WO2018094960A1 - Cinnamic acid benzoyl methyl ester compound and preparation method therefor and use thereof - Google Patents
Cinnamic acid benzoyl methyl ester compound and preparation method therefor and use thereof Download PDFInfo
- Publication number
- WO2018094960A1 WO2018094960A1 PCT/CN2017/081258 CN2017081258W WO2018094960A1 WO 2018094960 A1 WO2018094960 A1 WO 2018094960A1 CN 2017081258 W CN2017081258 W CN 2017081258W WO 2018094960 A1 WO2018094960 A1 WO 2018094960A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- alkyl
- alkylthio
- alkoxy
- alkynyl
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims description 7
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 title abstract description 6
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 title abstract description 5
- 229930016911 cinnamic acid Natural products 0.000 title abstract 4
- 235000013985 cinnamic acid Nutrition 0.000 title abstract 4
- 238000005886 esterification reaction Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 9
- -1 benzoylmethyl cinnamate compound Chemical class 0.000 claims description 126
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 45
- 229910052736 halogen Inorganic materials 0.000 claims description 45
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 42
- 150000002367 halogens Chemical class 0.000 claims description 34
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 32
- 125000005366 cycloalkylthio group Chemical group 0.000 claims description 30
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 claims description 29
- 125000005112 cycloalkylalkoxy group Chemical group 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- 125000004414 alkyl thio group Chemical group 0.000 claims description 26
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 26
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 25
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 22
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 22
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 21
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 claims description 21
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 21
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 21
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 150000002431 hydrogen Chemical class 0.000 claims description 20
- 125000000304 alkynyl group Chemical group 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 17
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 17
- UUEVFMOUBSLVJW-UHFFFAOYSA-N oxo-[[1-[2-[2-[2-[4-(oxoazaniumylmethylidene)pyridin-1-yl]ethoxy]ethoxy]ethyl]pyridin-4-ylidene]methyl]azanium;dibromide Chemical compound [Br-].[Br-].C1=CC(=C[NH+]=O)C=CN1CCOCCOCCN1C=CC(=C[NH+]=O)C=C1 UUEVFMOUBSLVJW-UHFFFAOYSA-N 0.000 claims description 17
- 125000005133 alkynyloxy group Chemical group 0.000 claims description 16
- 125000005109 alkynylthio group Chemical group 0.000 claims description 16
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 14
- 125000005843 halogen group Chemical group 0.000 claims description 14
- 150000003573 thiols Chemical group 0.000 claims description 14
- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 claims description 13
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 13
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 13
- 125000006650 (C2-C4) alkynyl group Chemical group 0.000 claims description 12
- 125000006766 (C2-C6) alkynyloxy 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
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 150000001721 carbon Chemical group 0.000 claims description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical compound [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 claims description 9
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 8
- 125000003320 C2-C6 alkenyloxy group Chemical group 0.000 claims description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical group [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 229940114081 cinnamate Drugs 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 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
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 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
- 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
- 125000004970 halomethyl group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 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
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- 125000006649 (C2-C20) alkynyl group Chemical group 0.000 claims description 2
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000103 lithium hydride Inorganic materials 0.000 claims description 2
- DIORMHZUUKOISG-UHFFFAOYSA-N sulfoformic acid Chemical compound OC(=O)S(O)(=O)=O DIORMHZUUKOISG-UHFFFAOYSA-N 0.000 claims description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 claims 1
- 238000013508 migration Methods 0.000 abstract description 12
- 230000005012 migration Effects 0.000 abstract description 12
- 239000003999 initiator Substances 0.000 abstract description 7
- 150000002576 ketones Chemical class 0.000 abstract description 5
- 238000004383 yellowing Methods 0.000 abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 49
- 238000006243 chemical reaction Methods 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- 229920006395 saturated elastomer Polymers 0.000 description 20
- 239000000706 filtrate Substances 0.000 description 19
- 238000005160 1H NMR spectroscopy Methods 0.000 description 17
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 17
- 239000012153 distilled water Substances 0.000 description 17
- 239000012074 organic phase Substances 0.000 description 17
- 238000001228 spectrum Methods 0.000 description 17
- 238000003756 stirring Methods 0.000 description 17
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 16
- 239000012295 chemical reaction liquid Substances 0.000 description 16
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 238000000016 photochemical curing Methods 0.000 description 11
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 238000001723 curing Methods 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 5
- WOGITNXCNOTRLK-VOTSOKGWSA-N (e)-3-phenylprop-2-enoyl chloride Chemical compound ClC(=O)\C=C\C1=CC=CC=C1 WOGITNXCNOTRLK-VOTSOKGWSA-N 0.000 description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 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 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000004434 sulfur atom Chemical group 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 3
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 3
- 125000004972 1-butynyl group Chemical group [H]C([H])([H])C([H])([H])C#C* 0.000 description 3
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 3
- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001345 alkine derivatives Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N phenyl propionaldehyde Natural products CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- SXNHDJZSIIUMBX-UHFFFAOYSA-N (1-hydroxycyclohexyl)-(4-propan-2-ylphenyl)methanone Chemical compound C1=CC(C(C)C)=CC=C1C(=O)C1(O)CCCCC1 SXNHDJZSIIUMBX-UHFFFAOYSA-N 0.000 description 2
- 125000006021 1-methyl-2-propenyl group Chemical group 0.000 description 2
- 125000006023 1-pentenyl group Chemical group 0.000 description 2
- 125000006017 1-propenyl group Chemical group 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- 125000006040 2-hexenyl group Chemical group 0.000 description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 2
- 125000006020 2-methyl-1-propenyl group Chemical group 0.000 description 2
- 125000006022 2-methyl-2-propenyl group Chemical group 0.000 description 2
- 125000006024 2-pentenyl group Chemical group 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 125000006041 3-hexenyl group Chemical group 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- NRUWOFDESMGKBK-UHFFFAOYSA-N (1-hydroxycyclohexyl)-(2-methylphenyl)methanone Chemical compound CC1=C(C=CC=C1)C(=O)C1(CCCCC1)O NRUWOFDESMGKBK-UHFFFAOYSA-N 0.000 description 1
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 description 1
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- AFDXODALSZRGIH-QPJJXVBHSA-N (E)-3-(4-methoxyphenyl)prop-2-enoic acid Chemical compound COC1=CC=C(\C=C\C(O)=O)C=C1 AFDXODALSZRGIH-QPJJXVBHSA-N 0.000 description 1
- 0 *=C1C=CC=C1 Chemical compound *=C1C=CC=C1 0.000 description 1
- 125000006079 1,1,2-trimethyl-2-propenyl group Chemical group 0.000 description 1
- 125000006059 1,1-dimethyl-2-butenyl group Chemical group 0.000 description 1
- 125000006033 1,1-dimethyl-2-propenyl group Chemical group 0.000 description 1
- 125000006060 1,1-dimethyl-3-butenyl group Chemical group 0.000 description 1
- 125000005919 1,2,2-trimethylpropyl group Chemical group 0.000 description 1
- 125000006061 1,2-dimethyl-1-butenyl group Chemical group 0.000 description 1
- 125000006034 1,2-dimethyl-1-propenyl group Chemical group 0.000 description 1
- 125000006062 1,2-dimethyl-2-butenyl group Chemical group 0.000 description 1
- 125000006035 1,2-dimethyl-2-propenyl group Chemical group 0.000 description 1
- 125000006063 1,2-dimethyl-3-butenyl group Chemical group 0.000 description 1
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- 125000006064 1,3-dimethyl-1-butenyl group Chemical group 0.000 description 1
- 125000006065 1,3-dimethyl-2-butenyl group Chemical group 0.000 description 1
- 125000006066 1,3-dimethyl-3-butenyl group Chemical group 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- 125000006073 1-ethyl-1-butenyl group Chemical group 0.000 description 1
- 125000006080 1-ethyl-1-methyl-2-propenyl group Chemical group 0.000 description 1
- 125000006036 1-ethyl-1-propenyl group Chemical group 0.000 description 1
- 125000006074 1-ethyl-2-butenyl group Chemical group 0.000 description 1
- 125000006081 1-ethyl-2-methyl-1-propenyl group Chemical group 0.000 description 1
- 125000006082 1-ethyl-2-methyl-2-propenyl group Chemical group 0.000 description 1
- 125000006037 1-ethyl-2-propenyl group Chemical group 0.000 description 1
- 125000006075 1-ethyl-3-butenyl group Chemical group 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006039 1-hexenyl group Chemical group 0.000 description 1
- 125000006025 1-methyl-1-butenyl group Chemical group 0.000 description 1
- 125000006044 1-methyl-1-pentenyl group Chemical group 0.000 description 1
- 125000006019 1-methyl-1-propenyl group Chemical group 0.000 description 1
- 125000006028 1-methyl-2-butenyl group Chemical group 0.000 description 1
- 125000006048 1-methyl-2-pentenyl group Chemical group 0.000 description 1
- 125000006030 1-methyl-3-butenyl group Chemical group 0.000 description 1
- 125000006052 1-methyl-3-pentenyl group Chemical group 0.000 description 1
- 125000006055 1-methyl-4-pentenyl group Chemical group 0.000 description 1
- IBXNCJKFFQIKKY-UHFFFAOYSA-N 1-pentyne Chemical compound CCCC#C IBXNCJKFFQIKKY-UHFFFAOYSA-N 0.000 description 1
- DTTDXHDYTWQDCS-UHFFFAOYSA-N 1-phenylcyclohexan-1-ol Chemical compound C=1C=CC=CC=1C1(O)CCCCC1 DTTDXHDYTWQDCS-UHFFFAOYSA-N 0.000 description 1
- 125000006067 2,2-dimethyl-3-butenyl group Chemical group 0.000 description 1
- 125000006068 2,3-dimethyl-1-butenyl group Chemical group 0.000 description 1
- 125000006069 2,3-dimethyl-2-butenyl group Chemical group 0.000 description 1
- 125000006070 2,3-dimethyl-3-butenyl group Chemical group 0.000 description 1
- 125000006076 2-ethyl-1-butenyl group Chemical group 0.000 description 1
- 125000006077 2-ethyl-2-butenyl group Chemical group 0.000 description 1
- 125000006078 2-ethyl-3-butenyl group Chemical group 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- IZGNAMNBBIETLY-UHFFFAOYSA-N 2-hydroxy-1-(4-methoxyphenyl)-2-methylpropan-1-one Chemical compound COC1=CC=C(C(=O)C(C)(C)O)C=C1 IZGNAMNBBIETLY-UHFFFAOYSA-N 0.000 description 1
- WLVPRARCUSRDNI-UHFFFAOYSA-N 2-hydroxy-1-phenyl-1-propanone Chemical compound CC(O)C(=O)C1=CC=CC=C1 WLVPRARCUSRDNI-UHFFFAOYSA-N 0.000 description 1
- RCHVDUSMVBWVNY-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-(4-methylsulfanylphenyl)propan-1-one Chemical compound CSC1=CC=C(C(=O)C(C)(C)O)C=C1 RCHVDUSMVBWVNY-UHFFFAOYSA-N 0.000 description 1
- OFIJHPVYJUDFGG-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-(4-phenylsulfanylphenyl)propan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1SC1=CC=CC=C1 OFIJHPVYJUDFGG-UHFFFAOYSA-N 0.000 description 1
- ZWVHTXAYIKBMEE-UHFFFAOYSA-N 2-hydroxyacetophenone Chemical compound OCC(=O)C1=CC=CC=C1 ZWVHTXAYIKBMEE-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 125000006026 2-methyl-1-butenyl group Chemical group 0.000 description 1
- 125000006045 2-methyl-1-pentenyl group Chemical group 0.000 description 1
- 125000006029 2-methyl-2-butenyl group Chemical group 0.000 description 1
- 125000006049 2-methyl-2-pentenyl group Chemical group 0.000 description 1
- 125000006031 2-methyl-3-butenyl group Chemical group 0.000 description 1
- 125000006053 2-methyl-3-pentenyl group Chemical group 0.000 description 1
- 125000006056 2-methyl-4-pentenyl group Chemical group 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- JKFFGXCJCMRHTJ-UHFFFAOYSA-N 3,3,3-trichloro-2-hydroxy-1-phenyl-2-(trichloromethyl)propan-1-one Chemical compound OC(C(=O)C1=CC=CC=C1)(C(Cl)(Cl)Cl)C(Cl)(Cl)Cl JKFFGXCJCMRHTJ-UHFFFAOYSA-N 0.000 description 1
- 125000006071 3,3-dimethyl-1-butenyl group Chemical group 0.000 description 1
- 125000006072 3,3-dimethyl-2-butenyl group Chemical group 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 125000006027 3-methyl-1-butenyl group Chemical group 0.000 description 1
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- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
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- 125000006051 4-methyl-2-pentenyl group Chemical group 0.000 description 1
- 125000003119 4-methyl-3-pentenyl group Chemical group [H]\C(=C(/C([H])([H])[H])C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000006043 5-hexenyl group Chemical group 0.000 description 1
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- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
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- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
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- 125000001246 bromo group Chemical group Br* 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
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- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001352 cyclobutyloxy group Chemical group C1(CCC1)O* 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000003113 cycloheptyloxy group Chemical group C1(CCCCCC1)O* 0.000 description 1
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000004410 cyclooctyloxy group Chemical group C1(CCCCCCC1)O* 0.000 description 1
- 125000001887 cyclopentyloxy group Chemical group C1(CCCC1)O* 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000000131 cyclopropyloxy group Chemical group C1(CC1)O* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 238000011907 photodimerization Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
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- 238000013112 stability test Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000004354 sulfur functional group Chemical group 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 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 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/22—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and doubly-bound oxygen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/612—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety
- C07C69/618—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety having unsaturation outside the six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/62—Halogen-containing esters
- C07C69/65—Halogen-containing esters of unsaturated acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
- C07C69/734—Ethers
-
- 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
- This invention relates to benzoylmethyl cinnamate compounds which are useful as photoinitiators and to the preparation and use of benzoylmethyl cinnamate compounds.
- Photocuring materials are widely accepted and paid attention to as a green, environmentally friendly, low-energy environmentally friendly material because they have no or only a small amount of solvent volatilization during the curing process.
- photocuring technology has been widely used in traditional fields such as coatings, inks, microelectronics, printing, etc., and is also used in the preparation of new fields such as laser recording and three-dimensional components.
- Photoinitiator also known as photosensitizer or photocuring agent, is an indispensable part of photocuring technology. It is a kind of energy that can absorb a certain wavelength in the ultraviolet (250-400nm) or visible (400-600nm) region. A compound which generates a radical, a cation, or the like to initiate polymerization of a monomer by polymerization crosslinking. In the photocuring system, the photoinitiator generally accounts for 3-5%, and although the content is low, it is a key component thereof, which plays a decisive role in the photocuring speed.
- the photoinitiator must meet the needs of different photocuring conditions and applications.
- the main objectives are: to improve light sensitivity, improve surface curing efficiency (antioxidation inhibition), improve deep curing properties, improve the solubility of photoinitiators in monomers and resins, and reduce toxicity and odor. It reduces the migration of the uncured initiator after curing and reduces the yellowing.
- Alpha-monohydroxyketone photoinitiators are commonly used photoinitiators, the most common of which are photoinitiators 1173 (2-hydroxy-2-methyl-1-phenylacetone) and 184 (1-hydroxycyclohexylbenzene). Ketone).
- Photoinitiator 1173 is a liquid, easy to use, is the main initiator in various types of photocurable varnish, excellent thermal stability, good yellowing resistance, and low price; the main disadvantage is that the benzaldehyde present in the photolysis product is bad. Odor, while having high volatility and strong migration.
- the photoinitiator 184 is a white powder and has a low volatility, but there is also a problem that the photolysis product has a heterogeneous and highly mobile property.
- the double bond in the cinnamoyl group opens under the action of ultraviolet light, and the double bonds on different molecules interact to form a four-membered ring, resulting in photodimerization crosslinking.
- the molecules in the exposed region are crosslinked to form a poorly soluble bulk network structure, and the molecular properties of the unexposed regions are unchanged, resulting in a difference in solubility in the developer. It is this feature that enables fine machining.
- the inventors of the present invention conducted extensive and intensive research in the field of photoinitiators in order to find a light which can improve the odor and migration of the ⁇ -monohydroxyketone photoinitiator.
- Initiator The present inventors have found that if a cinnamoyl group is introduced or attached to an ⁇ -monohydroxyketone photoinitiator, the cinnamoyl group can be polymerized and crosslinked under ultraviolet light, and the photoinitiator thus obtained retains ⁇ -single
- the advantages of the hydroxyketone photoinitiator also improve the problem of the odor and migration of the ⁇ -monohydroxyketone photoinitiator.
- the present invention has been achieved based on the foregoing findings.
- a novel benzoylmethyl ester cinnamate compound are useful as photoinitiators, capable of absorbing radiant heat in the range of 200-350 nm, good stability, resistance to yellowing, and, more importantly, such initiators compared to existing alpha-monohydroxyketones.
- the photoinitiator greatly improves the problem of strong odor and migration, and the ultraviolet red shift.
- Another object of the present invention is to provide a process for preparing the benzoylmethyl cinnamate compound of the present invention.
- Still another object of the present invention is to provide the use of the benzoyl methacrylate compound of the present invention as a photoinitiator.
- Using the benzoic acid benzoylmethyl ester compound of the present invention as a photoinitiator Compared with the existing ⁇ -monohydroxyketone photoinitiator, the problem of strong odor and migration is greatly improved, and the ultraviolet red shift.
- a benzoylmethyl cinnamate compound having the structure represented by the formula (I):
- R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from the group consisting of hydrogen, halogen, nitro, hydroxy, decyl, carboxyl, sulfonic acid, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 olefin Oxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 alkene a C 2 -C 20 alkynylthio group, a C 3 -C 20 cycloalkylthio group, a C 4 -C 20
- R 6 and R 7 are the same or different and are selected from a C 1 -C 6 alkyl group and a halogenated C 1 -C 6 alkyl group, or R 6 and R 7 together with the carbon atom to which they are attached form a C 3 -C 8 ring alkyl;
- R 8 , R 9 , R 10 , R 11 and R 12 are independently of each other selected from the group consisting of hydrogen, halogen, nitro, hydroxy, decyl, carboxyl, sulfonate, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 olefin Oxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 alkene a C 2 -C 20 alkynylthio group, a C 3 -C 20 cycloalkylthio group, a C 4 -C
- R 13 and R 14 are the same or different and are selected from the group consisting of H, C 1 -C 6 alkyl and halogenated C 1 -C 6 alkyl.
- R 6 and R 7 are the same or different and are selected from a C 1 -C 4 alkyl group and a halogenated C 1 -C 4 alkyl group, or R 6 and R 7 are attached thereto. Formation of C 5 -C 6 cycloalkyl group together with the carbon atom.
- R 13 and R 14 are the same or different and are selected from the group consisting of H, C 1 -C 4 alkyl and halogenated C 1 -C 4 alkyl, preferably R 13 And R 14 are both H.
- R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from the group consisting of hydrogen, halogen, nitro, hydroxy, decyl, carboxyl, sulfonic acid, amino, cyano, C 1 -C 6 alkyl, C 2- C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 olefin Oxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkene a C 2 -C 6 alkynylthio group, a C 3 -C 8 cycloalkylthio group, a C 4 -C 8 cyclo
- R 8 , R 9 , R 10 , R 11 and R 12 are independently of each other selected from the group consisting of hydrogen, halogen, nitro, hydroxy, decyl, carboxy, sulfonic acid, amino, cyano, C 1 -C 6 alkyl, C 2- C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 olefin Oxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkene a C 2 -C 6 alkynylthio group, a C 3 -C 8 cycloalkylthio group, a C 4 -C 8 cycl
- R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from the group consisting of hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1 -C 4 alkylthio, wherein The aforementioned C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1 -C 4 alkylthio may be optionally substituted by one or more groups independently selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1 -C 4 alkylthio; and/or
- R 8 , R 9 , R 10 , R 11 and R 12 are independently of each other selected from the group consisting of hydrogen, halogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 - a C 4 alkoxy group and a C 1 -C 4 alkylthio group, wherein the aforementioned C 1 -C 4 alkyl group, C 2 -C 4 alkenyl group, C 2 -C 4 alkynyl group, C 1 -C 4 alkoxy group and
- the C 1 -C 4 alkylthio group may be optionally substituted by one or more groups independently selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1- C 4 alkylthio group.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are as defined in items 1-7 One is defined, and X is a hydroxyl group or a halogen.
- the esterification reaction is carried out in the presence of a catalyst
- the catalyst is 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, sodium hydrogencarbonate, sodium t-butoxide, sodium ethoxide, sodium hydride, potassium hydride, calcium hydride and tertiary amines, such as trialkylamines, such as three Methylamine and triethylamine.
- Figure 1 is a UV absorption spectrum of Compounds 1173 and 1173CC
- Figure 2 is a UV absorption spectrum of Compounds 184 and 184-CC
- Figure 3 is a graph showing the relationship between the thermal decomposition rate of a compound and time
- Figure 4 is a graph showing the change in double bond of a polymerizable monomer obtained as a photoinitiator of compound 184-CC over time;
- Figure 5 is a graph showing the change in double bond conversion of a polymerizable monomer obtained by using a compound 1173-CC as a photoinitiator over time.
- R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from the group consisting of hydrogen, halogen, nitro, hydroxy, decyl, carboxyl, sulfonic acid, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 olefin Oxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 alkene a C 2 -C 20 alkynylthio group, a C 3 -C 20 cycloalkylthio group, a C 4 -C 20
- R 6 and R 7 are the same or different and are selected from a C 1 -C 6 alkyl group and a halogenated C 1 -C 6 alkyl group, or R 6 and R 7 together with the carbon atom to which they are attached form a C 3 -C 8 ring alkyl;
- R 8 , R 9 , R 10 , R 11 and R 12 are independently of each other selected from the group consisting of hydrogen, halogen, nitro, hydroxy, decyl, carboxyl, sulfonate, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 olefin Oxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 alkene a C 2 -C 20 alkynylthio group, a C 3 -C 20 cycloalkylthio group, a C 4 -C
- R 13 and R 14 are the same or different and are selected from the group consisting of H, C 1 -C 6 alkyl and halogenated C 1 -C 6 alkyl.
- the compound of the formula (I) retains the characteristics of the ⁇ -monohydroxyketone photoinitiator due to the presence of the ⁇ -monohydroxy ketone moiety, and additionally contains a cinnamoyl moiety which enables the compound to be in ultraviolet light.
- the polymerization cross-linking can occur under irradiation, and the compound of the formula (I) thus obtained improves the odor and migration of the ⁇ -monohydroxyketone photoinitiator while retaining the advantages of the ⁇ -monohydroxyketone photoinitiator. The problem.
- C n -C m in each case means that the number of carbon atoms contained in the group is nm.
- Halogen means fluoro, chloro, bromo and iodo. In the present invention, it is preferred that the halogen includes F, Cl or a combination thereof.
- C n -C m alkyl as used herein means having nm, for example 1-20, preferably 1-12, more preferably 1-8, particularly preferably 1-6, especially preferably 1-4 Branched or unbranched saturated hydrocarbon group of one carbon atom, 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-dimethylmethylmethylbut
- the C 1 -C 8 alkyl group may be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl and Its isomers.
- the C 1 -C 6 alkyl group may be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, pentyl, isopentyl, hexyl and isomers thereof.
- C 1 -C 4 alkyl may be methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl Base and its isomers.
- C 2 -C m alkenyl refers to a 2-m, for example 2-20, preferably 2-6, more preferably 2-4 carbon atoms and having one or more at any position Branched or unbranched unsaturated hydrocarbon groups of double bonds, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butyl Alkenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2 -pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3 -butenyl, 2-methyl-3 -buteny
- the C 2 -C 6 alkenyl group may be a vinyl group, a propenyl group, a 1-butenyl group, a 2-butenyl group, an isobutenyl group, a 1-pentenyl group, a 2-pentenyl group, a neopentenyl group, or a 1-hexyl group.
- the C 2 -C 4 alkenyl group may be a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-methylvinyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-methyl group.
- C 2 -C m alkynyl refers to having from 2 to m, for example from 2 to 20, preferably from 2 to 6, more preferably from 2 to 4, carbon atoms and having one or more positions at any position.
- a branched or unbranched unsaturated hydrocarbon group of a hydrazone bond such as an ethynyl group, a propynyl group, a 1-butynyl group, a 2-butynyl group, and isomers thereof.
- the C 2 -C 6 alkynyl group may be ethynyl, propynyl, 1-butynyl, 2-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentyne A group, a 1-hexynyl group, a 2-hexynyl group, a 3-hexynyl group, a 4-hexynyl group, a 5-hexynyl group, and isomers thereof.
- the C 2 -C 4 alkynyl group may be ethynyl, propynyl, 1-butynyl, 2-butynyl and isomers thereof.
- C 3 -C m cycloalkyl refers to a saturated alicyclic monocyclic group having 3 to m, for example 3 to 20, preferably 3 to 8, more preferably 5 to 6 ring carbon atoms. Groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.
- C 4 -C m cycloalkylalkyl denotes a cycloalkyl group substituted by an alkyl group and contains a total of 4 to m carbon atoms, for example 4 to 20, preferably 4 to 8 carbon atoms, wherein alkyl and Cycloalkyl is as defined herein.
- C n -C m alkoxy and “C n -C m alkylthio" mean that an oxygen atom or a sulfur atom is bonded as a linking group at any valence bond of a C n -C m alkyl group.
- C n -C m alkyl for example C 1 -C 20 alkoxy (or thio) group, preferably C 1 -C 12 alkoxy (or thio) group, more preferably C 1 -C 8 alkoxy (or sulphur)
- the group is particularly preferably a C 1 -C 6 alkoxy (or thio) group, particularly preferably a C 1 -C 4 alkoxy (or thio) group.
- the C 1 -C 8 alkoxy group may be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, pentyloxy, isopentyloxy Base, hexyloxy, heptyloxy, octyloxy, isooctyloxy and isomers thereof.
- the C 1 -C 4 alkoxy group may be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy and isomers thereof body.
- the C 1 -C 8 alkylthio group may be methylthio, ethylthio, propylthio, isopropylthio, n-butyl, 2-butylthio, tert-butylthio, pentylthio, isopentylthio. , hexylthio, heptylthio, octylthio, isooctylthio and isomers thereof.
- the C 1 -C 4 alkylthio group may be methylthio, ethylthio, propylthio, isopropylthio, n-butylthio and isomers thereof.
- C 2 -C m alkenyloxy and “C 2 -C m olefinylthio" mean that an oxygen atom or a sulfur atom is bonded as a linkage at any saturated valence bond in a C 2 -C m alkenyl group.
- a C 2 -C m alkenyl group of the group for example a C 2 -C 20 olefinic oxygen (or thio) group, preferably a C 2 -C 12 olefinic oxygen (or thio) group, more preferably a C 2 -C 8 olefinic oxygen (or A sulfur group, a C 2 -C 6 alkene (or sulfur) group is particularly preferred, and a C 2 -C 4 alkoxy (or sulfur) group is particularly preferred.
- the C 1 -C 4 alkenyloxy group may be a vinyloxy group, a propyleneoxy group, an isopropenyloxy group, a n-butenyloxy group, a sec-butenyloxy group, an isobutenyloxy group, a t-butenyloxy group, and an isomer thereof.
- the C 2 -C 4 alkenethio group may be an ethylenethio group, an acrylthio group, an isopropenylthio group, an n-butenylthio group, and an isomer thereof.
- C 2 -C m alkynyloxy and “C 2 -C m alkynylthio” mean that an oxygen atom or a sulfur atom is bonded as a linkage at any saturated valence bond in a C 2 -C m alkynyl group.
- a C 2 -C m alkynyl group of the group for example a C 2 -C 20 alkyne (or thio) group, preferably a C 2 -C 12 alkyne (or thio) group, more preferably a C 2 -C 8 alkyne (or Sulfur), particularly preferably C 2 -C 6 alkyne (or sulfur) group, particularly preferably C 2 -C 4 alkyne (or sulfur) group.
- the C 1 -C 4 alkynyloxy group may be ethynyloxy, propynyloxy, n-butynyloxy, sec-butynyloxy and isomers thereof.
- the C 2 -C 4 alkynylthio group may be acetylenethio, propynylthio, propynylthio, n-butynylthio, sec-butynylthio and isomers thereof.
- C 3 -C m cycloalkoxy and “C 3 -C m cycloalkylthio” mean that an oxygen atom or a sulfur atom is bonded as a linking group at any valence bond in a cycloalkyl group.
- C 3 -C m cycloalkyl for example C 3 -C 20 cycloalkoxy (or thio) group, preferably C 3 -C 8 cycloalkoxy (or thio) group, more preferably C 5 -C 6 cycloalkoxy ( Or sulfur).
- the C 3 -C 20 cycloalkoxy group may be a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group, a cyclodecyloxy group. Base and its isomers.
- the C 3 -C 20 cycloalkylthio group may be cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, cycloheptylthio, cyclooctylthio, cyclodecylthio Base and its isomers.
- C 6 -C m aryl refers to a monocyclic, bicyclic or tricyclic aromatic hydrocarbon group containing 6 to m carbon atoms, for example 6 to 18, preferably 6 to 10 carbon atoms.
- C 6 -C m aryl group examples include phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, xylyl, methylethylphenyl, diethylphenyl, a Propyl phenyl, naphthyl and the like; preferably phenyl or naphthyl, especially phenyl (also referred to as C 6 H 5 as a substituent).
- R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from the group consisting of hydrogen, halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 a -C 20 olefinylthio group, a C 2 -C 20 alkynylthio group, a C 3 -C 20 cycloalkylthi
- R 1 , R 2 , R 3 , R 4 and R 5 are independently of each other selected from the group consisting of hydrogen, halogen, nitro, hydroxy, thiol, carboxyl, sulfonate, amino, cyano, C 1 -C 6 Alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2 - a C 6 -alkylthio group, a C 2 -C 6 alkynylthio group, a C 3 -C 8 cycloalkylthio
- R 1 , R 2 , R 3 , R 4 and R 5 are independently of each other selected from the group consisting of hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1 -C 4 An alkylthio group, wherein the aforementioned C 1 -C 4 alkyl group, C 1 -C 4 alkoxy group and C 1 -C 4 alkylthio group are optionally substituted by one or more groups independently selected from the group consisting of Halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1 -C 4 alkylthio.
- R 6 and R 7 are the same or different and are selected from a C 1 -C 6 alkyl group and a halogenated C 1 -C 6 alkyl group, or R 6 and R 7 together with the carbon atom to which they are attached form a C 3- C 8 cycloalkyl.
- R 6 and R 7 are the same or different and are selected from a C 1 -C 4 alkyl group and a halogenated C 1 -C 4 alkyl group, or R 6 and R 7 together with the carbon atom to which they are attached form a C 5 -C 6 cycloalkyl. It is particularly preferred that R 6 and R 7 are the same or different and are methyl or halomethyl, or that R 6 and R 7 together with the carbon atom to which they are attached form a cyclopentyl or cyclohexyl group.
- R 8 , R 9 , R 10 , R 11 and R 12 are each independently selected from the group consisting of hydrogen, halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 a -C 20 olefinylthio group, a C 2 -C 20 alkynylthio group, a C 3 -C 20 cycloalkylthi
- R 8 , R 9 , R 10 , R 11 and R 12 are independently of each other selected from the group consisting of hydrogen, halogen, nitro, hydroxy, thiol, carboxyl, sulfonate, amino, cyano, C 1 -C 6 Alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2 - a C 6 -alkylthio group, a C 2 -C 6 alkynylthio group, a C 3 -C 8 cycloalkylthio
- R 8 , R 9 , R 10 , R 11 and R 12 are independently of each other selected from the group consisting of hydrogen, halogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkyne a C 1 -C 4 alkoxy group and a C 1 -C 4 alkylthio group, wherein the aforementioned C 1 -C 4 alkyl group, C 2 -C 4 alkenyl group, C 2 -C 4 alkynyl group, C 1 -C
- the 4 alkoxy group and the C 1 -C 4 alkylthio group may be optionally substituted by one or more groups independently selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1 -C 4 Alkoxy and C 1 -C 4 alkylthio.
- R 13 and R 14 are the same or different and are selected from the group consisting of H, C 1 -C 6 alkyl and halogenated C 1 -C 6 alkyl.
- R 14 and R 13 is selected from H, C 1 -C 4 alkyl and halo C 1 -C 4 alkyl. It is particularly preferred that both R 13 and R 14 are H.
- the compound of formula (I) is selected from the group consisting of
- a process for the preparation of a compound of the formula (I) according to the invention which comprises the esterification of a compound of the formula (II) with a compound of the formula (III) to give a compound of the formula (I),
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are as defined for the compound of formula (I) Definition, and X is hydroxy or halogen.
- the above esterification reaction is usually carried out in the presence of a catalyst suitable for the esterification reaction.
- a catalyst suitable for the esterification reaction.
- an acidic catalyst or a basic catalyst can 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 may be used.
- sodium hydrogencarbonate, sodium t-butoxide, sodium ethoxide, sodium hydride, potassium hydride, lithium 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 knowledge in the art or by several routine preliminary experiments.
- the above esterification reaction is usually carried out in a solvent, preferably in an organic solvent.
- the selection of the type of the solvent is not particularly limited as long as the compound of the formula (II) and the formula (III) can be dissolved and chemically inert to the esterification reaction, that is, it does not participate in the esterification reaction.
- the solvent mention may be made of tetrahydrofuran, benzene, toluene, N,N-dimethylformamide, dichloromethane and acetone.
- the solvent may be used singly or as a mixture of two or more solvents.
- the relative amounts of the compound of the formula (II) and the compound of the formula (III) are not particularly limited, and generally they are used in an equimolar amount.
- the esterification reaction can be carried out over a very wide temperature range.
- the ester is advantageously The reaction is carried out at a temperature of from -10 ° C to 150 ° C, preferably from 0 ° C to 100 ° C, preferably at room temperature.
- the esterification reaction time is also not particularly limited and is usually carried out for 1 to 24 hours, preferably 1 to 12 hours.
- reaction mixture comprising a compound of formula (I) is obtained. Therefore, the reaction mixture needs to be worked up to give a purified compound of formula (I).
- the reaction mixture obtained by the esterification reaction is first filtered, and the filtrate fraction is taken out. The filtrate is then washed to remove the catalyst and unreacted starting materials.
- the washing liquid is not particularly limited as long as the catalyst and the unreacted raw material can be removed.
- dilute hydrochloric acid (aqueous solution), saturated aqueous sodium hydrogencarbonate solution and water can be mentioned.
- the concentration of the dilute hydrochloric acid is not particularly limited, and generally, a dilute hydrochloric acid having a concentration of 5 to 12% is used.
- the washing with the washing liquid may be carried out once or several times; in the case of multiple times, a single washing liquid may be used, or different washing liquids may be used in sequence.
- the compound of formula (I) is obtained. If it is desired to further increase the purity of the compound of formula (I), the compound may be further purified, which may be carried out, for example, by recrystallization.
- the selection of the recrystallization solvent is conventional and is not particularly limited. According to the invention, it is advantageous to recrystallize the crude product of the compound of formula (I) with methanol.
- the compound of the formula (I) of the present invention contains both an ⁇ -monohydroxy ketone moiety and a cinnamoyl moiety, so that the compound can function as a photoinitiator of the ⁇ -monohydroxy ketone and also because of the cinnamoyl structure. Partial introduction improves the problem of the strong odor and migration inherent in the ⁇ -monohydroxyketone photoinitiator.
- the compound of the formula (I) of the present invention can absorb electromagnetic waves of 200 to 350 nm. After absorbing electromagnetic waves, the compound of formula (I) changes from a ground state to an excited state, such that the acyl group in the benzoyl moiety of the compound of formula (I) The carbon atom is cleaved with carbon atoms in the adjacent methoxy group to form two radicals, thereby initiating photopolymerization or photocrosslinking.
- the cinnamoyl moiety of the compound of the formula (I) contains an unsaturated carbon-carbon double bond, different intermolecular carbon-carbon double bonds are easily reacted to form a larger molecular or cross-linked structure upon exposure to electromagnetic waves, thereby greatly improving
- the problem of strong odor and migration caused by photoinitiators significantly reduces odor and significantly reduces migration.
- the compound of the formula (I) can be used as a photoinitiator in novel fields such as coatings, inks, microelectronics, printing, and the like, and in the preparation of laser recording and three-dimensional components.
- the amount thereof is conventional or can be determined by routine preliminary tests.
- reaction liquid was filtered, and the filtrate was washed successively with dilute hydrochloric acid (5%), saturated aqueous sodium hydrogen carbonate and distilled water, and then dried over anhydrous sodium sulfate and filtered, and the organic phase was evaporated under reduced pressure.
- the product was identified as the title compound by 1 H-NMR spectrum.
- reaction liquid was filtered, and the filtrate was washed successively with dilute hydrochloric acid (5%), saturated aqueous sodium hydrogen carbonate and distilled water, and then dried over anhydrous sodium sulfate and filtered, and the organic phase was evaporated under reduced pressure. Yellow crystals, a total of 18 g, were identified as the title compound by 1 H-NMR.
- reaction liquid was filtered, and the filtrate was washed successively with dilute hydrochloric acid (5%), saturated aqueous sodium hydrogen carbonate and distilled water, and then dried over anhydrous sodium sulfate and filtered, and the organic phase was evaporated under reduced pressure. Yellow crystals, a total of 23 g, were identified as the title compound by 1 H-NMR spectrum.
- reaction liquid was filtered, and the filtrate was washed successively with dilute hydrochloric acid (5%), saturated aqueous sodium hydrogen carbonate and distilled water, and then dried over anhydrous sodium sulfate and filtered, and the organic phase was evaporated under reduced pressure. Yellow crystals, a total of 21 g , were identified as the title compound by 1 H-NMR spectrum.
- reaction liquid was filtered, and the filtrate was washed successively with dilute hydrochloric acid (5%), saturated aqueous sodium hydrogen carbonate and distilled water, and then dried over anhydrous sodium sulfate and filtered, and the organic phase was evaporated under reduced pressure. Yellow crystals, a total of 23 g, were identified as the title compound by 1 H-NMR spectrum.
- reaction liquid was filtered, and the filtrate was washed successively with dilute hydrochloric acid (5%), saturated aqueous sodium hydrogen carbonate and distilled water, and then dried over anhydrous sodium sulfate and filtered, and the organic phase was evaporated under reduced pressure.
- the product was identified as the title compound by 1 H-NMR spectrum.
- reaction liquid was filtered, and the filtrate was washed successively with dilute hydrochloric acid (5%), saturated aqueous sodium hydrogen carbonate and distilled water, and then dried over anhydrous sodium sulfate and filtered, and the organic phase was evaporated under reduced pressure.
- the product was identified as the title compound by 1 H-NMR spectrum.
- reaction liquid was filtered, and the filtrate was washed successively with dilute hydrochloric acid (5%), saturated aqueous sodium hydrogen carbonate and distilled water, and then dried over anhydrous sodium sulfate and filtered, and the organic phase was evaporated under reduced pressure.
- the product was identified as the title compound by 1 H-NMR spectrum.
- reaction liquid was filtered, and the filtrate was washed successively with dilute hydrochloric acid (5%), saturated aqueous sodium hydrogen carbonate and distilled water, and then dried over anhydrous sodium sulfate and filtered, and the organic phase was evaporated under reduced pressure.
- the product was identified as the title compound by 1 H-NMR spectrum.
- reaction liquid was filtered, and the filtrate was washed successively with dilute hydrochloric acid (5%), saturated aqueous sodium hydrogen carbonate and distilled water, and then dried over anhydrous sodium sulfate and filtered, and the organic phase was evaporated under reduced pressure.
- the product was identified as the title compound by 1 H-NMR spectrum.
- reaction liquid was filtered, and the filtrate was washed successively with dilute hydrochloric acid (5%), saturated aqueous sodium hydrogen carbonate and distilled water, and then dried over anhydrous sodium sulfate and filtered, and the organic phase was evaporated under reduced pressure. pale yellow crystals, a total of 19g, the product was confirmed that 1 H-NMR spectrum of the title compound.
- reaction liquid was filtered, and the filtrate was washed successively with dilute hydrochloric acid (5%), saturated aqueous sodium hydrogen carbonate and distilled water, and then dried over anhydrous sodium sulfate and filtered, and the organic phase was evaporated under reduced pressure.
- the product was identified as the title compound by 1 H-NMR spectrum.
- reaction liquid was filtered, and the filtrate was washed successively with dilute hydrochloric acid (5%), saturated aqueous sodium hydrogen carbonate and distilled water, and then dried over anhydrous sodium sulfate and filtered, and the organic phase was evaporated under reduced pressure. Yellow crystals, a total of 25 g, were identified as the title compound by 1 H-NMR spectrum.
- thermogravimetric (TG) analysis of the thermal stability of each compound was carried out using a ZRY-2P type thermal analyzer (METTLER).
- the test conditions were as follows: starting from an initial temperature of 25 ° C, the temperature was raised to a final temperature of 500 K at a rate of 10 K/min. °C.
- the change in weight percent of the compound over time is shown in Figure 3.
- the photoinitiator properties of photoinitiators were tested using real-time infrared technology. Two compounds, 1173-CC and 184-CC, were selected as the representative initiator to initiate polymerization of the polymerizable monomer hydroxyethyl methacrylate (HEMA) under ultraviolet light irradiation. 5 ml of acetone was added to 2 g of HEMA, stirred, and after the monomer was dissolved, 0.06 g of a photoinitiator (1173-C or 184-CC) was added to prepare a 1173-CC-HEMA sample and a 184-CC-HEMA sample, respectively.
- HEMA polymerizable monomer hydroxyethyl methacrylate
- the double bond conversion rate of the monomer is collected by near-infrared real-time, and the real-time infrared parameter is set as follows: the data acquisition interval is 0.3985s, and each spectrum is scanned once, with a resolution of 4cm -1 .
- the characteristic absorption peak of carbon-carbon double bond in HEMA in the near-infrared spectrum is at 1630 cm -1 .
- the double bond conversion rate is calculated by combining omnic7.1 infrared software and origin6.1 data processing software with formula (1):
- a 0 and A are the areas of the characteristic absorption peak of the hydroxyethyl methacrylate double bond at 1630 cm -1 before and after the curing of the sample, respectively.
- EA Ethyl acrylate
- TPGDA tripropylene glycol diacrylate
- TMPTA trimethylol propyl triacrylate
- the light was irradiated with a 365 nm light source at a light intensity of 100 mW/cm 2 for 5 min, and allowed to stand at room temperature for 24 hours in a desiccator to fully solidify the cured film, and the four photoinitiators were weighed and weighed ( 184, 184-CC, 1173, 1173-CC) respective masses.
- the obtained acetonitrile solution was filtered, and the absorption at 300 nm was monitored by ultraviolet-visible absorption spectroscopy.
- c is the concentration of the initiator (mol/L); 1 is the length of the optical path, which is taken as 1 cm; the mass of the four photoinitiators extracted is calculated according to formula (3), and M is the relative molecule of the photoinitiator.
- Mass V0 is the volume of acetonitrile.
- R is the mobility of the photoinitiator, W is the initial added mass fraction of the photoinitiator, m0 is the mass of the cured film, and m 1 is the residual amount of the photoinitiator.
- Methyl methacrylate, tripropylene glycol diacrylate (TPGDA) and trimethylolpropane triacrylate (TMPTA) were mixed in a mass ratio of 3:3:4 to obtain a mixture, and the total amount thereof was added thereto.
- Two photosensitive compositions were prepared in an amount of 3% by weight of 184-CC or 1173-CC. Each of the above-mentioned photosensitive compositions was cured into a film under a light source having a wavelength of 395 nm, and the pencil hardness was 3H.
- the resulting photocurable composition was then applied to a 12 cm*12 cm white copper paperboard using a 10 micron wire bar coater and cured with a UV-LED source having an emission wavelength of 395 nm and a light intensity of 50 mW/cm 2 . The time required for curing. Then, the cardboard was cut into 10*10 cm size, and completely immersed in 100 ml of distilled water or 3% acetic acid aqueous solution, and sealed for 10 days at 40 °C. The printed matter was taken out, and after standing, the content of the photoinitiator in the simulated liquid was directly analyzed by HPLC. Using the EU model, assuming 1 kg of food in a 600 cm 2 printing area, the mobility measurement results are expressed in ppb or ug/kg food, and the results are shown in Table 5.
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Abstract
The present invention relates to a cinnamic acid benzoyl methyl ester compound of formula (I), wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13 and R14 are as defined in the description. The present invention also relates to a method for preparing the cinnamic acid benzoyl methyl ester compound of the present invention, comprising subjecting the compound of formula (II) and the compound of formula (III) to an esterification reaction. The compound of the present invention can be used as a photoinitiator, is capable of absorbing radiant heat in the range of 200-350 nm, has good stability and resistance to yellowing, and more importantly, such initiators have greatly improved in terms of odour and strong migration, compared with the existing α-monohydroxy ketone photoinitiators. The present invention also relates to a use of the cinnamic acid benzoyl methyl ester compound of the present invention as a photoinitiator.
Description
本发明涉及肉桂酸苯甲酰基甲酯类化合物，该类化合物可用作光引发剂，本发明还涉及肉桂酸苯甲酰基甲酯类化合物的制备及应用。This invention relates to benzoylmethyl cinnamate compounds which are useful as photoinitiators and to the preparation and use of benzoylmethyl cinnamate compounds.
当今社会环境和能源问题日益突出，光固化材料由于其在固化过程中，没有或者只有少量的溶剂挥发，作为一种绿色、环保、能耗低的环境友好型材料被人们广泛接受和关注。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。Today's social environment and energy issues are increasingly prominent. Photocuring materials are widely accepted and paid attention to as a green, environmentally friendly, low-energy environmentally friendly material because they have no or only a small amount of solvent volatilization during the curing process. At present, photocuring technology has been widely used in traditional fields such as coatings, inks, microelectronics, printing, etc., and is also used in the preparation of new fields such as laser recording and three-dimensional components.
光引发剂又称光敏剂或光固化剂，是光固化技术中必不可少的部分，它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。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 an indispensable part of photocuring technology. It is a kind of energy that can absorb a certain wavelength in the ultraviolet (250-400nm) or visible (400-600nm) region. A compound which generates a radical, a cation, or the like to initiate polymerization of a monomer by polymerization crosslinking. In the photocuring system, the photoinitiator generally accounts for 3-5%, and although the content is low, it is a key component thereof, which plays a decisive role in the photocuring speed. It is related to whether the oligomer and the diluent can be rapidly cross-linked and solidified in the formulation system during light irradiation, thereby changing from a liquid state to a solid state. As an important component of the photocuring system, the photoinitiator must meet the needs of different photocuring conditions and applications. In the field of free radical photoinitiators, the main objectives are: to improve light sensitivity, improve surface curing efficiency (antioxidation inhibition), improve deep curing properties, improve the solubility of photoinitiators in monomers and resins, and reduce toxicity and odor. It reduces the migration of the uncured initiator after curing and reduces the yellowing.
α-单羟基酮类光引发剂是常用的光引发剂，其中最常见的是光引发剂1173(2-羟基-2-甲基-1-苯基丙酮)和184(1-羟基环己基苯基甲酮)。光引发剂1173是液体，使用方便，在各类光固化清漆中是主引发剂，热稳定性优良，耐黄变性好，价格较低；缺点主要是，光解产物中存在的苯甲醛有不良气味，同时挥发性较大，迁移性强。光引发剂184是白色粉末，挥发性较低，但同样存在光解产物有异昧和迁移性强的问题。Alpha-monohydroxyketone photoinitiators are commonly used photoinitiators, the most common of which are photoinitiators 1173 (2-hydroxy-2-methyl-1-phenylacetone) and 184 (1-hydroxycyclohexylbenzene). Ketone). Photoinitiator 1173 is a liquid, easy to use, is the main initiator in various types of photocurable varnish, excellent thermal stability, good yellowing resistance, and low price; the main disadvantage is that the benzaldehyde present in the photolysis product is bad. Odor, while having high volatility and strong migration. The photoinitiator 184 is a white powder and has a low volatility, but there is also a problem that the photolysis product has a heterogeneous and highly mobile property.
1954年Eastman-Kodak公司生产出了世界上最早的用合成高分子
为原料的光刻胶-聚乙烯醇肉桂酸酯系负性光刻胶(US 2690966)。这是人类最先应用在电子工业上的光刻胶，其光聚合反应的原理如下式所示：In 1954 Eastman-Kodak produced the world's first synthetic polymer
A photoresist-polyvinyl alcohol cinnamate-based negative photoresist (US 2690966). This is the first photoresist applied by humans in the electronics industry. The principle of photopolymerization is as follows:
肉桂酰基中的双键在紫外光作用下打开，不同分子上的双键相互作用形成四元环，产生光二聚交联。这样，曝光区的分子间发生交联，形成难溶的体型网状结构，未曝光区的分子性质不变，在显影液中产生溶解性差异。正是利用这种特性可以实现微细加工。The double bond in the cinnamoyl group opens under the action of ultraviolet light, and the double bonds on different molecules interact to form a four-membered ring, resulting in photodimerization crosslinking. Thus, the molecules in the exposed region are crosslinked to form a poorly soluble bulk network structure, and the molecular properties of the unexposed regions are unchanged, resulting in a difference in solubility in the developer. It is this feature that enables fine machining.
发明内容Summary of the invention
鉴于现有技术的上述状况，本发明的发明人在光引发剂领域进行了广泛而又深入的研究，以期发现一种能够改善α-单羟基酮类光引发剂的异味和迁移性强的光引发剂。本发明人发现，如果在α-单羟基酮类光引发剂上引入或接上肉桂酰基，利用肉桂酰基在紫外光下可聚合交联的特性，如此得到的光引发剂在保留了α-单羟基酮类光引发剂的优点的同时还改善了α-单羟基酮类光引发剂的异味和迁移性强的问题。本发明正是基于前述发现得以实现。In view of the above-described state of the art, the inventors of the present invention conducted extensive and intensive research in the field of photoinitiators in order to find a light which can improve the odor and migration of the α-monohydroxyketone photoinitiator. Initiator. The present inventors have found that if a cinnamoyl group is introduced or attached to an α-monohydroxyketone photoinitiator, the cinnamoyl group can be polymerized and crosslinked under ultraviolet light, and the photoinitiator thus obtained retains α-single The advantages of the hydroxyketone photoinitiator also improve the problem of the odor and migration of the α-monohydroxyketone photoinitiator. The present invention has been achieved based on the foregoing findings.
因此，本发明的一个目的是提供一种新的肉桂酸苯甲酰基甲酯类化合物。该类化合物可用作光引发剂，能够吸收200-350nm范围内的辐射热、稳定性良好、耐黄变，而且更为重要的是，该类引发剂相比于现有α-单羟基酮类光引发剂，大大改善了异味和迁移性强的问题，而且紫外红移。Accordingly, it is an object of the present invention to provide a novel benzoylmethyl ester cinnamate compound. These compounds are useful as photoinitiators, capable of absorbing radiant heat in the range of 200-350 nm, good stability, resistance to yellowing, and, more importantly, such initiators compared to existing alpha-monohydroxyketones. The photoinitiator greatly improves the problem of strong odor and migration, and the ultraviolet red shift.
本发明的另一个目的是提供一种制备本发明肉桂酸苯甲酰基甲酯类化合物的方法。Another object of the present invention is to provide a process for preparing the benzoylmethyl cinnamate compound of the present invention.
本发明的又一个目的是提供本发明肉桂酸苯甲酰基甲酯类化合物作为光引发剂的用途。使用本发明肉桂酸苯甲酰基甲酯类化合物作为光引发剂，
相比于现有α-单羟基酮类光引发剂，大大改善了异味和迁移性强的问题，而且紫外红移。Still another object of the present invention is to provide the use of the benzoyl methacrylate compound of the present invention as a photoinitiator. Using the benzoic acid benzoylmethyl ester compound of the present invention as a photoinitiator,
Compared with the existing α-monohydroxyketone photoinitiator, the problem of strong odor and migration is greatly improved, and the ultraviolet red shift.
实现本发明上述目的的技术方案可以概括如下：The technical solution for achieving the above object of the present invention can be summarized as follows:
1.肉桂酸苯甲酰基甲酯类化合物，具有式(I)所示结构：1. A benzoylmethyl cinnamate compound having the structure represented by the formula (I):
其中among them
R1、R2、R3、R4和R5彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C1-C20烷基、C2-C20烯基、C2-C20炔基、C3-C20环烷基、C4-C20环烷基烷基、C1-C20烷氧基、C2-C20烯氧基、C2-C20炔氧基、C3-C20环烷氧基、C4-C20环烷基烷氧基、C1-C20烷硫基、C2-C20烯硫基、C2-C20炔硫基、C3-C20环烷硫基、C4-C20环烷基烷硫基和C6-C18芳基，其中前述C1-C20烷基、C2-C20烯基、C2-C20炔基、C3-C20环烷基、C4-C20环烷基烷基、C1-C20烷氧基、C2-C20烯氧基、C2-C20炔氧基、C3-C20环烷氧基、C4-C20环烷基烷氧基、C1-C20烷硫基、C2-C20烯硫基、C2-C20炔硫基、C3-C20环烷硫基、C4-C20环烷基烷硫基和C6-C18芳基基团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、羧基、磺酸基、氨基、氰基、C1-C6烷基、C1-C6烷氧基、C1-C6烷硫基、C2-C6烯基和C2-C6炔基；R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from the group consisting of hydrogen, halogen, nitro, hydroxy, decyl, carboxyl, sulfonic acid, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 olefin Oxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 alkene a C 2 -C 20 alkynylthio group, a C 3 -C 20 cycloalkylthio group, a C 4 -C 20 cycloalkylalkylthio group and a C 6 -C 18 aryl group, wherein the aforementioned C 1 -C 20 alkyl group , C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 Alkylthio, C 2 -C 20 alkynylthio, C 3 -C 20 cycloalkylthio, C 4 -C 20 cycloalkylalkylthio and C 6 -C 18 aryl groups may optionally be one Or a plurality of groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonate, amino, cyano, C 1- C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkenyl and C 2 -C 6 alkynyl;
R6和R7相同或不同且选自C1-C6烷基和卤代C1-C6烷基，或者R6和R7与它们所连接的碳原子一起形成C3-C8环烷基；R 6 and R 7 are the same or different and are selected from a C 1 -C 6 alkyl group and a halogenated C 1 -C 6 alkyl group, or R 6 and R 7 together with the carbon atom to which they are attached form a C 3 -C 8 ring alkyl;
R8、R9、R10、R11和R12彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C1-C20烷基、C2-C20烯基、C2-C20炔基、C3-C20环烷基、C4-C20环烷基烷基、C1-C20烷氧基、C2-C20烯氧基、C2-C20炔氧基、C3-C20环烷氧基、C4-C20环烷基烷氧基、C 1-C20烷硫基、C2-C20烯硫基、C2-C20炔硫基、C3-C20环烷硫基、C4-C20环烷基烷硫基和C6-C18
芳基，其中前述C1-C20烷基、C2-C20烯基、C2-C20炔基、C3-C20环烷基、C4-C20环烷基烷基、C1-C20烷氧基、C2-C20烯氧基、C2-C20炔氧基、C3-C20环烷氧基、C4-C20环烷基烷氧基、C1-C20烷硫基、C2-C20烯硫基、C2-C20炔硫基、C3-C20环烷硫基、C4-C20环烷基烷硫基和C6-C18芳基基团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、羧基、磺酸基、氨基、氰基、C1-C6烷基、C1-C6烷氧基、C1-C6烷硫基、C2-C6烯基和C2-C6炔基；以及R 8 , R 9 , R 10 , R 11 and R 12 are independently of each other selected from the group consisting of hydrogen, halogen, nitro, hydroxy, decyl, carboxyl, sulfonate, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 olefin Oxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 alkene a C 2 -C 20 alkynylthio group, a C 3 -C 20 cycloalkylthio group, a C 4 -C 20 cycloalkylalkylthio group and a C 6 -C 18 aryl group, wherein the aforementioned C 1 -C 20 alkyl group , C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 Alkylthio, C 2 -C 20 alkynylthio, C 3 -C 20 cycloalkylthio, C 4 -C 20 cycloalkylalkylthio and C 6 -C 18 aryl groups may optionally be one Or a plurality of groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, amino, cyano C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkenyl and C 2 -C 6 alkynyl group;
R13和R14相同或不同且选自H、C1-C6烷基和卤代C1-C6烷基。R 13 and R 14 are the same or different and are selected from the group consisting of H, C 1 -C 6 alkyl and halogenated C 1 -C 6 alkyl.
2.根据第1项的化合物，其中R6和R7相同或不同且选自C1-C4烷基和卤代C1-C4烷基，或者R6和R7与它们所连接的碳原子一起形成C5-C6环烷基。2. The compound according to item 1, wherein R 6 and R 7 are the same or different and are selected from a C 1 -C 4 alkyl group and a halogenated C 1 -C 4 alkyl group, or R 6 and R 7 are attached thereto. formation of C 5 -C 6 cycloalkyl group together with the carbon atom.
3.根据第2项的化合物，其中R6和R7相同且为甲基或卤代甲基，或者R6和R7与它们所连接的碳原子一起形成环戊基或环己基。3. The compound according to item 2, wherein R 6 and R 7 are the same and are methyl or halomethyl, or R 6 and R 7 together with the carbon atom to which they are attached form a cyclopentyl or cyclohexyl group.
4.根据第1-3项中任一项的化合物，其中R13和R14相同或不同且选自H、C1-C4烷基和卤代C1-C4烷基，优选R13和R14均为H。The compound according to any one of items 1 to 3, wherein R 13 and R 14 are the same or different and are selected from the group consisting of H, C 1 -C 4 alkyl and halogenated C 1 -C 4 alkyl, preferably R 13 And R 14 are both H.
5.根据第1-4项中任一项的化合物，其中5. A compound according to any one of items 1 to 4 wherein
R1、R2、R3、R4和R5彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C8环烷基、C4-C8环烷基烷基、C1-C6烷氧基、C2-C6烯氧基、C2-C6炔氧基、C3-C8环烷氧基、C4-C8环烷基烷氧基、C1-C6烷硫基、C2-C6烯硫基、C2-C6炔硫基、C3-C8环烷硫基、C4-C8环烷基烷硫基和C6-C10芳基，其中前述C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C8环烷基、C4-C8环烷基烷基、C1-C6烷氧基、C2-C6烯氧基、C2-C6炔氧基、C3-C8环烷氧基、C4-C8环烷基烷氧基、C1-C6烷硫基、C2-C6烯硫基、C2-C6炔硫基、C3-C8环烷硫基、C4-C8环烷基烷硫基和C6-C10芳基基团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、羧基、磺酸基、氨基、氰基、C1-C4烷基、C1-C4烷氧基、C1-C4烷硫基、C2-C4烯基和C2-C4炔基；和/或R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from the group consisting of hydrogen, halogen, nitro, hydroxy, decyl, carboxyl, sulfonic acid, amino, cyano, C 1 -C 6 alkyl, C 2- C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 olefin Oxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkene a C 2 -C 6 alkynylthio group, a C 3 -C 8 cycloalkylthio group, a C 4 -C 8 cycloalkylalkylthio group and a C 6 -C 10 aryl group, wherein the aforementioned C 1 -C 6 alkyl group , C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2 -C 6 Alkylthio, C 2 -C 6 alkynylthio, C 3 -C 8 cycloalkylthio, C 4 -C 8 cycloalkylalkylthio and C 6 -C 10 aryl groups may optionally be one Or a plurality of groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, amino, cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy a group, a C 1 -C 4 alkylthio group, a C 2 -C 4 alkenyl group, and a C 2 -C 4 alkynyl group; and/or
R8、R9、R10、R11和R12彼此独立地选自氢、卤素、硝基、羟基、巯基、
羧基、磺酸基、氨基、氰基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C8环烷基、C4-C8环烷基烷基、C1-C6烷氧基、C2-C6烯氧基、C2-C6炔氧基、C3-C8环烷氧基、C4-C8环烷基烷氧基、C1-C6烷硫基、C2-C6烯硫基、C2-C6炔硫基、C3-C8环烷硫基、C4-C8环烷基烷硫基和C6-C10芳基，其中前述C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C8环烷基、C4-C8环烷基烷基、C1-C6烷氧基、C2-C6烯氧基、C2-C6炔氧基、C3-C8环烷氧基、C4-C8环烷基烷氧基、C1-C6烷硫基、C2-C6烯硫基、C2-C6炔硫基、C3-C8环烷硫基、C4-C8环烷基烷硫基和C6-C10芳基基团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、羧基、磺酸基、氨基、氰基、C1-C4烷基、C1-C4烷氧基、C1-C4烷硫基、C2-C4烯基和C2-C4炔基。R 8 , R 9 , R 10 , R 11 and R 12 are independently of each other selected from the group consisting of hydrogen, halogen, nitro, hydroxy, decyl, carboxy, sulfonic acid, amino, cyano, C 1 -C 6 alkyl, C 2- C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 olefin Oxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkene a C 2 -C 6 alkynylthio group, a C 3 -C 8 cycloalkylthio group, a C 4 -C 8 cycloalkylalkylthio group and a C 6 -C 10 aryl group, wherein the aforementioned C 1 -C 6 alkyl group , C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2 -C 6 Alkylthio, C 2 -C 6 alkynylthio, C 3 -C 8 cycloalkylthio, C 4 -C 8 cycloalkylalkylthio and C 6 -C 10 aryl groups may optionally be one or more groups independently selected from the group: halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic, amino, cyano, C 1 -C 4 alkyl, C 1 -C 4 Alkoxy, C 1 -C 4 alkylthio, C 2 -C 4 alkenyl and C 2 -C 4 alkynyl group.
6.根据第1-4项中任一项的化合物，其中6. The compound according to any one of items 1 to 4, wherein
R1、R2、R3、R4和R5彼此独立地选自氢、卤素、C1-C4烷基、C1-C4烷氧基和C1-C4烷硫基，其中前述C1-C4烷基、C1-C4烷氧基和C1-C4烷硫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、C1-C4烷基、C1-C4烷氧基和C1-C4烷硫基；和/或R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from the group consisting of hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1 -C 4 alkylthio, wherein The aforementioned C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1 -C 4 alkylthio may be optionally substituted by one or more groups independently selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1 -C 4 alkylthio; and/or
R8、R9、R10、R11和R12彼此独立地选自氢、卤素、C1-C4烷基、C2-C4烯基、C2-C4炔基、C1-C4烷氧基和C1-C4烷硫基，其中前述C1-C4烷基、C2-C4烯基、C2-C4炔基、C1-C4烷氧基和C1-C4烷硫基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、C1-C4烷基、C1-C4烷氧基和C1-C4烷硫基。R 8 , R 9 , R 10 , R 11 and R 12 are independently of each other selected from the group consisting of hydrogen, halogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 - a C 4 alkoxy group and a C 1 -C 4 alkylthio group, wherein the aforementioned C 1 -C 4 alkyl group, C 2 -C 4 alkenyl group, C 2 -C 4 alkynyl group, C 1 -C 4 alkoxy group and The C 1 -C 4 alkylthio group may be optionally substituted by one or more groups independently selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1- C 4 alkylthio group.
7.根据第1项的化合物，其中该化合物选自下组：7. The compound according to item 1, wherein the compound is selected from the group consisting of:
8.一种制备根据第1-7项中任一项的式(I)化合物的方法，包括使式(II)化合物与式(III)化合物进行酯化反应，得到式(I)化合物，8. A process for the preparation of a compound of formula (I) according to any one of items 1 to 7, which comprises esterifying a compound of formula (II) with a compound of formula (III) to give a compound of formula (I),
其中R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13和R14如第1-7项中任一项所定义，以及X为羟基或卤素。Wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are as defined in items 1-7 One is defined, and X is a hydroxyl group or a halogen.
9.根据第8项的方法，其中酯化反应在催化剂存在下进行，优选催化剂为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。
9. The method according to item 8, wherein the esterification reaction is carried out in the presence of a catalyst, preferably the catalyst is 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, sodium hydrogencarbonate, sodium t-butoxide, sodium ethoxide, sodium hydride, potassium hydride, calcium hydride and tertiary amines, such as trialkylamines, such as three Methylamine and triethylamine.
10.根据第1-7项中任一项的化合物作为光引发剂的用途。10. Use of a compound according to any one of items 1 to 7 as a photoinitiator.
本发明的这些和其它目的、特征和优点在结合下文考虑本发明后，将易于为普通技术人员所明白。These and other objects, features and advantages of the present invention will become apparent to those skilled in
附图简述BRIEF DESCRIPTION OF THE DRAWINGS
图1是化合物1173和1173CC的紫外吸收光谱图；Figure 1 is a UV absorption spectrum of Compounds 1173 and 1173CC;
图2是化合物184和184-CC的紫外吸收光谱图；Figure 2 is a UV absorption spectrum of Compounds 184 and 184-CC;
图3是化合物的热分解率随时间变化的关系图；Figure 3 is a graph showing the relationship between the thermal decomposition rate of a compound and time;
图4是化合物184-CC作为光引发剂得到的可聚合单体的双键转化率随时间的变化；以及Figure 4 is a graph showing the change in double bond of a polymerizable monomer obtained as a photoinitiator of compound 184-CC over time;
图5是化合物1173-CC作为光引发剂得到的可聚合单体的双键转化率随时间的变化。Figure 5 is a graph showing the change in double bond conversion of a polymerizable monomer obtained by using a compound 1173-CC as a photoinitiator over time.
根据本发明的第一个方面，提供了一种下式(I)的肉桂酸苯甲酰基甲酯类化合物：According to a first aspect of the present invention, there is provided a benzoylmethyl cinnamate compound of the following formula (I):
其中among them
R1、R2、R3、R4和R5彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C1-C20烷基、C2-C20烯基、C2-C20炔基、C3-C20环烷基、C4-C20环烷基烷基、C1-C20烷氧基、C2-C20烯氧基、C2-C20炔氧基、C3-C20环烷氧基、C4-C20环烷基烷氧基、C1-C20烷硫基、C2-C20烯硫基、C2-C20炔硫基、C3-C20环烷硫基、C4-C20环烷基烷硫基和C6-C18芳基，其中前述C1-C20烷基、C2-C20烯基、C2-C20炔基、C3-C20环烷基、C4-C20环烷基烷基、C1-C20烷氧基、C2-C20烯氧基、C2-C20炔氧基、C3-C20环烷氧基、C4-C20环烷基烷氧基、C1-C20烷硫基、C2-C20烯硫基、C2-C20
炔硫基、C3-C20环烷硫基、C4-C20环烷基烷硫基和C6-C18芳基基团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、羧基、磺酸基、氨基、氰基、C1-C6烷基、C1-C6烷氧基、C1-C6烷硫基、C2-C6烯基和C2-C6炔基；R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from the group consisting of hydrogen, halogen, nitro, hydroxy, decyl, carboxyl, sulfonic acid, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 olefin Oxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 alkene a C 2 -C 20 alkynylthio group, a C 3 -C 20 cycloalkylthio group, a C 4 -C 20 cycloalkylalkylthio group and a C 6 -C 18 aryl group, wherein the aforementioned C 1 -C 20 alkyl group , C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 Alkylthio, C 2 -C 20 alkynylthio, C 3 -C 20 cycloalkylthio, C 4 -C 20 cycloalkylalkylthio and C 6 -C 18 aryl groups may optionally be one Or a plurality of groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonate, amino, cyano, C 1- C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkenyl and C 2 -C 6 alkynyl;
R6和R7相同或不同且选自C1-C6烷基和卤代C1-C6烷基，或者R6和R7与它们所连接的碳原子一起形成C3-C8环烷基；R 6 and R 7 are the same or different and are selected from a C 1 -C 6 alkyl group and a halogenated C 1 -C 6 alkyl group, or R 6 and R 7 together with the carbon atom to which they are attached form a C 3 -C 8 ring alkyl;
R8、R9、R10、R11和R12彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C1-C20烷基、C2-C20烯基、C2-C20炔基、C3-C20环烷基、C4-C20环烷基烷基、C1-C20烷氧基、C2-C20烯氧基、C2-C20炔氧基、C3-C20环烷氧基、C4-C20环烷基烷氧基、C1-C20烷硫基、C2-C20烯硫基、C2-C20炔硫基、C3-C20环烷硫基、C4-C20环烷基烷硫基和C6-C18芳基，其中前述C1-C20烷基、C2-C20烯基、C2-C20炔基、C3-C20环烷基、C4-C20环烷基烷基、C1-C20烷氧基、C2-C20烯氧基、C2-C20炔氧基、C3-C20环烷氧基、C4-C20环烷基烷氧基、C1-C20烷硫基、C2-C20烯硫基、C2-C20炔硫基、C3-C20环烷硫基、C4-C20环烷基烷硫基和C6-C18芳基基团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、羧基、磺酸基、氨基、氰基、C1-C6烷基、C1-C6烷氧基、C1-C6烷硫基、C2-C6烯基和C2-C6炔基；以及R 8 , R 9 , R 10 , R 11 and R 12 are independently of each other selected from the group consisting of hydrogen, halogen, nitro, hydroxy, decyl, carboxyl, sulfonate, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 olefin Oxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 alkene a C 2 -C 20 alkynylthio group, a C 3 -C 20 cycloalkylthio group, a C 4 -C 20 cycloalkylalkylthio group and a C 6 -C 18 aryl group, wherein the aforementioned C 1 -C 20 alkyl group , C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 Alkylthio, C 2 -C 20 alkynylthio, C 3 -C 20 cycloalkylthio, C 4 -C 20 cycloalkylalkylthio and C 6 -C 18 aryl groups may optionally be one Or a plurality of groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, amino, cyano C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkenyl and C 2 -C 6 alkynyl group;
R13和R14相同或不同且选自H、C1-C6烷基和卤代C1-C6烷基。R 13 and R 14 are the same or different and are selected from the group consisting of H, C 1 -C 6 alkyl and halogenated C 1 -C 6 alkyl.
式(I)化合物中由于α-单羟基酮类结构部分的存在，使得该化合物保留了α-单羟基酮类光引发剂的特性，另外其中包含的肉桂酰基结构部分使得该化合物能够在紫外光辐射下可发生聚合交联，如此得到的式(I)化合物在保留了α-单羟基酮类光引发剂的优点的同时还改善了α-单羟基酮类光引发剂的异味和迁移性强的问题。The compound of the formula (I) retains the characteristics of the α-monohydroxyketone photoinitiator due to the presence of the α-monohydroxy ketone moiety, and additionally contains a cinnamoyl moiety which enables the compound to be in ultraviolet light. The polymerization cross-linking can occur under irradiation, and the compound of the formula (I) thus obtained improves the odor and migration of the α-monohydroxyketone photoinitiator while retaining the advantages of the α-monohydroxyketone photoinitiator. The problem.
在本发明中，前缀“Cn-Cm”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 means 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" means fluoro, chloro, bromo and iodo. In the present invention, it is preferred that the halogen includes F, Cl or a combination thereof.
本文所用的术语“Cn-Cm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。C1-C8烷基可以是甲基、乙基、丙基、异丙基、正丁基、2-丁基、叔丁基、戊基、异戊基、己基、庚基、辛基及其异构体。C1-C6烷基可以是甲基、乙基、丙基、异丙基、正丁基、2-丁基、叔丁基、戊基、异戊基、己基及其异构体。C1-C4烷基可以是甲基、乙基、丙基、1-甲基乙基、丁基、1-甲基丙基、2-甲基丙基、1，1-二甲基乙基及其异构体。The term "C n -C m alkyl" as used herein means having nm, for example 1-20, preferably 1-12, more preferably 1-8, particularly preferably 1-6, especially preferably 1-4 Branched or unbranched saturated hydrocarbon group of one carbon atom, 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, decyl, decyl, undecyl, dodecyl and their Structure. The C 1 -C 8 alkyl group may be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl and Its isomers. The C 1 -C 6 alkyl group may be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, pentyl, isopentyl, hexyl and isomers thereof. C 1 -C 4 alkyl may be methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl Base and its isomers.
本文所用术语“C2-Cm链烯基”是指具有2-m个，例如2-20个，优选2-6个，更优选2-4个碳原子并且具有一个或多个位于任何位置的双键的支化或未支化不饱和烃基，如乙烯基、1-丙烯基、2-丙烯基、1-甲基乙烯基、1-丁烯基、2-丁烯基、3-丁烯基、1-甲基-1-丙烯基、2-甲基-1-丙烯基、1-甲基-2-丙烯基、2-甲基-2-丙烯基、1-戊烯基、2-戊烯基、3-戊烯基、4-戊烯基、1-甲基-1-丁烯基、2-甲基-1-丁烯基、3-甲基-1-丁烯基、1-甲基-2-丁烯基、2-甲基-2-丁烯基、3-甲基-2-丁烯基、1-甲基-3-丁烯基、2-甲基-3-丁烯基、3-甲基-3-丁烯基、1，1-二甲基-2-丙烯基、1，2-二甲基-1-丙烯基、1，2-二甲基-2-丙烯基、1-乙基-1-丙烯基、1-乙基-2-丙烯基、1-己烯基、2-己烯基、3-己烯基、4-己烯基、5-己烯基、1-甲基-1-戊烯基、2-甲基-1-戊烯基、3-甲基-1-戊烯基、4-甲基-1-戊烯基、1-甲基-2-戊烯基、2-甲基-2-戊烯基、3-甲基-2-戊烯基、4-甲基-2-戊烯基、1-甲基-3-戊烯基、2-甲基-3-戊烯基、3-甲基-3-戊烯基、4-甲基-3-戊烯基、1-甲基-4-戊烯基、2-甲基-4-戊烯基、3-甲基-4-戊烯基、4-甲基-4-戊烯基、1，1-二甲基-2-丁烯基、1，1-二甲基-3-丁烯基、1，2-二甲基-1-丁烯基、1，2-二甲基-2-丁烯基、1，2-二甲基-3-丁烯基、1，3-二
甲基-1-丁烯基、1，3-二甲基-2-丁烯基、1，3-二甲基-3-丁烯基、2，2-二甲基-3-丁烯基、2，3-二甲基-1-丁烯基、2，3-二甲基-2-丁烯基、2，3-二甲基-3-丁烯基、3，3-二甲基-1-丁烯基、3，3-二甲基-2-丁烯基、1-乙基-1-丁烯基、1-乙基-2-丁烯基、1-乙基-3-丁烯基、2-乙基-1-丁烯基、2-乙基-2-丁烯基、2-乙基-3-丁烯基、1，1，2-三甲基-2-丙烯基、1-乙基-1-甲基-2-丙烯基、1-乙基-2-甲基-1-丙烯基、1-乙基-2-甲基-2-丙烯基及其异构体。C2-C6烯基可以是乙烯基、丙烯基、1-丁烯基、2-丁烯基、异丁烯基、1-戊烯基、2-戊烯基、新戊烯基、1-己烯基、2-己烯基、3-己烯基、异己烯基、新己烯基及其异构体。C2-C4烯基可以是乙烯基、1-丙烯基、2-丙烯基、1-甲基乙烯基、1-丁烯基、2-丁烯基、3-丁烯基、1-甲基-1-丙烯基、2-甲基-1-丙烯基、1-甲基-2-丙烯基、2-甲基-2-丙烯基及其异构体。As used herein, the term "C 2 -C m alkenyl" refers to a 2-m, for example 2-20, preferably 2-6, more preferably 2-4 carbon atoms and having one or more at any position Branched or unbranched unsaturated hydrocarbon groups of double bonds, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butyl Alkenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2 -pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3 -butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl- 2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5 -hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1 -methyl-2-pentenyl, 2-methyl- 2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4 -pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl 1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-Dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl- 1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3, 3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl- 1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1- Methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, 1-ethyl-2-methyl-2-propenyl and isomers thereof. The C 2 -C 6 alkenyl group may be a vinyl group, a propenyl group, a 1-butenyl group, a 2-butenyl group, an isobutenyl group, a 1-pentenyl group, a 2-pentenyl group, a neopentenyl group, or a 1-hexyl group. Alkenyl, 2-hexenyl, 3-hexenyl, isohexenyl, neohexenyl and isomers thereof. The C 2 -C 4 alkenyl group may be a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-methylvinyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-methyl group. Alkyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl and isomers thereof.
本文所用术语“C2-Cm炔基”是指具有2-m个，例如2-20个，优选2-6个，更优选2-4个碳原子并且具有一个或多个位于任何位置的叁键的支化或未支化不饱和烃基，如乙炔基、丙炔基、1-丁炔基、2-丁炔基及其异构体。C2-C6炔基可以是乙炔基、丙炔基、1-丁炔基、2-丁炔基、1-戊炔基、2-戊炔基、3-戊炔基、4-戊炔基、1-己炔基、2-己炔基、3-己炔基、4-己炔基、5-己炔基及其异构体。C2-C4炔基可以是乙炔基、丙炔基、1-丁炔基、2-丁炔基及其异构体。The term "C 2 -C m alkynyl" as used herein, refers to having from 2 to m, for example from 2 to 20, preferably from 2 to 6, more preferably from 2 to 4, carbon atoms and having one or more positions at any position. A branched or unbranched unsaturated hydrocarbon group of a hydrazone bond, such as an ethynyl group, a propynyl group, a 1-butynyl group, a 2-butynyl group, and isomers thereof. The C 2 -C 6 alkynyl group may be ethynyl, propynyl, 1-butynyl, 2-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentyne A group, a 1-hexynyl group, a 2-hexynyl group, a 3-hexynyl group, a 4-hexynyl group, a 5-hexynyl group, and isomers thereof. The C 2 -C 4 alkynyl group may be ethynyl, propynyl, 1-butynyl, 2-butynyl and isomers thereof.
本文所用术语“C3-Cm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, for example 3 to 20, preferably 3 to 8, more preferably 5 to 6 ring carbon atoms. Groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.
术语“C4-Cm环烷基烷基”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4-20个，优选4-8个碳原子，其中烷基和环烷基适用本文所定义。The term "C 4 -C m cycloalkylalkyl" denotes a cycloalkyl group substituted by an alkyl group and contains a total of 4 to m carbon atoms, for example 4 to 20, preferably 4 to 8 carbon atoms, wherein alkyl and Cycloalkyl is as defined herein.
“Cn-Cm烷氧基”和“Cn-Cm烷硫基”是指在Cn-Cm烷基的任何价键处键合有一个氧原子或一个硫原子作为连接基团的Cn-Cm烷基，例如C1-C20烷氧(或硫)基，优选C1-C12烷氧(或硫)基，更优选C1-C8烷氧(或硫)基，特别优选C1-C6烷氧(或硫)基，尤其优选C1-C4烷氧(或硫)基。C1-C8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。C1-C4烷氧基可以是甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、仲丁氧基、异丁氧基、叔丁氧基及其异构体。C1-C8烷硫基可以是甲硫基、乙硫基、丙硫基、异丙硫基、正丁基、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。C1-C4烷硫基可以是甲硫基、乙硫基、丙硫基、异丙硫基、正丁硫基及其异构体。"C n -C m alkoxy" and "C n -C m alkylthio" mean that an oxygen atom or a sulfur atom is bonded as a linking group at any valence bond of a C n -C m alkyl group. C n -C m alkyl, for example C 1 -C 20 alkoxy (or thio) group, preferably C 1 -C 12 alkoxy (or thio) group, more preferably C 1 -C 8 alkoxy (or sulphur) The group is particularly preferably a C 1 -C 6 alkoxy (or thio) group, particularly preferably a C 1 -C 4 alkoxy (or thio) group. The C 1 -C 8 alkoxy group may be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, pentyloxy, isopentyloxy Base, hexyloxy, heptyloxy, octyloxy, isooctyloxy and isomers thereof. The C 1 -C 4 alkoxy group may be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy and isomers thereof body. The C 1 -C 8 alkylthio group may be methylthio, ethylthio, propylthio, isopropylthio, n-butyl, 2-butylthio, tert-butylthio, pentylthio, isopentylthio. , hexylthio, heptylthio, octylthio, isooctylthio and isomers thereof. The C 1 -C 4 alkylthio group may be methylthio, ethylthio, propylthio, isopropylthio, n-butylthio and isomers thereof.
“C2-Cm烯氧基”和“C2-Cm烯硫基”是指在C2-Cm烯基中的任何饱和价键处键合有一个氧原子或一个硫原子作为连接基团的C2-Cm烯基，例如C2-C20烯氧(或硫)基，优选C2-C12烯氧(或硫)基，更优选C2-C8烯氧(或硫)基，特别优选C2-C6烯氧(或硫)基，尤其优选C2-C4烯氧(或硫)基。C1-C4烯氧基可以是乙烯氧基、丙烯氧基、异丙烯氧基、正丁烯氧基、仲丁烯氧基、异丁烯氧基、叔丁烯氧基及其异构体。C2-C4烯硫基可以是乙烯硫基、丙烯硫基、异丙烯硫基、正丁烯硫基及其异构体。"C 2 -C m alkenyloxy" and "C 2 -C m olefinylthio" mean that an oxygen atom or a sulfur atom is bonded as a linkage at any saturated valence bond in a C 2 -C m alkenyl group. a C 2 -C m alkenyl group of the group, for example a C 2 -C 20 olefinic oxygen (or thio) group, preferably a C 2 -C 12 olefinic oxygen (or thio) group, more preferably a C 2 -C 8 olefinic oxygen (or A sulfur group, a C 2 -C 6 alkene (or sulfur) group is particularly preferred, and a C 2 -C 4 alkoxy (or sulfur) group is particularly preferred. The C 1 -C 4 alkenyloxy group may be a vinyloxy group, a propyleneoxy group, an isopropenyloxy group, a n-butenyloxy group, a sec-butenyloxy group, an isobutenyloxy group, a t-butenyloxy group, and an isomer thereof. The C 2 -C 4 alkenethio group may be an ethylenethio group, an acrylthio group, an isopropenylthio group, an n-butenylthio group, and an isomer thereof.
“C2-Cm炔氧基”和“C2-Cm炔硫基”是指在C2-Cm炔基中的任何饱和价键处键合有一个氧原子或一个硫原子作为连接基团的C2-Cm炔基，例如C2-C20炔氧(或硫)基，优选C2-C12炔氧(或硫)基，更优选C2-C8炔氧(或硫)基，特别优选C2-C6炔氧(或硫)基，尤其优选C2-C4炔氧(或硫)基。C1-C4炔氧基可以是乙炔氧基、丙炔氧基、正丁炔氧基、仲丁炔氧基及其异构体。C2-C4炔硫基可以是乙炔硫基、丙炔硫基、丙炔硫基、正丁炔硫基、仲丁炔硫基及其异构体。"C 2 -C m alkynyloxy" and "C 2 -C m alkynylthio" mean that an oxygen atom or a sulfur atom is bonded as a linkage at any saturated valence bond in a C 2 -C m alkynyl group. a C 2 -C m alkynyl group of the group, for example a C 2 -C 20 alkyne (or thio) group, preferably a C 2 -C 12 alkyne (or thio) group, more preferably a C 2 -C 8 alkyne (or Sulfur), particularly preferably C 2 -C 6 alkyne (or sulfur) group, particularly preferably C 2 -C 4 alkyne (or sulfur) group. The C 1 -C 4 alkynyloxy group may be ethynyloxy, propynyloxy, n-butynyloxy, sec-butynyloxy and isomers thereof. The C 2 -C 4 alkynylthio group may be acetylenethio, propynylthio, propynylthio, n-butynylthio, sec-butynylthio and isomers thereof.
“C3-Cm环烷氧基”和“C3-Cm环烷硫基”是指在环烷基中的任何价键处键合有一个氧原子或一个硫原子作为连接基团的C3-Cm环烷基，例如C3-C20环烷氧(或硫)基，优选C3-C8环烷氧(或硫)基，更优选C5-C6环烷氧(或硫)基。C3-C20环烷氧基可以是环丙基氧基、环丁基氧基、环戊基氧基、环己基氧基、环庚基氧基、环辛基氧基、环癸基氧基及其异构体。C3-C20环烷硫基可以是环丙基硫基、环丁基硫基、环戊基硫基、环己基硫基、环庚基硫基、环辛基硫基、环癸基硫基及其异构体。"C 3 -C m cycloalkoxy" and "C 3 -C m cycloalkylthio" mean that an oxygen atom or a sulfur atom is bonded as a linking group at any valence bond in a cycloalkyl group. C 3 -C m cycloalkyl, for example C 3 -C 20 cycloalkoxy (or thio) group, preferably C 3 -C 8 cycloalkoxy (or thio) group, more preferably C 5 -C 6 cycloalkoxy ( Or sulfur). The C 3 -C 20 cycloalkoxy group may be a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group, a cyclodecyloxy group. Base and its isomers. The C 3 -C 20 cycloalkylthio group may be cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, cycloheptylthio, cyclooctylthio, cyclodecylthio Base and its isomers.
本文所用术语“C6-Cm芳基”是指含有6-m个碳原子，例如6-18个，优选6-10个碳原子的单环、双环或三环芳族烃基。作为C6-Cm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、甲基丙基苯基和萘基等；优选苯基或萘基，尤其是苯基(作为取代基也称为C6H5)。The term "C 6 -C m aryl" as used herein refers to a monocyclic, bicyclic or tricyclic aromatic hydrocarbon group containing 6 to m carbon atoms, for example 6 to 18, preferably 6 to 10 carbon atoms. As examples of the C 6 -C m aryl group, mention may be made of phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, xylyl, methylethylphenyl, diethylphenyl, a Propyl phenyl, naphthyl and the like; preferably phenyl or naphthyl, especially phenyl (also referred to as C 6 H 5 as a substituent).
在本发明中，R1、R2、R3、R4和R5彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C1-C20烷基、C2-C20烯基、C2-C20炔基、C3-C20环烷基、C4-C20环烷基烷基、C1-C20烷氧基、C2-C20烯氧基、C2-C20炔氧基、C3-C20环烷氧基、C4-C20环烷基烷氧基、C1-C20烷硫基、C2-C20烯硫基、C2-C20炔硫基、C3-C20环烷硫基、C4-C20环烷基烷硫基和C6-C18芳基，其中前述C1-C20烷基、C2-C20烯基、C2-C20炔基、C3-C20环烷基、C4-C20环烷基烷基、C1-C20烷氧基、C2-C20烯氧基、C2-C20炔氧基、C3-C20环烷氧基、C4-C20环烷基烷氧基、C1-C20烷硫基、C2-C20烯硫基、C2-C20炔硫基、C3-C20环烷硫基、C4-C20环烷基烷硫基和C6-C18芳基基团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、羧基、磺酸基、氨基、氰基、C1-C6烷基、C1-C6烷氧基、C1-C6烷硫基、C2-C6烯基和C2-C6炔基。优选的是，R1、R2、R3、R4和R5彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C8环烷基、C4-C8环烷基烷基、C1-C6烷氧基、C2-C6烯氧基、C2-C6炔氧基、C3-C8环烷氧基、C4-C8环烷基烷氧基、C1-C6烷硫基、C2-C6烯硫基、C2-C6炔硫基、C3-C8环烷硫基、C4-C8环烷基烷硫基和C6-C10芳基，其中前述C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C8环烷基、C4-C8环烷基烷基、C1-C6烷氧基、C2-C6烯氧基、C2-C6炔氧基、C3-C8环烷氧基、C4-C8环烷基烷氧基、C1-C6烷硫基、C2-C6烯硫基、C2-C6炔硫基、C3-C8环烷硫基、C4-C8环烷基烷硫基和C6-C10芳基基团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、羧基、磺酸基、氨基、氰基、C1-C4烷基、C1-C4烷氧基、C1-C4烷硫基、C2-C4烯基和C2-C4炔基。特别优选的是，R1、R2、R3、R4和R5彼此独立地选自氢、卤素、C1-C4烷基、C1-C4烷氧基和C1-C4烷硫基，其中前述C1-C4烷基、C1-C4烷氧基和C1-C4烷硫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、C1-C4烷基、C1-C4烷氧基和C1-C4烷硫基。
In the present invention, R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from the group consisting of hydrogen, halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 a -C 20 olefinylthio group, a C 2 -C 20 alkynylthio group, a C 3 -C 20 cycloalkylthio group, a C 4 -C 20 cycloalkylalkylthio group, and a C 6 -C 18 aryl group, wherein the aforementioned C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy , C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 alkenyl group, C 2 -C 20 alkynyl group, C 3 -C 20 cycloalkylthio, C 4 -C 20 cycloalkyl, alkylthio and C 6 -C 18 aryl group may be Optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, Group, a cyano group, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkenyl and C 2 -C 6 alkynyl group. Preferably, R 1 , R 2 , R 3 , R 4 and R 5 are independently of each other selected from the group consisting of hydrogen, halogen, nitro, hydroxy, thiol, carboxyl, sulfonate, amino, cyano, C 1 -C 6 Alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2 - a C 6 -alkylthio group, a C 2 -C 6 alkynylthio group, a C 3 -C 8 cycloalkylthio group, a C 4 -C 8 cycloalkylalkylthio group, and a C 6 -C 10 aryl group, wherein the aforementioned C 1 - C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2 -C 6 -alkylthio, C 2 -C 6 alkynylthio, C 3 -C 8 cycloalkylthio, C 4 -C 8 cycloalkylalkylthio and C 6 -C 10 aryl groups optionally substituted with one or more groups independently selected from the group: halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic, amino, cyano, C 1 -C 4 alkyl C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 2 -C 4 alkenyl and C 2 -C 4 alkynyl group. It is particularly preferred that R 1 , R 2 , R 3 , R 4 and R 5 are independently of each other selected from the group consisting of hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1 -C 4 An alkylthio group, wherein the aforementioned C 1 -C 4 alkyl group, C 1 -C 4 alkoxy group and C 1 -C 4 alkylthio group are optionally substituted by one or more groups independently selected from the group consisting of Halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1 -C 4 alkylthio.
在本发明中，R6和R7相同或不同且选自C1-C6烷基和卤代C1-C6烷基，或者R6和R7与它们所连接的碳原子一起形成C3-C8环烷基。优选的是，R6和R7相同或不同且选自C1-C4烷基和卤代C1-C4烷基，或者R6和R7与它们所连接的碳原子一起形成C5-C6环烷基。特别优选的是，R6和R7相同或不同且为甲基或卤代甲基，或者R6和R7与它们所连接的碳原子一起形成环戊基或环己基。In the present invention, R 6 and R 7 are the same or different and are selected from a C 1 -C 6 alkyl group and a halogenated C 1 -C 6 alkyl group, or R 6 and R 7 together with the carbon atom to which they are attached form a C 3- C 8 cycloalkyl. Preferably, R 6 and R 7 are the same or different and are selected from a C 1 -C 4 alkyl group and a halogenated C 1 -C 4 alkyl group, or R 6 and R 7 together with the carbon atom to which they are attached form a C 5 -C 6 cycloalkyl. It is particularly preferred that R 6 and R 7 are the same or different and are methyl or halomethyl, or that R 6 and R 7 together with the carbon atom to which they are attached form a cyclopentyl or cyclohexyl group.
在本发明中，R8、R9、R10、R11和R12彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C1-C20烷基、C2-C20烯基、C2-C20炔基、C3-C20环烷基、C4-C20环烷基烷基、C1-C20烷氧基、C2-C20烯氧基、C2-C20炔氧基、C3-C20环烷氧基、C4-C20环烷基烷氧基、C1-C20烷硫基、C2-C20烯硫基、C2-C20炔硫基、C3-C20环烷硫基、C4-C20环烷基烷硫基和C6-C18芳基，其中前述C1-C20烷基、C2-C20烯基、C2-C20炔基、C3-C20环烷基、C4-C20环烷基烷基、C1-C20烷氧基、C2-C20烯氧基、C2-C20炔氧基、C3-C20环烷氧基、C4-C20环烷基烷氧基、C1-C20烷硫基、C2-C20烯硫基、C2-C20炔硫基、C3-C20环烷硫基、C4-C20环烷基烷硫基和C6-C18芳基基团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、羧基、磺酸基、氨基、氰基、C1-C6烷基、C1-C6烷氧基、C1-C6烷硫基、C2-C6烯基和C2-C6炔基。优选的是，R8、R9、R10、R11和R12彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C8环烷基、C4-C8环烷基烷基、C1-C6烷氧基、C2-C6烯氧基、C2-C6炔氧基、C3-C8环烷氧基、C4-C8环烷基烷氧基、C1-C6烷硫基、C2-C6烯硫基、C2-C6炔硫基、C3-C8环烷硫基、C4-C8环烷基烷硫基和C6-C10芳基，其中前述C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C8环烷基、C4-C8环烷基烷基、C1-C6烷氧基、C2-C6烯氧基、C2-C6炔氧基、C3-C8环烷氧基、C4-C8环烷基烷氧基、C1-C6烷硫基、C2-C6烯硫基、C2-C6炔硫基、C3-C8环烷硫基、C4-C8环烷基烷硫基和C6-C10芳基基团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、羧基、磺酸基、氨基、氰基、C1-C4烷基、C1-C4烷氧基、C1-C4烷硫基、C2-C4烯基和C2-C4炔基。特别优选的是，R8、R9、R10、R11和R12
彼此独立地选自氢、卤素、C1-C4烷基、C2-C4烯基、C2-C4炔基、C1-C4烷氧基和C1-C4烷硫基，其中前述C1-C4烷基、C2-C4烯基、C2-C4炔基、C1-C4烷氧基和C1-C4烷硫基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、C1-C4烷基、C1-C4烷氧基和C1-C4烷硫基。In the present invention, R 8 , R 9 , R 10 , R 11 and R 12 are each independently selected from the group consisting of hydrogen, halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 a -C 20 olefinylthio group, a C 2 -C 20 alkynylthio group, a C 3 -C 20 cycloalkylthio group, a C 4 -C 20 cycloalkylalkylthio group, and a C 6 -C 18 aryl group, wherein the aforementioned C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy , C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 olefinylthio group, C 2 -C 20 alkynylthio group, C 3 -C 20 cycloalkylthio group, C 4 -C 20 cycloalkylalkylthio group and C 6 -C 18 aryl group Optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonate Amino, cyano, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkenyl and C 2 -C 6 alkynyl group. Preferably, R 8 , R 9 , R 10 , R 11 and R 12 are independently of each other selected from the group consisting of hydrogen, halogen, nitro, hydroxy, thiol, carboxyl, sulfonate, amino, cyano, C 1 -C 6 Alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2 - a C 6 -alkylthio group, a C 2 -C 6 alkynylthio group, a C 3 -C 8 cycloalkylthio group, a C 4 -C 8 cycloalkylalkylthio group, and a C 6 -C 10 aryl group, wherein the aforementioned C 1 - C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2 -C 6 -alkylthio, C 2 -C 6 alkynylthio, C 3 -C 8 cycloalkylthio, C 4 -C 8 cycloalkylalkylthio and C 6 -C 10 aryl groups optionally substituted with one or more groups independently selected from the group: halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic, amino, cyano, C 1 -C 4 alkoxy , C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 2 -C 4 alkenyl and C 2 -C 4 alkynyl group. It is particularly preferred that R 8 , R 9 , R 10 , R 11 and R 12 are independently of each other selected from the group consisting of hydrogen, halogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkyne a C 1 -C 4 alkoxy group and a C 1 -C 4 alkylthio group, wherein the aforementioned C 1 -C 4 alkyl group, C 2 -C 4 alkenyl group, C 2 -C 4 alkynyl group, C 1 -C The 4 alkoxy group and the C 1 -C 4 alkylthio group may be optionally substituted by one or more groups independently selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1 -C 4 Alkoxy and C 1 -C 4 alkylthio.
在本发明中，R13和R14相同或不同且选自H、C1-C6烷基和卤代C1-C6烷基。优选的是，R13和R14相同或不同且选自H、C1-C4烷基和卤代C1-C4烷基。特别优选的是，R13和R14均为H。In the present invention, R 13 and R 14 are the same or different and are selected from the group consisting of H, C 1 -C 6 alkyl and halogenated C 1 -C 6 alkyl. Preferably, the same or different, and R 14 and R 13 is selected from H, C 1 -C 4 alkyl and halo C 1 -C 4 alkyl. It is particularly preferred that both R 13 and R 14 are H.
在本发明的一个特别优选的实施方案中，式(I)化合物选自下组：In a particularly preferred embodiment of the invention, the compound of formula (I) is selected from the group consisting of
根据本发明的第二个方面，提供了一种制备本发明式(I)化合物的方法，包括使式(II)化合物与式(III)化合物进行酯化反应，得到式(I)化合物，According to a second aspect of the present invention, there is provided a process for the preparation of a compound of the formula (I) according to the invention, which comprises the esterification of a compound of the formula (II) with a compound of the formula (III) to give a compound of the formula (I),
其中R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13和R14如对式(I)化合物所定义，以及X为羟基或卤素。Wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are as defined for the compound of formula (I) Definition, and X is hydroxy or halogen.
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、氢化锂、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 esterification reaction is usually carried out in the presence of a catalyst suitable for the esterification reaction. As the catalyst, an acidic catalyst or a basic catalyst can 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 may be used. And sodium hydrogencarbonate, sodium t-butoxide, sodium ethoxide, sodium hydride, potassium hydride, lithium 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 knowledge in the art or by several routine preliminary experiments.
为了提高式(I)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 compound of the formula (I), it is advantageous to remove the water produced by the esterification reaction during the esterification reaction. This can be done, for example, by distillation 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(II)和式(III)化合物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 esterification reaction is usually carried out in a solvent, preferably in an organic solvent. The selection of the type of the solvent is not particularly limited as long as the compound of the formula (II) and the formula (III) can be dissolved and chemically inert to the esterification reaction, that is, it does not participate in the esterification reaction. As examples of the solvent, mention may be made of tetrahydrofuran, benzene, toluene, N,N-dimethylformamide, dichloromethane and acetone. The solvent may be used singly or as a mixture of two or more solvents.
式(II)化合物与式(III)化合物的相对用量没有特别的限制，通常而言它们以等摩尔量使用。The relative amounts of the compound of the formula (II) and the compound of the formula (III) are not particularly limited, and generally they are used in an equimolar amount.
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 over a very wide temperature range. According to the invention, the ester is advantageously
The reaction is carried out at a temperature of from -10 ° C to 150 ° C, preferably from 0 ° C to 100 ° C, preferably at room temperature. The esterification reaction time is also not particularly limited and is usually carried out for 1 to 24 hours, preferably 1 to 12 hours.
在酯化反应完成之后，获得包含式(I)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)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，得到了式(I)化合物的粗产物。如果想要进一步提高式(I)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)化合物的粗产物进行重结晶。After the esterification reaction is completed, a reaction mixture comprising a compound of formula (I) is obtained. Therefore, the reaction mixture needs to be worked up to give a purified compound of formula (I). Generally, the reaction mixture obtained by the esterification reaction is first filtered, and the filtrate fraction is taken out. The filtrate is then washed to remove the catalyst and unreacted starting materials. The washing liquid is not particularly limited as long as the catalyst and the unreacted raw material can be removed. As examples of the washing liquid, dilute hydrochloric acid (aqueous solution), saturated aqueous sodium hydrogencarbonate solution and water can be mentioned. The concentration of the dilute hydrochloric acid is not particularly limited, and generally, a dilute hydrochloric acid having a concentration of 5 to 12% is used. The washing with the washing liquid may be carried out once or several times; in the case of multiple times, a single washing liquid may be used, or different washing liquids may be used in sequence. According to the present invention, it is advantageous to wash the filtrate obtained by filtering the reaction mixture obtained by the esterification reaction with dilute hydrochloric acid, a saturated aqueous sodium hydrogencarbonate solution and water. Of course, each time after washing with the washing liquid, it is necessary to pour off the aqueous phase and then wash the organic phase with the next washing liquid. After washing, drying is required to remove residual water. For this purpose, it is usually dried using anhydrous sodium sulfate. After drying, the residual organic solvent is removed. The means for removing the organic solvent herein is not particularly limited, and the organic solvent can usually be removed by distillation under reduced pressure. After removal of the residual organic solvent, the crude product of the compound of formula (I) is obtained. If it is desired to further increase the purity of the compound of formula (I), the compound may be further purified, which may be carried out, for example, by recrystallization. The selection of the recrystallization solvent is conventional and is not particularly limited. According to the invention, it is advantageous to recrystallize the crude product of the compound of formula (I) with methanol.
本发明的式(I)化合物中既包含α-单羟基酮类结构部分，又包含肉桂酰基结构部分，因此该化合物即可发挥α-单羟基酮类的光引发剂作用，又因为肉桂酰基结构部分的引入而改善α-单羟基酮类光引发剂固有存在的异味和迁移性强的问题。The compound of the formula (I) of the present invention contains both an α-monohydroxy ketone moiety and a cinnamoyl moiety, so that the compound can function as a photoinitiator of the α-monohydroxy ketone and also because of the cinnamoyl structure. Partial introduction improves the problem of the strong odor and migration inherent in the α-monohydroxyketone photoinitiator.
因此，根据本发明的第三个方面，提供了本发明式(I)化合物作为光引发剂的用途。Thus, according to a third aspect of the invention, there is provided the use of a compound of formula (I) according to the invention as a photoinitiator.
本发明式(I)化合物可吸收200-350nm的电磁波。在吸收电磁波后，式(I)化合物由基态变为激发态，使得式(I)化合物中苯甲酰结构部分中的酰基
碳原子与相邻甲氧基中的碳原子断裂，形成两个自由基，从而引发光聚合或光交联。另外，由于式(I)化合物的肉桂酰基结构部分含有不饱和的碳碳双键，因此不同分子间碳碳双键在受到电磁波辐射时容易反应形成更大的分子或交联结构，从而大大改善光引发剂导致的异味和迁移性强的问题，显著减少了异味和显著降低了迁移性。The compound of the formula (I) of the present invention can absorb electromagnetic waves of 200 to 350 nm. After absorbing electromagnetic waves, the compound of formula (I) changes from a ground state to an excited state, such that the acyl group in the benzoyl moiety of the compound of formula (I)
The carbon atom is cleaved with carbon atoms in the adjacent methoxy group to form two radicals, thereby initiating photopolymerization or photocrosslinking. In addition, since the cinnamoyl moiety of the compound of the formula (I) contains an unsaturated carbon-carbon double bond, different intermolecular carbon-carbon double bonds are easily reacted to form a larger molecular or cross-linked structure upon exposure to electromagnetic waves, thereby greatly improving The problem of strong odor and migration caused by photoinitiators significantly reduces odor and significantly reduces migration.
式(I)化合物可在涂料、油墨、微电子、印刷等领域以及制备激光录像及三维元件等新型领域用作光引发剂。当式(I)化合物用作光引发剂时，其用量是常规的，或者通过例行的预备试验即可确定。The compound of the formula (I) can be used as a photoinitiator in novel fields such as coatings, inks, microelectronics, printing, and the like, and in the preparation of laser recording and three-dimensional components. When the compound of the formula (I) is used as a photoinitiator, the amount thereof 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 invention is further illustrated by the following examples, which are not to be construed as limiting the scope of the invention.
实施例1：3-苯基-2-丙烯酸苯甲酰基异丙酯Example 1: 3-Phenyl-2-acrylic acid benzoyl isopropyl ester
将16.4g(0.1mol)2-羟基-2-甲基-1-苯基-1-丙酮置于250ml三口瓶中，加入100ml二氯甲烷和10.1g(0.1mol)三乙胺。搅拌均匀后，加入16.6g(0.1mol)3-苯基-2-丙烯酰氯，于室温下搅拌反应3h。然后，过滤反应液，将滤液依次用稀盐酸(5％)，饱和碳酸氢钠水溶液和蒸馏水洗涤，然后用无水硫酸钠干燥过夜后过滤，减压蒸馏除去有机相，甲醇重结晶后，得淡黄色晶体，共13g，该产物经1H-NMR谱确认为标题化合物，称作1173-CC。16.4 g (0.1 mol) of 2-hydroxy-2-methyl-1-phenyl-1-propanone was placed in a 250 ml three-necked flask, and 100 ml of dichloromethane and 10.1 g (0.1 mol) of triethylamine were added. After stirring uniformly, 16.6 g (0.1 mol) of 3-phenyl-2-acryloyl chloride was added, and the reaction was stirred at room temperature for 3 h. Then, the reaction liquid was filtered, and the filtrate was washed successively with dilute hydrochloric acid (5%), saturated aqueous sodium hydrogen carbonate and distilled water, and then dried over anhydrous sodium sulfate and filtered, and the organic phase was evaporated under reduced pressure. The pale yellow crystals were a total of 13 g, and the product was confirmed to be the title compound by the 1 H-NMR spectrum.
1H-NMR(谱)(在Acetone-d6中测定)(δppm)：1.80(s，6H)，6.56(d，1H)，7.45(m，9H)，8.11(d，2H)。 1 H-NMR (spectrum) (measured in Acetone-d6) (δ ppm): 1.80 (s, 6H), 6.56 (d, 1H), 7.45 (m, 9H), 8.11 (d, 2H).
实施例2：3-(4-甲氧基)苯基-2-丙烯酸苯甲酰基异丙酯Example 2: 3-(4-methoxy)phenyl-2-acrylic acid benzoyl isopropyl ester
将16.4g(0.1mol)2-羟基-2-甲基-1-苯基-1-丙酮置于250ml三口瓶中，加入100ml二氯甲烷和10.1g(0.1mol)三乙胺。搅拌均匀后，加入18g(0.1mol)3-(4-甲氧基)苯基-2-丙烯酰氯，于室温下搅拌反应3h。然后，过滤反应液，将滤液依次用稀盐酸(5％)，饱和碳酸氢钠水溶液和蒸馏水洗涤，然后用无水硫酸钠干燥过夜后过滤，减压蒸馏除去有机相，甲醇重结晶后，得淡黄色晶体，共18g，该产物经1H-NMR谱确认为标题化合物。16.4 g (0.1 mol) of 2-hydroxy-2-methyl-1-phenyl-1-propanone was placed in a 250 ml three-necked flask, and 100 ml of dichloromethane and 10.1 g (0.1 mol) of triethylamine were added. After stirring uniformly, 18 g (0.1 mol) of 3-(4-methoxy)phenyl-2-acryloyl chloride was added, and the reaction was stirred at room temperature for 3 h. Then, the reaction liquid was filtered, and the filtrate was washed successively with dilute hydrochloric acid (5%), saturated aqueous sodium hydrogen carbonate and distilled water, and then dried over anhydrous sodium sulfate and filtered, and the organic phase was evaporated under reduced pressure. The pale yellow crystals, a total of 18 g, were identified as the title compound by 1 H-NMR spectrum.
1H-NMR(谱)(在Acetone-d6中测定)：1.60(s，6H)，3.80(s，3H)，6.31(d，1H)，7.48(m，9H)，7.97(d，2H)。 1 H-NMR (spectrum) (measured in Acetone-d6): 1.60 (s, 6H), 3.80 (s, 3H), 6.31 (d, 1H), 7.48 (m, 9H), 7.97 (d, 2H) .
实施例3：3-苯基-2-丙烯酸4-甲基苯基甲酰基异丙酯Example 3: 4-methylphenylformic acid isopropyl 3-phenyl-2-acrylate
将17.7g(0.1mol)2-羟基-2-甲基-1-(4-甲基)苯基-1-丙酮置于250ml三口瓶中，加入100ml二氯甲烷和10.1g(0.1mol)三乙胺。搅拌均匀后，加入16.6g(0.1mol)肉桂酰氯，于室温下搅拌反应3h。然后，过滤反应液，将滤液依次用稀盐酸(5％)，饱和碳酸氢钠水溶液和蒸馏水洗涤，然后用无水硫酸钠干燥过夜后过滤，减压蒸馏除去有机相，甲醇重结晶后，得淡黄色晶体，共16g，该产物经1H-NMR谱确认为标题化合物。17.7 g (0.1 mol) of 2-hydroxy-2-methyl-1-(4-methyl)phenyl-1-propanone was placed in a 250 ml three-necked flask, and 100 ml of dichloromethane and 10.1 g (0.1 mol) of three were added. Ethylamine. After stirring uniformly, 16.6 g (0.1 mol) of cinnamoyl chloride was added, and the reaction was stirred at room temperature for 3 h. Then, the reaction liquid was filtered, and the filtrate was washed successively with dilute hydrochloric acid (5%), saturated aqueous sodium hydrogen carbonate and distilled water, and then dried over anhydrous sodium sulfate and filtered, and the organic phase was evaporated under reduced pressure. The product was identified as the title compound by 1 H-NMR spectrum.
1H-NMR(谱)(在Acetone-d6中测定)：1.78(s，6H)，2.34(s，6H)，6.54(d，1H)，7.35(m，9H)，8.11(d，2H)。 1 H-NMR (spectrum) (measured in Acetone-d6): 1.78 (s, 6H), 2.34 (s, 6H), 6.54 (d, 1H), 7.35 (m, 9H), 8.11 (d, 2H) .
实施例4：3-苯基-2-丙烯酸4-甲硫基苯基甲酰基异丙酯Example 4: 4-methylthiophenylformate isopropyl 3-phenyl-2-acrylate
将21g(0.1mol)2-羟基-2-甲基-1-(4-甲硫基苯基)-1-丙酮置于250ml三口瓶中，加入100ml-二氯甲烷和10.1g(0.1mol)三乙胺。搅拌均匀后，加入16.6g(0.1mol)肉桂酰氯，于室温下搅拌反应3h。然后，过滤反应液，将滤液依次用稀盐酸(5％)，饱和碳酸氢钠水溶液和蒸馏水洗涤，然后用无水硫
酸钠干燥过夜后过滤，减压蒸馏除去有机相，甲醇重结晶后，得黄色晶体，共18g，该产物经1H-NMR谱确认为标题化合物。21 g (0.1 mol) of 2-hydroxy-2-methyl-1-(4-methylthiophenyl)-1-propanone was placed in a 250 ml three-necked flask, and 100 ml-dichloromethane and 10.1 g (0.1 mol) were added. Triethylamine. After stirring uniformly, 16.6 g (0.1 mol) of cinnamoyl chloride was added, and the reaction was stirred at room temperature for 3 h. Then, the reaction liquid was filtered, and the filtrate was washed successively with dilute hydrochloric acid (5%), saturated aqueous sodium hydrogen carbonate and distilled water, and then dried over anhydrous sodium sulfate and filtered, and the organic phase was evaporated under reduced pressure. Yellow crystals, a total of 18 g, were identified as the title compound by 1 H-NMR.
1H-NMR(谱)(在Acetone-d6中测定)：1.80(s，6H)，2.53(s，6H)，6.56(d，1H)，7.45(m，9H)，8.11(d，2H)。 1 H-NMR (spectrum) (measured in Acetone-d6): 1.80 (s, 6H), 2.53 (s, 6H), 6.56 (d, 1H), 7.45 (m, 9H), 8.11 (d, 2H) .
实施例5：3-苯基-2-丙烯酸1-苯甲酰基环己基酯Example 5: 1-Benzoylcyclohexyl ester of 3-phenyl-2-propenoic acid
将20.4g(0.1mol)(1-羟基环己基)(苯基)甲酮置于250ml三口瓶中，加入100ml二氯甲烷和10.1g(0.1mol)三乙胺。搅拌均匀后，加入16.6g(0.1mol)肉桂酰氯，于室温下搅拌反应3h。然后，过滤反应液，将滤液依次用稀盐酸，饱和碳酸氢钠水溶液和蒸馏水洗涤。然后，用无水硫酸钠干燥过夜后过滤，减压蒸馏除去有机相，甲醇重结晶后，得黄色晶体，共20g，该产物经1H-NMR谱确认为标题化合物，称作184-CC。20.4 g (0.1 mol) of (1-hydroxycyclohexyl)(phenyl)methanone was placed in a 250 ml three-necked flask, and 100 ml of dichloromethane and 10.1 g (0.1 mol) of triethylamine were added. After stirring uniformly, 16.6 g (0.1 mol) of cinnamoyl chloride was added, and the reaction was stirred at room temperature for 3 h. Then, the reaction liquid was filtered, and the filtrate was washed successively with dilute hydrochloric acid, saturated aqueous sodium hydrogen carbonate and distilled water. Then, after filtered and dried overnight over anhydrous sodium sulfate, the organic phase evaporated under reduced pressure, and recrystallized from methanol was removed to give yellow crystals, a total of 20g, the product was confirmed that 1 H-NMR spectrum of the title compound, referred to as 184-CC.
1H-NMR(谱)(在Acetone-d6中测定)：1.36(m，6H)，1.69(m，2H)，2.42(d，2H)，6.59(d，1H)，7.39(m，6H)，7.65(m，3H)，8.06(d，2H)。 1 H-NMR (spectrum) (measured in Acetone-d6): 1.36 (m, 6H), 1.69 (m, 2H), 2.42 (d, 2H), 6.59 (d, 1H), 7.39 (m, 6H) , 7.65 (m, 3H), 8.06 (d, 2H).
实施例6：3-(4-甲氧基苯基)-2-丙烯酸1-苯甲酰基环己基酯Example 6: 1-Benzylcyclohexyl ester of 3-(4-methoxyphenyl)-2-propenoic acid
将20.4g(0.1mol)(1-羟基环己基)(苯基)甲酮置于250ml三口瓶中，加入100ml二氯甲烷和10.1g(0.1mol)三乙胺。搅拌均匀后，加入18g(0.1mol)3-(4-甲氧基)苯基-2-丙烯酰氯，于室温下搅拌反应3h。然后，过滤反应液，将滤液依次用稀盐酸(5％)，饱和碳酸氢钠水溶液和蒸馏水洗涤，然后用无水硫酸钠干燥过夜后过滤，减压蒸馏除去有机相，甲醇重结晶后，得黄色晶体，共23g，该产物经1H-NMR谱确认为标题化合物。
20.4 g (0.1 mol) of (1-hydroxycyclohexyl)(phenyl)methanone was placed in a 250 ml three-necked flask, and 100 ml of dichloromethane and 10.1 g (0.1 mol) of triethylamine were added. After stirring uniformly, 18 g (0.1 mol) of 3-(4-methoxy)phenyl-2-acryloyl chloride was added, and the reaction was stirred at room temperature for 3 h. Then, the reaction liquid was filtered, and the filtrate was washed successively with dilute hydrochloric acid (5%), saturated aqueous sodium hydrogen carbonate and distilled water, and then dried over anhydrous sodium sulfate and filtered, and the organic phase was evaporated under reduced pressure. Yellow crystals, a total of 23 g, were identified as the title compound by 1 H-NMR spectrum.
1H-NMR(谱)(在Acetone-d6中测定)：1.35(m，6H)，1.70(m，2H)，2.41(d，2H)，3.75(s，3H)，6.60(d，1H)，7.41(m，6H)，7.64(m，3H)，8.05(d，2H)。 1 H-NMR (spectrum) (measured in Acetone-d6): 1.35 (m, 6H), 1.70 (m, 2H), 2.41 (d, 2H), 3.75 (s, 3H), 6.60 (d, 1H) , 7.41 (m, 6H), 7.64 (m, 3H), 8.05 (d, 2H).
实施例7：3-苯基-2-丙烯酸1-(2-甲基苯甲酰基)环己基酯Example 7: 1-(2-methylbenzoyl)cyclohexyl 3-phenyl-2-acrylate
将21.8g(0.1mol)(1-羟基环己基)(2-甲基苯基)甲酮置于250ml三口瓶中，加入100ml二氯甲烷和10.1g(0.1mol)三乙胺。搅拌均匀后，加入16.6g(0.1mol)肉桂酰氯，于室温下搅拌反应3h。然后，过滤反应液，将滤液依次用稀盐酸(5％)，饱和碳酸氢钠水溶液和蒸馏水洗涤，然后用无水硫酸钠干燥过夜后过滤，减压蒸馏除去有机相，甲醇重结晶后，得黄色晶体，共21g，该产物经1H-NMR谱确认为标题化合物。21.8 g (0.1 mol) of (1-hydroxycyclohexyl)(2-methylphenyl)methanone was placed in a 250 ml three-necked flask, and 100 ml of dichloromethane and 10.1 g (0.1 mol) of triethylamine were added. After stirring uniformly, 16.6 g (0.1 mol) of cinnamoyl chloride was added, and the reaction was stirred at room temperature for 3 h. Then, the reaction liquid was filtered, and the filtrate was washed successively with dilute hydrochloric acid (5%), saturated aqueous sodium hydrogen carbonate and distilled water, and then dried over anhydrous sodium sulfate and filtered, and the organic phase was evaporated under reduced pressure. Yellow crystals, a total of 21 g , were identified as the title compound by 1 H-NMR spectrum.
1H-NMR(谱)(在Acetone-d6中测定)：1.36(m，6H)，1.69(m，2H)，2.42(d，2H)，2.48(s，3H)，6.59(d，1H)，7.39(m，6H)，7.65(m，3H)，8.06(d，2H)。 1 H-NMR (spectrum) (measured in Acetone-d6): 1.36 (m, 6H), 1.69 (m, 2H), 2.42 (d, 2H), 2.48 (s, 3H), 6.59 (d, 1H) , 7.39 (m, 6H), 7.65 (m, 3H), 8.06 (d, 2H).
实施例8：3-苯基-2-丙烯酸1-(4-异丙基苯甲酰基)环己基酯Example 8: 1-(4-isopropylbenzoyl)cyclohexyl 3-phenyl-2-propenoate
将24.6g(0.1mol)(1-羟基环己基)(4-异丙基苯基)甲酮置于250ml三口瓶中，加入100ml二氯甲烷和10.1g(0.1mol)三乙胺。搅拌均匀后，加入24.6g(0.1mol)肉桂酰氯，于室温下搅拌反应3h。然后，过滤反应液，将滤液依次用稀盐酸(5％)，饱和碳酸氢钠水溶液和蒸馏水洗涤，然后用无水硫酸钠干燥过夜后过滤，减压蒸馏除去有机相，甲醇重结晶后，得黄色晶体，共23g，该产物经1H-NMR谱确认为标题化合物。24.6 g (0.1 mol) of (1-hydroxycyclohexyl)(4-isopropylphenyl)methanone was placed in a 250 ml three-necked flask, and 100 ml of dichloromethane and 10.1 g (0.1 mol) of triethylamine were added. After stirring uniformly, 24.6 g (0.1 mol) of cinnamoyl chloride was added, and the reaction was stirred at room temperature for 3 hours. Then, the reaction liquid was filtered, and the filtrate was washed successively with dilute hydrochloric acid (5%), saturated aqueous sodium hydrogen carbonate and distilled water, and then dried over anhydrous sodium sulfate and filtered, and the organic phase was evaporated under reduced pressure. Yellow crystals, a total of 23 g, were identified as the title compound by 1 H-NMR spectrum.
1H-NMR(谱)(在Acetone-d6中测定)：1.01(d，6H)，1.36(m，6H)，1.69(m，2H)，2.42(d，2H)，2.51(q，2H)，6.59(d，1H)，7.40(m，6H)，7.64(m，3H)，
8.05(d，2H)。 1 H-NMR (spectrum) (measured in Acetone-d6): 1.01 (d, 6H), 1.36 (m, 6H), 1.69 (m, 2H), 2.42 (d, 2H), 2.51 (q, 2H) , 6.59 (d, 1H), 7.40 (m, 6H), 7.64 (m, 3H), 8.05 (d, 2H).
实施例9：3-(4-甲氧基)苯基-2-丙烯酸4-甲氧基苯甲酰基异丙酯Example 9: 4-methoxybenzoyl isopropyl 3-(4-methoxy)phenyl-2-acrylate
将19.4g(0.1mol)2-羟基-2-甲基-1-(4-甲氧基苯基)-1-丙酮置于250ml三口瓶中，加入100ml二氯甲烷和10.1g(0.1mol)三乙胺。搅拌均匀后，加入18g(0.1mol)3-(4-甲氧基)苯基-2-丙烯酰氯，于室温下搅拌反应3h。然后，过滤反应液，将滤液依次用稀盐酸(5％)，饱和碳酸氢钠水溶液和蒸馏水洗涤，然后用无水硫酸钠干燥过夜后过滤，减压蒸馏除去有机相，甲醇重结晶后，得淡黄色晶体，共15.5g，该产物经1H-NMR谱确认为标题化合物。19.4 g (0.1 mol) of 2-hydroxy-2-methyl-1-(4-methoxyphenyl)-1-propanone was placed in a 250 ml three-necked flask, and 100 ml of dichloromethane and 10.1 g (0.1 mol) were added. Triethylamine. After stirring uniformly, 18 g (0.1 mol) of 3-(4-methoxy)phenyl-2-acryloyl chloride was added, and the reaction was stirred at room temperature for 3 h. Then, the reaction liquid was filtered, and the filtrate was washed successively with dilute hydrochloric acid (5%), saturated aqueous sodium hydrogen carbonate and distilled water, and then dried over anhydrous sodium sulfate and filtered, and the organic phase was evaporated under reduced pressure. The product was identified as the title compound by 1 H-NMR spectrum.
1H-NMR(谱)(在Acetone-d6中测定)：1.50(s，6H)，3.83(s，6H)，5.75(s，2H)，6.54(d，1H)，7.35(m，9H)，8.11(d，2H)。 1 H-NMR (spectrum) (measured in Acetone-d6): 1.50 (s, 6H), 3.83 (s, 6H), 5.75 (s, 2H), 6.54 (d, 1H), 7.35 (m, 9H) , 8.11 (d, 2H).
对比例9：3-(4-甲氧基)苯基-2-丙烯酸苯甲酰基甲酯Comparative Example 9: 3-(4-methoxy)phenyl-2-acrylic acid benzoylmethyl ester
将13.6g(0.1mol)2-羟基-1-苯基-1-乙酮置于250ml三口瓶中，加入100ml二氯甲烷和10.1g(0.1mol)三乙胺。搅拌均匀后，加入18g(0.1mol)3-(4-甲氧基)苯基-2-丙烯酰氯，于室温下搅拌反应3h。然后，过滤反应液，将滤液依次用稀盐酸(5％)，饱和碳酸氢钠水溶液和蒸馏水洗涤，然后用无水硫酸钠干燥过夜后过滤，减压蒸馏除去有机相，甲醇重结晶后，得淡黄色晶体，共15.5g，该产物经1H-NMR谱确认为标题化合物。13.6 g (0.1 mol) of 2-hydroxy-1-phenyl-1-ethanone was placed in a 250 ml three-necked flask, and 100 ml of dichloromethane and 10.1 g (0.1 mol) of triethylamine were added. After stirring uniformly, 18 g (0.1 mol) of 3-(4-methoxy)phenyl-2-acryloyl chloride was added, and the reaction was stirred at room temperature for 3 h. Then, the reaction liquid was filtered, and the filtrate was washed successively with dilute hydrochloric acid (5%), saturated aqueous sodium hydrogen carbonate and distilled water, and then dried over anhydrous sodium sulfate and filtered, and the organic phase was evaporated under reduced pressure. The product was identified as the title compound by 1 H-NMR spectrum.
1H-NMR(谱)(在Acetone-d6中测定)：3.83(s，3H)，5.75(s，2H)，6.54(d，1H)，7.35(m，9H)，8.11(d，2H)。 1 H-NMR (spectrum) (measured in Acetone-d6): 3.83 (s, 3H), 5.75 (s, 2H), 6.54 (d, 1H), 7.35 (m, 9H), 8.11 (d, 2H) .
实施例10：3-(4-甲氧基)苯基-2-丙烯酸(1-苯甲酰基-1，1-双(三氯甲基))甲酯
Example 10: 3-(4-methoxy)phenyl-2-acrylic acid (1-benzoyl-1,1-bis(trichloromethyl))methyl ester
将36.7g(0.1mol)2-羟基-2，2-双(三氯甲基)-1-苯基-1-乙酮置于250ml三口瓶中，加入100ml二氯甲烷和10.1g(0.1mol)三乙胺。搅拌均匀后，加入18g(0.1mol)3-(4-甲氧基)苯基-2-丙烯酰氯，于室温下搅拌反应3h。然后，过滤反应液，将滤液依次用稀盐酸(5％)，饱和碳酸氢钠水溶液和蒸馏水洗涤，然后用无水硫酸钠干燥过夜后过滤，减压蒸馏除去有机相，甲醇重结晶后，得淡黄色晶体，共28g，该产物经1H-NMR谱确认为标题化合物。36.7 g (0.1 mol) of 2-hydroxy-2,2-bis(trichloromethyl)-1-phenyl-1-ethanone was placed in a 250 ml three-necked flask, 100 ml of dichloromethane and 10.1 g (0.1 mol) were added. ) Triethylamine. After stirring uniformly, 18 g (0.1 mol) of 3-(4-methoxy)phenyl-2-acryloyl chloride was added, and the reaction was stirred at room temperature for 3 h. Then, the reaction liquid was filtered, and the filtrate was washed successively with dilute hydrochloric acid (5%), saturated aqueous sodium hydrogen carbonate and distilled water, and then dried over anhydrous sodium sulfate and filtered, and the organic phase was evaporated under reduced pressure. The product was identified as the title compound by 1 H-NMR spectrum.
1H-NMR(谱)(在Acetone-d6中测定)：3.83(s，3H)，6.54(d，1H)，7.35(m，9H)，8.11(d，2H)。 1 H-NMR (spectrum) (measured in Acetone-d6): 3.83 (s, 3H), 6.54 (d, 1H), 7.35 (m, 9H), 8.11 (d, 2H).
实施例11：3-(4-甲氧基)苯基-2-丙烯酸4-苯硫基苯基甲酰基异丙酯Example 11: 4-phenylthiophenylformate isopropyl 3-(4-methoxy)phenyl-2-acrylate
将15g(0.1mol)2-羟基-2-甲基-1-(4-苯硫基苯基)-1-丙酮置于250ml三口瓶中，加入100ml二氯甲烷和10.1g(0.1mol)三乙胺。搅拌均匀后，加入18g(0.1mol)3-(4-甲氧基)苯基-2-丙烯酰氯，于室温下搅拌反应3h。然后，过滤反应液，将滤液依次用稀盐酸(5％)，饱和碳酸氢钠水溶液和蒸馏水洗涤，然后用无水硫酸钠干燥过夜后过滤，减压蒸馏除去有机相，甲醇重结晶后，得淡黄色晶体，共16g，该产物经1H-NMR谱确认为标题化合物。15 g (0.1 mol) of 2-hydroxy-2-methyl-1-(4-phenylthiophenyl)-1-propanone was placed in a 250 ml three-necked flask, and 100 ml of dichloromethane and 10.1 g (0.1 mol) of three were added. Ethylamine. After stirring uniformly, 18 g (0.1 mol) of 3-(4-methoxy)phenyl-2-acryloyl chloride was added, and the reaction was stirred at room temperature for 3 h. Then, the reaction liquid was filtered, and the filtrate was washed successively with dilute hydrochloric acid (5%), saturated aqueous sodium hydrogen carbonate and distilled water, and then dried over anhydrous sodium sulfate and filtered, and the organic phase was evaporated under reduced pressure. The product was identified as the title compound by 1 H-NMR spectrum.
1H-NMR(谱)(在Acetone-d6中测定)：1.58(d，6H)，3.83(s，3H)，5.64(q，1H)，6.54(d，1H)，7.35(m，13H)，8.11(d，2H)。 1 H-NMR (spectrum) (measured in Acetone-d6): 1.58 (d, 6H), 3.83 (s, 3H), 5.64 (q, 1H), 6.54 (d, 1H), 7.35 (m, 13H) , 8.11 (d, 2H).
对比例11：3-(4-甲氧基)苯基-2-丙烯酸(1-苯甲酰基)乙酯Comparative Example 11: (1-Benzoyl)ethyl 3-(4-methoxy)phenyl-2-acrylate
将15g(0.1mol)2-羟基-1-苯基-1-丙酮置于250ml三口瓶中，加入100ml二氯甲烷和10.1g(0.1mol)三乙胺。搅拌均匀后，加入18g(0.1mol)3-(4-甲
氧基)苯基-2-丙烯酰氯，于室温下搅拌反应3h。然后，过滤反应液，将滤液依次用稀盐酸(5％)，饱和碳酸氢钠水溶液和蒸馏水洗涤，然后用无水硫酸钠干燥过夜后过滤，减压蒸馏除去有机相，甲醇重结晶后，得淡黄色晶体，共16g，该产物经1H-NMR谱确认为标题化合物。15 g (0.1 mol) of 2-hydroxy-1-phenyl-1-propanone was placed in a 250 ml three-necked flask, and 100 ml of dichloromethane and 10.1 g (0.1 mol) of triethylamine were added. After stirring uniformly, 18 g (0.1 mol) of 3-(4-methoxy)phenyl-2-acryloyl chloride was added, and the reaction was stirred at room temperature for 3 h. Then, the reaction liquid was filtered, and the filtrate was washed successively with dilute hydrochloric acid (5%), saturated aqueous sodium hydrogen carbonate and distilled water, and then dried over anhydrous sodium sulfate and filtered, and the organic phase was evaporated under reduced pressure. The product was identified as the title compound by 1 H-NMR spectrum.
1H-NMR(谱)(在Acetone-d6中测定)：1.58(d，3H)，3.83(s，3H)，5.64(q，1H)，6.54(d，1H)，7.35(m，9H)，8.11(d，2H)。 1 H-NMR (spectrum) (measured in Acetone-d6): 1.58 (d, 3H), 3.83 (s, 3H), 5.64 (q, 1H), 6.54 (d, 1H), 7.35 (m, 9H) , 8.11 (d, 2H).
实施例12：3-甲基-3-(4-乙烯基)苯基-2-丙烯酸2-氯苯基甲酰基异丙酯Example 12: 2-Chlorophenylformylisopropyl 3-methyl-3-(4-vinyl)phenyl-2-acrylate
将19.8g(0.1mol)2-羟基-2-甲基-1-(2-氯)苯基-1-丙酮置于250ml三口瓶中，加入100ml二氯甲烷和10.1g(0.1mol)三乙胺。搅拌均匀后，加入20.6g(0.1mol)3-甲基-3-(4-乙烯基)苯基-2-丙烯酰氯，于室温下搅拌反应3h。然后，过滤反应液，将滤液依次用稀盐酸(5％)，饱和碳酸氢钠水溶液和蒸馏水洗涤，然后用无水硫酸钠干燥过夜后过滤，减压蒸馏除去有机相，甲醇重结晶后，得淡黄色晶体，共19g，该产物经1H-NMR谱确认为标题化合物。19.8 g (0.1 mol) of 2-hydroxy-2-methyl-1-(2-chloro)phenyl-1-propanone was placed in a 250 ml three-necked flask, and 100 ml of dichloromethane and 10.1 g (0.1 mol) of triethyl were added. amine. After stirring uniformly, 20.6 g (0.1 mol) of 3-methyl-3-(4-vinyl)phenyl-2-acryloyl chloride was added, and the reaction was stirred at room temperature for 3 h. Then, the reaction liquid was filtered, and the filtrate was washed successively with dilute hydrochloric acid (5%), saturated aqueous sodium hydrogen carbonate and distilled water, and then dried over anhydrous sodium sulfate and filtered, and the organic phase was evaporated under reduced pressure. pale yellow crystals, a total of 19g, the product was confirmed that 1 H-NMR spectrum of the title compound.
1H-NMR(谱)(在Acetone-d6中测定)：1.78(s，6H)，2.34(s，6H)，6.54(d，1H)，7.35(m，9H)，8.11(d，2H)。 1 H-NMR (spectrum) (measured in Acetone-d6): 1.78 (s, 6H), 2.34 (s, 6H), 6.54 (d, 1H), 7.35 (m, 9H), 8.11 (d, 2H) .
实施例13：3-甲基-3-(4-乙炔基)苯基-2-丙烯酸2-甲基苯基甲酰基异丙酯Example 13: 2-methylphenylformylisopropyl 3-methyl-3-(4-ethynyl)phenyl-2-propenoate
将17.7g(0.1mol)2-羟基-2-甲基-1-(2-甲基)苯基-1-丙酮置于250ml三口瓶中，加入100ml二氯甲烷和10.1g(0.1mol)三乙胺。搅拌均匀后，加入16.6g(0.1mol)3-甲基-3-(4-乙炔基)苯基-2-丙烯酰氯，于室温下搅拌反应3h。然后，过滤反应液，将滤液依次用稀盐酸(5％)，饱和碳酸氢钠水溶液和蒸馏水洗涤，然后用无水硫酸钠干燥过夜后过滤，减压蒸馏除去有机相，甲
醇重结晶后，得淡黄色晶体，共16g，该产物经1H-NMR谱确认为标题化合物。17.7 g (0.1 mol) of 2-hydroxy-2-methyl-1-(2-methyl)phenyl-1-propanone was placed in a 250 ml three-necked flask, and 100 ml of dichloromethane and 10.1 g (0.1 mol) of three were added. Ethylamine. After stirring uniformly, 16.6 g (0.1 mol) of 3-methyl-3-(4-ethynyl)phenyl-2-acryloyl chloride was added, and the reaction was stirred at room temperature for 3 h. Then, the reaction liquid was filtered, and the filtrate was washed successively with dilute hydrochloric acid (5%), saturated aqueous sodium hydrogen carbonate and distilled water, and then dried over anhydrous sodium sulfate and filtered, and the organic phase was evaporated under reduced pressure. The product was identified as the title compound by 1 H-NMR spectrum.
1H-NMR(谱)(在Acetone-d6中测定)：1.78(s，6H)，2.42(s，3H)，2.48(s，3H)4.05(s，1H)，6.11(d，1H)，7.35(m，9H)。 1 H-NMR (spectrum) (measured in Acetone-d6): 1.78 (s, 6H), 2.42 (s, 3H), 2.48 (s, 3H) 4.05 (s, 1H), 6.11 (d, 1H), 7.35 (m, 9H).
实施例14：2-甲基-3-(4-氯苯基)-2-丙烯酸1-(4-异丙基苯甲酰基)环己基酯Example 14: 1-(4-isopropylbenzoyl)cyclohexyl 2-methyl-3-(4-chlorophenyl)-2-acrylate
将29.2g(1-羟基环己基)(4-异丙基苯基)甲酮置于250ml三口瓶中，加入100ml二氯甲烷和10.1g(0.1mol)三乙胺。搅拌均匀后，加入24.6g(0.1mol)2-甲基-3-(4-氯苯基)-2-丙烯酰氯，于室温下搅拌反应3h。然后，过滤反应液，将滤液依次用稀盐酸(5％)，饱和碳酸氢钠水溶液和蒸馏水洗涤，然后用无水硫酸钠干燥过夜后过滤，减压蒸馏除去有机相，甲醇重结晶后，得黄色晶体，共25g，该产物经1H-NMR谱确认为标题化合物。29.2 g of (1-hydroxycyclohexyl)(4-isopropylphenyl)methanone was placed in a 250 ml three-necked flask, and 100 ml of dichloromethane and 10.1 g (0.1 mol) of triethylamine were added. After stirring uniformly, 24.6 g (0.1 mol) of 2-methyl-3-(4-chlorophenyl)-2-acryloyl chloride was added, and the reaction was stirred at room temperature for 3 h. Then, the reaction liquid was filtered, and the filtrate was washed successively with dilute hydrochloric acid (5%), saturated aqueous sodium hydrogen carbonate and distilled water, and then dried over anhydrous sodium sulfate and filtered, and the organic phase was evaporated under reduced pressure. Yellow crystals, a total of 25 g, were identified as the title compound by 1 H-NMR spectrum.
1H-NMR(谱)(在Acetone-d6中测定)：1.20(d，6H)，1.44(s，10H)，1.80(s，3H)，1.69(m，2H)，2.42(d，2H)，2.51(q，2H)，6.59(d，1H)，7.40(m，6H)，7.64(m，3H)，8.05(d，2H)。 1 H-NMR (spectrum) (measured in Acetone-d6): 1.20 (d, 6H), 1.44 (s, 10H), 1.80 (s, 3H), 1.69 (m, 2H), 2.42 (d, 2H) , 2.51 (q, 2H), 6.59 (d, 1H), 7.40 (m, 6H), 7.64 (m, 3H), 8.05 (d, 2H).
紫外吸收光谱实验：UV absorption spectroscopy experiment:
对比了1173与1173-CC以及184与184-CC(化学结构式参见表一)，发现接入肉桂酰基后的化合物1173-CC和184-CC的紫外吸收有了明显的红移，而现有技术曝光的可聚合羟烷基苯酮衍生物光引发剂AC1173(例如公开于中国专利申请公开CN 105646224A)的紫外吸收波段仅与1173相当。紫外吸收红移会大大提高紫外光源的利用效率，还可用于UV-LED曝光光源中。实验数据见图1和图2。
Comparing 1173 and 1173-CC and 184 and 184-CC (see Table 1 for chemical structural formula), it was found that the UV absorption of the compounds 1173-CC and 184-CC after the addition of cinnamoyl group showed a significant red shift, whereas the prior art The ultraviolet absorbing band of the exposed polymerizable hydroxyalkylphenone derivative photoinitiator AC1173 (for example, disclosed in Chinese Patent Application Publication No. CN 105646224A) is only equivalent to 1173. Ultraviolet absorption red shift will greatly improve the utilization efficiency of the ultraviolet light source, and can also be used in the UV-LED exposure light source. The experimental data is shown in Figures 1 and 2.
表一Table I
热稳定性实验：Thermal stability test:
利用ZRY-2P型热分析仪(梅特勒)对各化合物的热稳定性进行了热重(TG)分析，测试条件：从初始温度25℃开始，以10K/min的速度升温至最终温度500℃。化合物重量百分比随时间的变化见图3。The thermogravimetric (TG) analysis of the thermal stability of each compound was carried out using a ZRY-2P type thermal analyzer (METTLER). The test conditions were as follows: starting from an initial temperature of 25 ° C, the temperature was raised to a final temperature of 500 K at a rate of 10 K/min. °C. The change in weight percent of the compound over time is shown in Figure 3.
实验数据表明，当在化合物1173和184的结构中引入肉桂酰基后，所得化合物的热稳定性有了明显改善。起始热分解温度如下表二所示：Experimental data shows that when the cinnamoyl group is introduced into the structures of the compounds 1173 and 184, the thermal stability of the resulting compound is remarkably improved. The initial thermal decomposition temperature is shown in Table 2 below:
表二Table II
| 化合物名称Compound name |
起始分解温度/℃Initial decomposition temperature / ° |
| 11731173 | 8080 |
| 1173-CC1173-CC | 170170 |
| 184184 | 125125 |
| 184-CC184-CC | 175175 |
光引发性能实验：Photoinitiation performance experiment:
利用实时红外技术对光引发剂的光引发性能进行了测试。选取1173-CC和184-CC两种化合物为代表引发剂，在紫外光照射下引发可聚合单体甲基丙烯酸羟乙酯(HEMA)聚合。取5ml丙酮加入2g HEMA，搅拌，待单体溶解后，加入0.06g光引发剂(1173-C或184-CC)，分别配成1173-CC-HEMA试样和184-CC-HEMA试样。取少许试样涂于KBr盐片上，然后放入Nicolet5700型红外光谱仪中，用紫外光点光源(高压汞灯)照射样品，调节样品表面的紫外光光强为30mW/cm2(光强由HonleUV光强计测得)。单体的双键转化率用近红外实时采集，实时红外参数设置为：数据采集间隔0.3985s，每个光谱扫描1次，分辨率为4cm-1。HEMA在近红外谱图中碳碳双键的特征吸收峰在1630cm-1处，随着光固化反应的进行，碳碳双键变成碳碳单键，双键的吸收峰强度随光照时间增加而变弱，所以利用碳碳双键的特征吸收峰的变化来反映其聚合反应的变化程度。双键转化率(DC)由omnic7.1红外软件和origin6.1数据处理软件结合式(1)计算得到：The photoinitiator properties of photoinitiators were tested using real-time infrared technology. Two compounds, 1173-CC and 184-CC, were selected as the representative initiator to initiate polymerization of the polymerizable monomer hydroxyethyl methacrylate (HEMA) under ultraviolet light irradiation. 5 ml of acetone was added to 2 g of HEMA, stirred, and after the monomer was dissolved, 0.06 g of a photoinitiator (1173-C or 184-CC) was added to prepare a 1173-CC-HEMA sample and a 184-CC-HEMA sample, respectively. Take a little sample coated on a KBr salt tablets, and then placed Nicolet5700 IR spectrometer, (a high pressure mercury lamp) irradiating the sample with a UV spot light source, the surface of the sample was adjusted ultraviolet light intensity of 30mW / cm 2 (intensity of HonleUV The light meter measured). The double bond conversion rate of the monomer is collected by near-infrared real-time, and the real-time infrared parameter is set as follows: the data acquisition interval is 0.3985s, and each spectrum is scanned once, with a resolution of 4cm -1 . The characteristic absorption peak of carbon-carbon double bond in HEMA in the near-infrared spectrum is at 1630 cm -1 . As the photo-curing reaction proceeds, the carbon-carbon double bond becomes a carbon-carbon single bond, and the absorption peak intensity of the double bond increases with the illumination time. However, it is weakened, so the change in the characteristic absorption peak of the carbon-carbon double bond is used to reflect the degree of change in the polymerization reaction. The double bond conversion rate (DC) is calculated by combining omnic7.1 infrared software and origin6.1 data processing software with formula (1):
DC(％)＝[1-(At/A0)]×100％ (1)DC(%)=[1-(At/A 0 )]×100% (1)
式中，A0和A分别为样品在固化前和光照后t时刻在1630cm-1处甲基丙烯酸羟乙酯双键特征吸收峰的面积。In the formula, A 0 and A are the areas of the characteristic absorption peak of the hydroxyethyl methacrylate double bond at 1630 cm -1 before and after the curing of the sample, respectively.
化合物184-CC作为光引发剂得到的可聚合单体的双键转化率随时间的变化见图4，化合物1173-CC作为光引发剂得到的可聚合单体的双键转化率随时间的变化见图5。The change of double bond conversion of polymerizable monomer obtained by using compound 184-CC as photoinitiator with time is shown in Fig. 4. The double bond conversion ratio of polymerizable monomer obtained by compound 1173-CC as photoinitiator changes with time. See Figure 5.
图4和图5的实验数据表明，化合物184-CC与1173-CC具有很好的光引发效果。The experimental data of Figures 4 and 5 show that the compounds 184-CC and 1173-CC have a good photoinitiating effect.
耐迁移性实验：Migration resistance test:
将丙烯酸乙酯(EA)、三缩丙二醇双丙烯酸酯(TPGDA)和三羟甲基丙基三丙烯酸酯(TMPTA)按3∶3∶4的质量比混合，得到混合物，分别向其中加入占其总量为3重量％的184、184-CC、1173、1173-CC，分别配制得到a、a’、b和b’四种光固化体系。Ethyl acrylate (EA), tripropylene glycol diacrylate (TPGDA) and trimethylol propyl triacrylate (TMPTA) were mixed in a mass ratio of 3:3:4 to obtain a mixture, which was separately added thereto. A total of 3% by weight of 184, 184-CC, 1173, and 1173-CC were prepared to obtain four photocuring systems of a, a', b, and b', respectively.
在氮气保护下用365nm光源在光强为100mW/cm2下光照5min，并在室
温下在干燥器中放置24h使其充分固化，将固化膜捣碎，称重并计算四种光引发剂(184、184-CC、1173、1173-CC)各自的质量。用50mL乙腈浸泡96h，所得乙腈溶液过滤后用紫外-可见吸收光谱监控300nm处的吸收。将吸光度A和摩尔吸光系数ε代入公式(2)和(3)，可得乙腈溶液中四种光引发剂各自的浓度与质量。Under a nitrogen atmosphere, the light was irradiated with a 365 nm light source at a light intensity of 100 mW/cm 2 for 5 min, and allowed to stand at room temperature for 24 hours in a desiccator to fully solidify the cured film, and the four photoinitiators were weighed and weighed ( 184, 184-CC, 1173, 1173-CC) respective masses. After soaking in 50 mL of acetonitrile for 96 h, the obtained acetonitrile solution was filtered, and the absorption at 300 nm was monitored by ultraviolet-visible absorption spectroscopy. By substituting the absorbance A and the molar absorptivity ε into the formulas (2) and (3), the respective concentrations and qualities of the four photoinitiators in the acetonitrile solution can be obtained.
c＝A/(εl) (2)c=A/(εl) (2)
m1＝M×c×10-2×V0 (3)M1=M×c×10 -2 ×V0 (3)
R＝(m1/(W×m0))＊100％ (4)R=(m1/(W×m0))*100% (4)
c为析出的引发剂浓度(mol/L)；1为光程长度，此处取为1cm；萃取出的四种光引发剂质量m1按公式(3)计算，M为光引发剂的相对分子质量，V0为乙腈的体积。R为光引发剂的迁移率，W为光引发剂的初始添加质量分数，m0为固化膜的质量，m1为光引发剂的残留量。实验结果如下表三所示：c is the concentration of the initiator (mol/L); 1 is the length of the optical path, which is taken as 1 cm; the mass of the four photoinitiators extracted is calculated according to formula (3), and M is the relative molecule of the photoinitiator. Mass, V0 is the volume of acetonitrile. R is the mobility of the photoinitiator, W is the initial added mass fraction of the photoinitiator, m0 is the mass of the cured film, and m 1 is the residual amount of the photoinitiator. The experimental results are shown in Table 3 below:
表三Table 3
| 物质名称Substance name | 迁移率(％)Mobility (%) |
| 184184 | 0.1230.123 |
| 184-CC184-CC | 0.00750.0075 |
| 11731173 | 0.1040.104 |
| 1173-CC1173-CC | 0.0240.024 |
固化膜性能测试：Cured film performance test:
将甲基丙烯酸甲酯、三缩丙二醇双丙烯酸酯(TPGDA)和三羟甲基丙烷三丙烯酸酯(TMPTA)按3∶3∶4的质量比混合，得到混合物，向其中分别加入占其总量为3重量％的184-CC或1173-CC，配制得到两种感光组合物。将上述感光组合物各自在395nm波长的光源下固化成膜，铅笔硬度均达到3H。Methyl methacrylate, tripropylene glycol diacrylate (TPGDA) and trimethylolpropane triacrylate (TMPTA) were mixed in a mass ratio of 3:3:4 to obtain a mixture, and the total amount thereof was added thereto. Two photosensitive compositions were prepared in an amount of 3% by weight of 184-CC or 1173-CC. Each of the above-mentioned photosensitive compositions was cured into a film under a light source having a wavelength of 395 nm, and the pencil hardness was 3H.
固化速度和印刷品迁移率测定：Curing speed and print mobility measurement:
按照表四中配方分别称取本发明实施例和对比例中制备的每种光引发剂及市场上买到的光引发剂184、1173，羟乙基丙烯酸酯、三羟甲基丙烷
三丙烯酸酯和三乙二醇双丙烯酸酯在100ml三角瓶中，利用电磁搅拌器搅拌0.5小时固体完全溶解后，再加入聚酯丙烯酸树脂(RJ513)，继续搅拌2小时，制得光固化组合物，其为无色粘稠液体。然后将所得的光固化组合物用10微米线棒涂布器施印到12cm＊12cm白色铜纸板上，用发射波长为395nm、光强为50mW/cm2的UV-LED光源进行固化，记录彻底固化需要的时间。然后将纸板剪裁为10＊10cm大小，分别完全浸入100ml蒸馏水或3％醋酸水溶液两种模拟液中，密封好在40℃条件下放置10天。取出印刷物，静置后直接进行HPLC分析模拟液中光引发剂的含量。使用欧盟模型，假定600cm2印刷面积包装1Kg食品，迁移率测量结果以ppb或ug/Kg食品表示，结果如表五所示。Each photoinitiator prepared in the examples and comparative examples of the present invention and commercially available photoinitiators 184, 1173, hydroxyethyl acrylate, trimethylolpropane triacrylate were weighed according to the formula in Table 4. And triethylene glycol diacrylate in a 100 ml flask, stirred for 0.5 hour with a magnetic stirrer, completely dissolved, then added polyester acrylic resin (RJ513), and continued to stir for 2 hours to obtain a photocurable composition, which is Colorless viscous liquid. The resulting photocurable composition was then applied to a 12 cm*12 cm white copper paperboard using a 10 micron wire bar coater and cured with a UV-LED source having an emission wavelength of 395 nm and a light intensity of 50 mW/cm 2 . The time required for curing. Then, the cardboard was cut into 10*10 cm size, and completely immersed in 100 ml of distilled water or 3% acetic acid aqueous solution, and sealed for 10 days at 40 °C. The printed matter was taken out, and after standing, the content of the photoinitiator in the simulated liquid was directly analyzed by HPLC. Using the EU model, assuming 1 kg of food in a 600 cm 2 printing area, the mobility measurement results are expressed in ppb or ug/kg food, and the results are shown in Table 5.
表四Table 4
表五Table 5
＊：方法检测限为0.5％*: Method detection limit is 0.5%
从表五的性能评价实验结果可以看出，本发明所提供的肉桂酸苯甲酰基甲酯类化合物作为原料制备的各种光固化组合物，完全固化所需要的时间短，光固化效率高；而且，较现有光引发剂1173和184，本发明光引发剂在迁移率方面表现尤为突出，甚至实现零迁移率。
It can be seen from the results of the performance evaluation experiments of Table 5 that the various photocurable compositions prepared by using the benzoyl methacrylate compound of the present invention as a raw material have a short time required for complete curing and high photocuring efficiency; Moreover, the photoinitiators of the present invention are particularly outstanding in terms of mobility compared to existing photoinitiators 1173 and 184, even achieving zero mobility.
Claims (10)
- 肉桂酸苯甲酰基甲酯类化合物，具有式(I)所示结构：a benzoylmethyl cinnamate compound having the structure represented by the formula (I):
其中among themR1、R2、R3、R4和R5彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C1-C20烷基、C2-C20烯基、C2-C20炔基、C3-C20环烷基、C4-C20环烷基烷基、C1-C20烷氧基、C2-C20烯氧基、C2-C20炔氧基、C3-C20环烷氧基、C4-C20环烷基烷氧基、C1-C20烷硫基、C2-C20烯硫基、C2-C20炔硫基、C3-C20环烷硫基、C4-C20环烷基烷硫基和C6-C18芳基，其中前述C1-C20烷基、C2-C20烯基、C2-C20炔基、C3-C20环烷基、C4-C20环烷基烷基、C1-C20烷氧基、C2-C20烯氧基、C2-C20炔氧基、C3-C20环烷氧基、C4-C20环烷基烷氧基、C1-C20烷硫基、C2-C20烯硫基、C2-C20炔硫基、C3-C20环烷硫基、C4-C20环烷基烷硫基和C6-C18芳基基团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、羧基、磺酸基、氨基、氰基、C1-C6烷基、C1-C6烷氧基、C1-C6烷硫基、C2-C6烯基和C2-C6炔基；R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from the group consisting of hydrogen, halogen, nitro, hydroxy, decyl, carboxyl, sulfonic acid, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 olefin Oxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 alkene a C 2 -C 20 alkynylthio group, a C 3 -C 20 cycloalkylthio group, a C 4 -C 20 cycloalkylalkylthio group and a C 6 -C 18 aryl group, wherein the aforementioned C 1 -C 20 alkyl group , C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 Alkylthio, C 2 -C 20 alkynylthio, C 3 -C 20 cycloalkylthio, C 4 -C 20 cycloalkylalkylthio and C 6 -C 18 aryl groups may optionally be one Or a plurality of groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonate, amino, cyano, C 1- C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkenyl and C 2 -C 6 alkynyl;R6和R7相同或不同且选自C1-C6烷基和卤代C1-C6烷基，或者R6和R7与它们所连接的碳原子一起形成C3-C8环烷基；R 6 and R 7 are the same or different and are selected from C 1 -C 6 alkyl and halo C 1 -C 6 alkyl group, or R 6 and R 7 are the carbon atoms to which they are attached form a ring together with C 3 -C 8 alkyl;R8、R9、R10、R11和R12彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C1-C20烷基、C2-C20烯基、C2-C20炔基、C3-C20环烷基、C4-C20环烷基烷基、C1-C20烷氧基、C2-C20烯氧基、C2-C20炔氧基、C3-C20环烷氧基、C4-C20环烷基烷氧基、C 1-C20烷硫基、C2-C20烯硫基、C2-C20炔硫基、C3-C20环烷硫基、C4-C20环烷基烷硫基和C6-C18 芳基，其中前述C1-C20烷基、C2-C20烯基、C2-C20炔基、C3-C20环烷基、C4-C20环烷基烷基、C1-C20烷氧基、C2-C20烯氧基、C2-C20炔氧基、C3-C20环烷氧基、C4-C20环烷基烷氧基、C1-C20烷硫基、C2-C20烯硫基、C2-C20炔硫基、C3-C20环烷硫基、C4-C20环烷基烷硫基和C6-C18芳基基团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、羧基、磺酸基、氨基、氰基、C1-C6烷基、C1-C6烷氧基、C1-C6烷硫基、C2-C6烯基和C2-C6炔基；以及R 8 , R 9 , R 10 , R 11 and R 12 are independently of each other selected from the group consisting of hydrogen, halogen, nitro, hydroxy, decyl, carboxyl, sulfonate, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 olefin Oxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 alkene a C 2 -C 20 alkynylthio group, a C 3 -C 20 cycloalkylthio group, a C 4 -C 20 cycloalkylalkylthio group and a C 6 -C 18 aryl group, wherein the aforementioned C 1 -C 20 alkyl group , C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyl group, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkyl alkoxy, C 1 -C 20 alkylthio, C 2 -C 20 Alkylthio, C 2 -C 20 alkynylthio, C 3 -C 20 cycloalkylthio, C 4 -C 20 cycloalkylalkylthio and C 6 -C 18 aryl groups may optionally be one Or a plurality of groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, amino, cyano C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkenyl and C 2 -C 6 alkynyl group;R13和R14相同或不同且选自H、C1-C6烷基和卤代C1-C6烷基。R 13 and R 14 are the same or different and are selected from the group consisting of H, C 1 -C 6 alkyl and halogenated C 1 -C 6 alkyl. - 根据权利要求1的化合物，其中R6和R7相同或不同且选自C1-C4烷基和卤代C1-C4烷基，或者R6和R7与它们所连接的碳原子一起形成C5-C6环烷基。A compound according to claim 1 wherein R 6 and R 7 are the same or different and are selected from the group consisting of C 1 -C 4 alkyl and halo C 1 -C 4 alkyl, or R 6 and R 7 are bonded to the carbon atom to which they are attached. Together, a C 5 -C 6 cycloalkyl group is formed.
- 根据权利要求2的化合物，其中R6和R7相同且为甲基或卤代甲基，或者R6和R7与它们所连接的碳原子一起形成环戊基或环己基。The compound according to claim 2, wherein R 6 and R 7 are the same and are methyl or halomethyl, or R 6 and R 7 form a cyclopentyl or cyclohexyl group together with the carbon atoms to which they are attached.
- 根据权利要求1-3中任一项的化合物，其中R13和R14相同或不同且选自H、C1-C4烷基和卤代C1-C4烷基，优选R13和R14均为H。The compound according to any one of claims 1 to 3, wherein R 13 and R 14 are the same or different and are selected from the group consisting of H, C 1 -C 4 alkyl and halogenated C 1 -C 4 alkyl, preferably R 13 and R 14 is H.
- 根据权利要求1-4中任一项的化合物，其中A compound according to any one of claims 1 to 4, whereinR1、R2、R3、R4和R5彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C8环烷基、C4-C8环烷基烷基、C1-C6烷氧基、C2-C6烯氧基、C2-C6炔氧基、C3-C8环烷氧基、C4-C8环烷基烷氧基、C1-C6烷硫基、C2-C6烯硫基、C2-C6炔硫基、C3-C8环烷硫基、C4-C8环烷基烷硫基和C6-C10芳基，其中前述C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C8环烷基、C4-C8环烷基烷基、C1-C6烷氧基、C2-C6烯氧基、C2-C6炔氧基、C3-C8环烷氧基、C4-C8环烷基烷氧基、C1-C6烷硫基、C2-C6烯硫基、C2-C6炔硫基、C3-C8环烷硫基、C4-C8环烷基烷硫基和C6-C10芳基基团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、羧基、磺酸基、氨基、氰基、C1-C4烷基、C1-C4烷氧基、C1-C4烷硫基、C2-C4烯基和C2-C4炔基；和/或R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from the group consisting of hydrogen, halogen, nitro, hydroxy, decyl, carboxyl, sulfonic acid, amino, cyano, C 1 -C 6 alkyl, C 2- C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 olefin Oxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkene a C 2 -C 6 alkynylthio group, a C 3 -C 8 cycloalkylthio group, a C 4 -C 8 cycloalkylalkylthio group and a C 6 -C 10 aryl group, wherein the aforementioned C 1 -C 6 alkyl group , C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2 -C 6 Alkylthio, C 2 -C 6 alkynylthio, C 3 -C 8 cycloalkylthio, C 4 -C 8 cycloalkylalkylthio and C 6 -C 10 aryl groups may optionally be one Or a plurality of groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, amino, cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy a group, a C 1 -C 4 alkylthio group, a C 2 -C 4 alkenyl group, and a C 2 -C 4 alkynyl group; and/orR8、R9、R10、R11和R12彼此独立地选自氢、卤素、硝基、羟基、巯基、 羧基、磺酸基、氨基、氰基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C8环烷基、C4-C8环烷基烷基、C1-C6烷氧基、C2-C6烯氧基、C2-C6炔氧基、C3-C8环烷氧基、C4-C8环烷基烷氧基、C1-C6烷硫基、C2-C6烯硫基、C2-C6炔硫基、C3-C8环烷硫基、C4-C8环烷基烷硫基和C6-C10芳基，其中前述C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C8环烷基、C4-C8环烷基烷基、C1-C6烷氧基、C2-C6烯氧基、C2-C6炔氧基、C3-C8环烷氧基、C4-C8环烷基烷氧基、C1-C6烷硫基、C2-C6烯硫基、C2-C6炔硫基、C3-C8环烷硫基、C4-C8环烷基烷硫基和C6-C10芳基基团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、羧基、磺酸基、氨基、氰基、C1-C4烷基、C1-C4烷氧基、C1-C4烷硫基、C2-C4烯基和C2-C4炔基。R 8 , R 9 , R 10 , R 11 and R 12 are independently of each other selected from the group consisting of hydrogen, halogen, nitro, hydroxy, decyl, carboxy, sulfonic acid, amino, cyano, C 1 -C 6 alkyl, C 2- C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 olefin Oxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkene a C 2 -C 6 alkynylthio group, a C 3 -C 8 cycloalkylthio group, a C 4 -C 8 cycloalkylalkylthio group and a C 6 -C 10 aryl group, wherein the aforementioned C 1 -C 6 alkyl group , C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2 -C 6 Alkylthio, C 2 -C 6 alkynylthio, C 3 -C 8 cycloalkylthio, C 4 -C 8 cycloalkylalkylthio and C 6 -C 10 aryl groups may optionally be one or more groups independently selected from the group: halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic, amino, cyano, C 1 -C 4 alkyl, C 1 -C 4 Alkoxy, C 1 -C 4 alkylthio, C 2 -C 4 alkenyl and C 2 -C 4 alkynyl group.
- 根据权利要求1-4中任一项的化合物，其中A compound according to any one of claims 1 to 4, whereinR1、R2、R3、R4和R5彼此独立地选自氢、卤素、C1-C4烷基、C1-C4烷氧基和C1-C4烷硫基，其中前述C1-C4烷基、C1-C4烷氧基和C1-C4烷硫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、C1-C4烷基、C1-C4烷氧基和C1-C4烷硫基；和/或R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from the group consisting of hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1 -C 4 alkylthio, wherein The aforementioned C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1 -C 4 alkylthio may be optionally substituted by one or more groups independently selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1 -C 4 alkylthio; and/orR8、R9、R10、R11和R12彼此独立地选自氢、卤素、C1-C4烷基、C2-C4烯基、C2-C4炔基、C1-C4烷氧基和C1-C4烷硫基，其中前述C1-C4烷基、C2-C4烯基、C2-C4炔基、C1-C4烷氧基和C1-C4烷硫基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、C1-C4烷基、C1-C4烷氧基和C1-C4烷硫基。R 8 , R 9 , R 10 , R 11 and R 12 are independently of each other selected from the group consisting of hydrogen, halogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 - a C 4 alkoxy group and a C 1 -C 4 alkylthio group, wherein the aforementioned C 1 -C 4 alkyl group, C 2 -C 4 alkenyl group, C 2 -C 4 alkynyl group, C 1 -C 4 alkoxy group and The C 1 -C 4 alkylthio group may be optionally substituted by one or more groups independently selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1 -C 4 alkylthio group.
- 根据权利要求1的化合物，其中该化合物选自下组：A compound according to claim 1 wherein the compound is selected from the group consisting of:
- 一种制备根据权利要求1-7中任一项的式(I)化合物的方法，包括使式(II)化合物与式(III)化合物进行酯化反应，得到式(I)化合物，A process for the preparation of a compound of formula (I) according to any one of claims 1 to 7 which comprises esterifying a compound of formula (II) with a compound of formula (III) to give a compound of formula (I),
其中R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13和R14如权利要求1-7中任一项所定义，以及X为羟基或卤素。Wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are as defined in claims 1-7 One is defined, and X is a hydroxyl group or a halogen. - 根据权利要求8的方法，其中酯化反应在催化剂存在下进行，优选催化剂为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、氢化锂、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。A process according to claim 8 wherein the esterification reaction is carried out in the presence of a catalyst, preferably the catalyst is one or more selected from the group consisting of sulfuric acid, perchloric acid, zinc chloride, ferric chloride, pyridine, and para Benzobenzenesulfonic acid, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium t-butoxide, sodium ethoxide, lithium hydride, sodium hydride, potassium hydride, calcium hydride and tertiary amines, such as trialkylamines, such as Trimethylamine and triethylamine.
- 根据权利要求1-7中任一项的化合物作为光引发剂的用途。 Use of a compound according to any one of claims 1 to 7 as a photoinitiator.
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