structural formulas are as follows:
由表3中的实验结果可以明显看出，本发明化合物1-65在365nm、385nm、395nm和405nm处灰阶数均高于商购的光引发剂OXE-01和OXE-02。也就是说，本发明的包含五元芳杂环结构的肟酯类光引发剂，其在365nm、385nm、395nm和405nm波长处感光性能更为优异，适合用于365nm、385nm、395nm、405nm的UV-LED光源。It can be clearly seen from the experimental results in Table 3 that the number of gray levels at 365 nm, 385 nm, 395 nm and 405 nm of Compound 1-65 of the present invention is higher than that of the commercially available photoinitiators OXE-01 and OXE-02. That is to say, the oxime ester photoinitiator containing the five-membered aromatic heterocyclic structure of the present invention has better photosensitive performance at 365nm, 385nm, 395nm and 405nm wavelengths, and is suitable for use in 365nm, 385nm, 395nm, 405nm wavelengths. UV-LED light source.
综上所述，本发明式(I)和(II)所示的包含五元芳杂环结构的肟酯类光引发剂在365nm、385nm、395nm和405nm波长处具有较好的感光性能，优于现阶段可商购的OXE-01和OXE-02等酮肟酯类光引发剂。另外本发明公开的化合物生产工艺简单，产率高，非常适合于工业生产。此类化合物与365nm、385nm、395nm、405nm的UV-LED光源匹配性良好，可广泛应用于UV-LED光固化所涉及的领域。鉴于目前可应用于UV-LED的光引发剂品种较少，从一定程度上限制了UV-LED光源在紫外光固化领域的推广应用，故本发明光引发剂可为推动绿色环保的UV-LED光源在UV光固化行业的广泛应用做出贡献。In summary, the oxime ester photoinitiator containing a five-membered aromatic heterocyclic structure represented by formulas (I) and (II) of the present invention has good photosensitive properties at wavelengths of 365nm, 385nm, 395nm and 405nm, and At this stage, ketoxime ester photoinitiators such as OXE-01 and OXE-02 are commercially available. In addition, the compound disclosed in the invention has a simple production process and a high yield, which is very suitable for industrial production. Such compounds have good compatibility with UV-LED light sources of 365nm, 385nm, 395nm, 405nm, and can be widely used in the fields involved in UV-LED light curing. In view of the fact that there are fewer types of photoinitiators that can be applied to UV-LEDs, which limits the promotion and application of UV-LED light sources in the field of UV curing to a certain extent, the photoinitiators of the present invention can be used to promote green and environmentally friendly UV-LEDs The light source contributes to the wide application of UV curing industry.
Claims (14)
- 式(I)和(II)的包含不饱和五元杂环结构的肟酯化合物：The oxime ester compounds of formula (I) and (II) containing an unsaturated five-membered heterocyclic structure:
其中among themm为0-8的整数；m is an integer of 0-8;n和n’相同并且为0或1；n and n’ are the same and are 0 or 1;m个A 1以及A 2相同或不同，并且相互独立地表示O、S和NR a，其中R a为H或C 1-C 6烷基； m of A 1 and A 2 are the same or different, and each independently represents O, S and NR a, wherein R a is H or C 1 -C 6 alkyl;R 1、R 2、R 3、R 4相同或不同，并且相互独立地表示氢、卤素、硝基、氨基、氰基、C 1-C 20烷基、C 1-C 20烷氧基、C 1-C 20烷硫基、单C 1-C 12烷基氨基、二C 1-C 12烷基氨基、C 6-C 18芳氧基或C 6-C 18芳硫基，其中前述C 6-C 18芳氧基和C 6-C 18芳硫基基团中的芳基可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、NH 2、氰基、C 1-C 6烷基、C 1-C 6烷氧基和C 1-C 6烷硫基； R 1 , R 2 , R 3 , and R 4 are the same or different, and independently represent hydrogen, halogen, nitro, amino, cyano, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, mono C 1 -C 12 alkylamino, di C 1 -C 12 alkylamino, C 6 -C 18 aryloxy or C 6 -C 18 arylthio, wherein the aforementioned C 6 The aryl groups in the -C 18 aryloxy and C 6 -C 18 arylthio groups may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, NH 2 , cyano, C 1 -C 6 alkyl, C 1 -C 6 alkoxy and C 1 -C 6 alkylthio;R 5是氢、卤素、硝基、氰基、C 1-C 20烷基、C 1-C 20烷氧基、C 1-C 20烷硫基、C 6-C 18芳基、C 6-C 18芳基C 1-C 6烷基、C 6-C 18芳基C 1-C 6亚烷基、C 6-C 18芳氧基、C 6-C 18芳硫基、9H-咔唑-9基-C 1-C 6烷基、9H-咔唑-9基-C 1-C 6亚烷基、9H-芴-9基-C 1-C 6烷基或9H-芴-9基-C 1-C 6亚烷基，其中前述C 6-C 18芳基、C 6-C 18芳基C 1-C 6烷基、C 6-C 18芳基C 1-C 6亚烷基、C 6-C 18芳氧基、C 6-C 18芳硫基、9H-咔唑-9基-C 1-C 6烷基、9H-咔唑-9基-C 1-C 6亚烷基、9H-芴-9基-C 1-C 6烷基和9H-芴-9基-C 1-C 6亚烷基基团中的芳基可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、NH 2、氰基、C 1-C 6烷基、C 1-C 6烷氧基、C 1-C 6烷硫基和二苯基氨基，其中二苯基氨基中的苯基各自独立地任选包含一个或多个选自卤素、C 1-C 6烷基、C 1-C 6烷氧基和C 1-C 6烷硫基的取代基取代； R 5 is hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, C 6 -C 18 aryl, C 6- C 18 aryl C 1 -C 6 alkyl, C 6 -C 18 aryl C 1 -C 6 alkylene, C 6 -C 18 aryloxy, C 6 -C 18 arylthio, 9H-carbazole -9 group-C 1 -C 6 alkyl group, 9H-carbazol-9 group-C 1 -C 6 alkylene group, 9H-fluoren-9 group-C 1 -C 6 alkyl group or 9H-fluoren-9 group -C 1 -C 6 alkylene group, wherein the aforementioned C 6 -C 18 aryl group, C 6 -C 18 aryl group, C 1 -C 6 alkyl group, C 6 -C 18 aryl group, C 1 -C 6 alkylene group , C 6 -C 18 aryloxy group, C 6 -C 18 arylthio group, 9H-carbazol-9 group-C 1 -C 6 alkyl group, 9H-carbazol-9 group-C 1 -C 6 alkylene Group, 9H-fluoren-9 group-C 1 -C 6 alkyl group and 9H-fluoren-9 group-C 1 -C 6 alkylene group in the aryl group can be optionally selected by one or more independently Substitution from the following group: halogen, nitro, hydroxyl, mercapto, NH 2 , cyano, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio and two Phenylamino, wherein each of the phenyl groups in the diphenylamino group independently optionally contains one or more selected from halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy and C 1 -C 6 alkane Substituent substitution of thio group;R 6与R 6’相同或不同，并且相互独立地表示H、氰基、C 1-C 20烷基、C 3-C 10环烷基、C 4-C 10环烷基烷基、C 4-C 10烷基环烷基、C 6-C 20芳基、C 7-C 20芳烷基或C 7-C 20烷基芳基，其中前述C 1-C 20烷基、C 3-C 10环烷基、C 4-C 10环烷基烷基、C 4-C 10烷基环烷基、C 6-C 20芳基、C 7-C 20芳烷基和C 7-C 20烷基芳基任选地被一个或多个独立地选自下组的基团取代：C 1-C 6烷基、C 1-C 6烷硫基、C 1-C 6烷氧基、卤素、硝基、氨基、单(C 1-C 6烷基)氨基、二(C 1-C 6烷基)氨基和巯基；以及 R 6 and R 6 ′ are the same or different, and independently represent H, cyano, C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkyl alkyl, C 4 -C 10 alkyl cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl or C 7 -C 20 alkyl aryl, wherein the aforementioned C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkyl alkyl, C 4 -C 10 alkyl cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkane Alkylaryl is optionally substituted with one or more groups independently selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 alkylthio, C 1 -C 6 alkoxy, halogen, Nitro, amino, mono(C 1 -C 6 alkyl)amino, di(C 1 -C 6 alkyl)amino, and mercapto; andR 7与R 7’相同或不同，并且相互独立地表示C 1-C 20烷基、C 3-C 10环烷基、C 4-C 10环烷基烷基、C 4-C 10烷基环烷基、C 6-C 20芳基、C 7-C 20芳烷基或C 7-C 20烷基芳基，其中前述C 1-C 20 烷基、C 3-C 10环烷基、C 4-C 10环烷基烷基、C 4-C 10烷基环烷基、C 6-C 20芳基、C 7-C 20芳烷基和C 7-C 20烷基芳基任选地被一个或多个独立地选自下组的基团取代：C 1-C 6烷基、C 1-C 6烷硫基、C 1-C 6烷氧基、卤素、硝基、氨基、单(C 1-C 6烷基)氨基、二(C 1-C 6烷基)氨基和巯基。 R 7 and R 7 'are the same or different, and independently represent C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkyl alkyl, C 4 -C 10 alkyl Cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl or C 7 -C 20 alkyl aryl, wherein the aforementioned C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkylalkyl, C 4 -C 10 alkylcycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkyl aryl are optional Ground is substituted by one or more groups independently selected from the following group: C 1 -C 6 alkyl, C 1 -C 6 alkylthio, C 1 -C 6 alkoxy, halogen, nitro, amino, Mono(C 1 -C 6 alkyl)amino, di(C 1 -C 6 alkyl)amino and mercapto groups. - 根据权利要求1的化合物，其中m为0-4的整数，优选为0、1或2。The compound according to claim 1, wherein m is an integer of 0-4, preferably 0, 1, or 2.
- 根据权利要求1或2的化合物，其中R a为H或C 1-C 4烷基；优选的是，m个A 1以及A 2彼此相同，并且表示O、S或NR a，其中R a为H或C 1-C 4烷基，优选H、甲基或乙基。 The compound of claim 1 or claim 2, wherein R a is H or C 1 -C 4 alkyl; preferably is, m of A 1 and A 2 identical to each other, and represent O, S or NR a, wherein R a is H or C 1 -C 4 alkyl, preferably H, methyl or ethyl.
- 根据权利要求1-3中任一项的化合物，其中The compound according to any one of claims 1-3, whereinR 1、R 2、R 3、R 4相同或不同，并且相互独立地表示氢、卤素、硝基、氨基、氰基、C 1-C 6烷基、C 1-C 6烷氧基、C 1-C 6烷硫基、单C 1-C 6烷基氨基、二C 1-C 6烷基氨基、C 6-C 10芳氧基或C 6-C 10芳硫基，其中前述C 6-C 10芳氧基和C 6-C 10芳硫基基团中的芳基可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、NH 2、氰基、C 1-C 4烷基、C 1-C 4烷氧基和C 1-C 4烷硫基； R 1 , R 2 , R 3 , R 4 are the same or different, and independently represent hydrogen, halogen, nitro, amino, cyano, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, mono C 1 -C 6 alkylamino, di C 1 -C 6 alkylamino, C 6 -C 10 aryloxy or C 6 -C 10 arylthio, wherein the aforementioned C 6 The aryl groups in the -C 10 aryloxy and C 6 -C 10 arylthio groups may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, NH 2 , cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1 -C 4 alkylthio;优选的是，R 1、R 2、R 3、R 4相同或不同，并且相互独立地表示氢、卤素、硝基、氨基、氰基、C 1-C 4烷基、C 1-C 4烷氧基、C 1-C 4烷硫基、单C 1-C 4烷基氨基、二C 1-C 4烷基氨基、苯氧基或苯硫基，其中前述苯氧基和苯硫基基团中的苯基可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、NH 2、氰基、C 1-C 4烷基、C 1-C 4烷氧基和C 1-C 4烷硫基。 Preferably, R 1 , R 2 , R 3 , and R 4 are the same or different, and independently represent hydrogen, halogen, nitro, amino, cyano, C 1 -C 4 alkyl, C 1 -C 4 alkane Oxy, C 1 -C 4 alkylthio, mono C 1 -C 4 alkylamino, di C 1 -C 4 alkylamino, phenoxy or phenylthio, wherein the aforementioned phenoxy and phenylthio The phenyl group in the group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, NH 2 , cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1 -C 4 alkylthio.
- 根据权利要求1-4中任一项的化合物，其中The compound according to any one of claims 1-4, whereinR 5表示氢、卤素、硝基、氰基、C 1-C 6烷基、C 1-C 6烷氧基、C 1-C 6烷硫基、C 6-C 13芳基、C 6-C 13芳基C 1-C 4烷基、C 6-C 13芳基C 1-C 4亚烷基、C 6-C 13芳氧基、C 6-C 13芳硫基、9H-咔唑-9基-C 1-C 4烷基、9H-咔唑-9基-C 1-C 4亚烷基、9H-芴-9基-C 1-C 4烷基或9H-芴-9基-C 1-C 4亚烷基，其中前述C 6-C 13芳基、C 6-C 13芳基C 1-C 4烷基、C 6-C 13芳基C 1-C 4亚烷基、C 6-C 13芳氧基、C 6-C 13芳硫基、9H-咔唑-9基-C 1-C 4烷基、9H-咔唑-9基-C 1-C 4亚烷基、9H-芴-9基-C 1-C 4烷基和9H-芴-9基-C 1-C 4亚烷基基团中的芳基可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、NH 2、氰基、C 1-C 4烷基、C 1-C 4烷氧基、C 1-C 4烷硫基和二苯基氨基，其中二苯基氨基中的苯基各自独立地任选包含一个或多个选自卤素、C 1-C 4烷基、C 1-C 4烷氧基和C 1-C 4烷硫基的取代基取代； R 5 represents hydrogen, halogen, nitro, cyano, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 6 -C 13 aryl, C 6- C 13 aryl, C 1 -C 4 alkyl, C 6 -C 13 aryl, C 1 -C 4 alkylene, C 6 -C 13 aryloxy, C 6 -C 13 arylthio, 9H-carbazole -9 group-C 1 -C 4 alkyl group, 9H-carbazol-9 group-C 1 -C 4 alkylene group, 9H-fluoren-9 group-C 1 -C 4 alkyl group or 9H-fluoren-9 group -C 1 -C 4 alkylene, wherein the aforementioned C 6 -C 13 aryl, C 6 -C 13 aryl C 1 -C 4 alkyl, C 6 -C 13 aryl C 1 -C 4 alkylene , C 6 -C 13 aryloxy group, C 6 -C 13 arylthio group, 9H-carbazol-9 group-C 1 -C 4 alkyl group, 9H-carbazol-9 group-C 1 -C 4 alkylene Group, 9H-fluoren-9 group-C 1 -C 4 alkyl group and 9H-fluoren-9 group-C 1 -C 4 alkylene group in the aryl group can be optionally selected by one or more independently Substitution from the following group: halogen, nitro, hydroxyl, mercapto, NH 2 , cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio and two Phenylamino, wherein each of the phenyl groups in the diphenylamino group independently optionally contains one or more selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1 -C 4 alkane Substituent substitution of thio group;优选的是，R 5表示氢、卤素、硝基、氰基、C 1-C 4烷基、C 1-C 4烷氧基、C 1-C 4烷硫基、苯基、C 6-C 13芳基C 1-C 2烷基、C 6-C 13芳基C 1-C 2亚烷基、C 6-C 10芳氧基、C 6-C 10芳硫基、9H-咔唑-9基-C 1-C 2烷基、9H-咔唑-9基-C 1-C 2亚烷基、9H-芴-9基-C 1-C 2烷基或9H-芴-9基-C 1-C 2亚烷基，其中前述苯基、C 6-C 13芳基C 1-C 2烷基、C 6-C 13芳基C 1-C 2亚烷基、C 6-C 10芳氧基、C 6-C 10芳硫基、9H-咔唑-9基-C 1-C 2烷基、9H-咔唑-9基-C 1-C 2亚烷基、9H-芴-9基-C 1-C 2烷基和9H-芴-9基-C 1-C 2亚烷基基团中的芳基可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、NH 2、氰基、C 1-C 4烷基、C 1-C 4烷氧基、C 1-C 4烷硫基和二苯基氨基，其中二苯基氨基中的苯基各自独立地任选包含一个或多个选自卤素、C 1-C 4烷基、C 1-C 4烷氧基和C 1-C 4烷硫基的取代基。 Preferably, R 5 represents hydrogen, halogen, nitro, cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, phenyl, C 6 -C 13 aryl C 1 -C 2 alkyl, C 6 -C 13 aryl C 1 -C 2 alkylene, C 6 -C 10 aryloxy, C 6 -C 10 arylthio, 9H-carbazole- 9 group-C 1 -C 2 alkyl group, 9H-carbazol-9 group-C 1 -C 2 alkylene group, 9H-fluoren-9 group-C 1 -C 2 alkyl group or 9H-fluoren-9 group- C 1 -C 2 alkylene group, wherein the aforementioned phenyl group, C 6 -C 13 aryl group C 1 -C 2 alkyl group, C 6 -C 13 aryl group C 1 -C 2 alkylene group, C 6 -C 10 Aryloxy group, C 6 -C 10 arylthio group, 9H-carbazol-9 group-C 1 -C 2 alkyl group, 9H-carbazol-9 group-C 1 -C 2 alkylene group, 9H-fluorene- The aryl group in the 9 group-C 1 -C 2 alkyl group and the 9H-fluoren-9 group-C 1 -C 2 alkylene group may optionally be one or more groups independently selected from the following group Substitution: halogen, nitro, hydroxyl, mercapto, NH 2 , cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio and diphenylamino, two of which The phenyl groups in the phenylamino group each independently optionally include one or more substituents selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, and C 1 -C 4 alkylthio.
- 根据权利要求1-5中任一项的方法，其中The method according to any one of claims 1-5, whereinR 6与R 6’相同或不同，并且相互独立地表示H、氰基、C 1-C 6烷基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 4-C 8烷基环烷基、C 6-C 10芳基、C 7-C 11芳烷基或C 7-C 11烷基芳基，其中前述C 1-C 6烷基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 4-C 8烷基环烷基、C 6-C 10芳基、C 7-C 11芳烷基和C 7-C 11烷基芳基任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、C 1-C 4烷硫基、C 1-C 4烷氧基、卤素、硝基、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基和巯基； R 6 and R 6 ′ are the same or different, and independently represent H, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkyl alkyl, C 4 -C 8 alkyl cycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl or C 7 -C 11 alkyl aryl, wherein the aforementioned C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl, and C 7 -C 11 alkane Alkylaryl is optionally substituted with one or more groups independently selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkylthio, C 1 -C 4 alkoxy, halogen, Nitro, amino, mono(C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkyl)amino, and mercapto;优选的是，R 6与R 6’相同或不同，并且相互独立地表示H、氰基、C 1-C 6烷基、C 3-C 6环烷基或C 3-C 6环烷基C 1-C 2烷基，其中前述C 1-C 6烷基、C 3-C 6环烷基和C 3-C 6环烷基C 1-C 2烷基任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、C 1-C 4烷硫基、C 1-C 4烷氧基、卤素、硝基、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基和巯基。 Preferably, R 6 and R 6 ′ are the same or different and independently represent H, cyano, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl or C 3 -C 6 cycloalkyl C 1 -C 2 alkyl, wherein the aforementioned C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl and C 3 -C 6 cycloalkyl C 1 -C 2 alkyl are optionally separated by one or more Substitution by a group selected from the following group: C 1 -C 4 alkyl, C 1 -C 4 alkylthio, C 1 -C 4 alkoxy, halogen, nitro, amino, mono (C 1 -C 4 Alkyl)amino, di(C 1 -C 4 alkyl)amino and mercapto.
- 根据权利要求1-6中任一项的化合物，其中The compound according to any one of claims 1-6, whereinR 7与R 7’相同或不同，并且相互独立地表示C 1-C 6烷基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 4-C 8烷基环烷基、C 6-C 10芳基、C 7-C 11芳烷基或C 7-C 11烷基芳基，其中前述C 1-C 6烷基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 4-C 8烷基环烷基、C 6-C 10芳基、C 7-C 11芳烷基和C 7-C 11烷基芳基任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、C 1-C 4烷硫基、C 1-C 4烷氧基、卤素、硝基、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基和巯基； R 7 and R 7 'are the same or different, and independently represent C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkyl alkyl, C 4 -C 8 alkyl Cycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl or C 7 -C 11 alkyl aryl, wherein the aforementioned C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl and C 7 -C 11 alkyl aryl optionally Ground is substituted by one or more groups independently selected from the following group: C 1 -C 4 alkyl, C 1 -C 4 alkylthio, C 1 -C 4 alkoxy, halogen, nitro, amino, Mono(C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkyl)amino and mercapto;优选的是，R 7与R 7’相同或不同，并且相互独立地表示C 1-C 4烷基或苯基，其中前述C 1-C 4烷基和苯基任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、C 1-C 4烷硫基、C 1-C 4烷氧基、卤素、硝基、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基和巯基。 Preferably, R 7 and R 7 ′ are the same or different, and independently represent C 1 -C 4 alkyl or phenyl, wherein the aforementioned C 1 -C 4 alkyl and phenyl are optionally substituted by one or more Substitution groups independently selected from the following group: C 1 -C 4 alkyl, C 1 -C 4 alkylthio, C 1 -C 4 alkoxy, halogen, nitro, amino, mono (C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkyl)amino and mercapto.
- 根据权利要求1的化合物，其中式(I)和(II)化合物选自下组：The compound according to claim 1, wherein the compounds of formula (I) and (II) are selected from the group consisting of:
- 一种制备如权利要求1-8中任一项所要求的化合物的方法，包括以下步骤：A method for preparing a compound as claimed in any one of claims 1-8, comprising the following steps:(1)肟化反应：当n和n’为0时，使式(III)和(IV)化合物各自与羟胺和/或盐酸羟胺进行肟化反应，分别得到式(IIIa)和(IVa)化合物，(1) Oximation reaction: when n and n'are 0, the compounds of formula (III) and (IV) are oximated with hydroxylamine and/or hydroxylamine hydrochloride to obtain compounds of formula (IIIa) and (IVa) respectively ,
当n和n’为1时，使式(III)和(IV)化合物各自与选自亚硝酸、亚硝酸盐和亚硝酸烷基酯中的试剂进行肟化反应，分别得到式(IIIb)和(IVb)化合物，When n and n'are 1, the compounds of formula (III) and (IV) are each reacted with a reagent selected from the group consisting of nitrous acid, nitrite and alkyl nitrite to obtain formula (IIIb) and (IVb) compound,
其中式(III)、(IV)、(IIIa)、(IVa)、(IIIb)和(IVb)中的m、A 1、A 2、R 1-R 4和R 6，式(III)、(IIIa)和(IIIb)中的R 5以及式(IV)、(IVa)和(IVb)中的R 6’如权利要求1-8中任一项所定义；以及 Where m, A 1 , A 2 , R 1 -R 4 and R 6 in formulas (III), (IV), (IIIa), (IVa), (IIIb) and (IVb), formulas (III), ( R 5 in IIIa) and (IIIb) and R 6 ′ in formulas (IV), (IVa) and (IVb) are as defined in any one of claims 1-8; and(2)将式(IIIa)和(IIIb)酯化，将式(IVa)和(IVb)化合物酯化，分别得到式(I)和(II)化合物。(2) Esterification of formula (IIIa) and (IIIb), and esterification of compounds of formula (IVa) and (IVb) to obtain compounds of formula (I) and (II), respectively. - 根据权利要求9的方法，其中The method according to claim 9, wherein当n和n’为0时：肟化反应在乙酸钠、吡啶、哌啶、三乙胺、四甲基氢氧化铵或其混合物存在下进行；和/或，肟化反应在乙醇或含水的乙醇作为溶剂存在下进行；和/或，肟化反应的温度为60-120℃；和/或，肟化反应时间为0.1-20小时，优选0.5-10小时；和/或，式(III)和(IV)化合物各自与选自羟胺和/或盐酸羟胺的化合物的摩尔比为1:1.5-1.5:1，优选为1:1.2-1.2:1；When n and n'are 0: the oximation reaction is carried out in the presence of sodium acetate, pyridine, piperidine, triethylamine, tetramethylammonium hydroxide or a mixture thereof; and/or, the oximation reaction is carried out in ethanol or water It is carried out in the presence of ethanol as a solvent; and/or, the temperature of the oximation reaction is 60-120°C; and/or, the oximation reaction time is 0.1-20 hours, preferably 0.5-10 hours; and/or, formula (III) The molar ratio of each of and (IV) compound to a compound selected from hydroxylamine and/or hydroxylamine hydrochloride is 1:1.5-1.5:1, preferably 1:1.2-1.2:1;当n和n’为1时，肟化反应在20-40％的浓盐酸存在下进行；和/或，肟化反应在四氢呋喃、乙醇或含水的乙醇作为溶剂存在下进行；和/或，肟化反应的温度为-30至20℃，优选5-20℃；和/或，肟化反应时间为0.1-20小时，优选0.5-10小时；和/或，式(III)和(IV)化合物各自与选自亚硝酸、亚硝酸盐和/或亚硝酸烷基酯的化合物的摩尔比为1:1.5-1.5:1，优选为1:1.2-1.2:1。When n and n'are 1, the oximation reaction is carried out in the presence of 20-40% concentrated hydrochloric acid; and/or, the oximation reaction is carried out in the presence of tetrahydrofuran, ethanol or water-containing ethanol as a solvent; and/or, oxime The temperature of the reaction is -30 to 20°C, preferably 5-20°C; and/or, the oximation reaction time is 0.1-20 hours, preferably 0.5-10 hours; and/or, compounds of formula (III) and (IV) The molar ratio of each to the compound selected from nitrous acid, nitrite and/or alkyl nitrite is 1:1.5-1.5:1, preferably 1:1.2-1.2:1.
- 根据权利要求9或10的方法，其中亚硝酸烷基酯为亚硝酸C 1-C 6烷基酯，例如亚硝酸甲酯、亚硝酸乙酯、亚硝酸异丙酯、亚硝酸丁酯、亚硝酸异戊酯；和/或，步骤(2)的酯化采用选自下式(Va)、(IVb)和(Vc)化合物的酯化试剂进行： The method according to claim 9 or 10, wherein the alkyl nitrite is a C 1 -C 6 alkyl nitrite, such as methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, Isoamyl nitrate; and/or, the esterification of step (2) is performed with an esterification reagent selected from the following formulas (Va), (IVb) and (Vc):
其中X为卤素，尤其是氯，和R 7如权利要求1-8中任一项的R 7和R 7’所定义。 Wherein X is halogen, especially chlorine, and R 7 is as defined for R 7 and R 7 ′ in any one of claims 1-8. - 根据权利要求9-11中任一项的方法，其中酯化反应在选自下组的一种或多种催化剂存在下进行：硫酸、高氯酸、氯化锌、三氯化铁、吡啶、对甲基苯磺酸、氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、叔丁醇钠、乙醇钠、氢化钠、氢化钾、氢化钙和叔胺，例如三烷基胺，如三甲基胺和三乙胺。The method according to any one of claims 9-11, wherein the esterification reaction is carried out in the presence of one or more catalysts selected from the group consisting of sulfuric acid, perchloric acid, zinc chloride, ferric chloride, pyridine, P-toluene sulfonic acid, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium tert-butoxide, sodium ethoxide, sodium hydride, potassium hydride, calcium hydride and tertiary amines, such as trialkylamines, such as Methylamine and triethylamine.
- 根据权利要求9-12中任一项的方法，其中酯化反应在选自四氢呋喃、苯、甲苯、N，N-二甲基甲酰胺、二氯甲烷和丙酮的溶剂中进行；和/或，式(IIIa)、(IIIb)、(IVa)和(IVb)化合物各自与选自(Va)、(Vb)和(Vc)化合物的酯化试剂的摩尔比为1:1.5-1.5:1，优选为1:1.2-1.2:1。The method according to any one of claims 9-12, wherein the esterification reaction is carried out in a solvent selected from the group consisting of tetrahydrofuran, benzene, toluene, N,N-dimethylformamide, dichloromethane and acetone; and/or, The molar ratio of each compound of formula (IIIa), (IIIb), (IVa) and (IVb) to the esterification agent selected from the group consisting of (Va), (Vb) and (Vc) compounds is 1:1.5-1.5:1, preferably It is 1:1.2-1.2:1.
- 如权利要求1-8中任一项所要求的式(I)和(II)化合物各自作为光引发剂的用途，尤其是在UV-LED光固化体系中作为光引发剂的用途，特别是在辐射波长为350-450nm、尤其365-420nm的光固化体系中作为光引发剂的用途。The use of the compounds of formula (I) and (II) as claimed in any one of claims 1 to 8 as photoinitiators, especially in UV-LED light curing systems, especially in Use as a photoinitiator in a light curing system with a radiation wavelength of 350-450nm, especially 365-420nm.
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