CN106278967A - For the acyl group oxime ester compound of UV curing materials and synthetic method thereof and application - Google Patents
For the acyl group oxime ester compound of UV curing materials and synthetic method thereof and application Download PDFInfo
- Publication number
- CN106278967A CN106278967A CN201510297585.2A CN201510297585A CN106278967A CN 106278967 A CN106278967 A CN 106278967A CN 201510297585 A CN201510297585 A CN 201510297585A CN 106278967 A CN106278967 A CN 106278967A
- Authority
- CN
- China
- Prior art keywords
- carbon atom
- alkyl
- acyl group
- alkylene
- alkoxyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 acyl group oxime ester compound Chemical class 0.000 title claims description 63
- 239000000463 material Substances 0.000 title claims description 24
- 238000010189 synthetic method Methods 0.000 title abstract description 5
- 238000003848 UV Light-Curing Methods 0.000 title description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 93
- 230000000694 effects Effects 0.000 claims abstract description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 171
- 229910052799 carbon Inorganic materials 0.000 claims description 104
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 38
- 125000000217 alkyl group Chemical group 0.000 claims description 37
- 125000003545 alkoxy group Chemical group 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000000016 photochemical curing Methods 0.000 claims description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 25
- 238000002360 preparation method Methods 0.000 claims description 25
- 125000002947 alkylene group Chemical group 0.000 claims description 24
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 24
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 230000000977 initiatory effect Effects 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 claims description 7
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 229960003116 amyl nitrite Drugs 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- CSDTZUBPSYWZDX-UHFFFAOYSA-N n-pentyl nitrite Chemical compound CCCCCON=O CSDTZUBPSYWZDX-UHFFFAOYSA-N 0.000 claims description 3
- QQZWEECEMNQSTG-UHFFFAOYSA-N Ethyl nitrite Chemical compound CCON=O QQZWEECEMNQSTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 42
- 150000002367 halogens Chemical group 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 108091008695 photoreceptors Proteins 0.000 abstract description 3
- 230000001988 toxicity Effects 0.000 abstract description 3
- 231100000419 toxicity Toxicity 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 150000001721 carbon Chemical group 0.000 description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical class O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- 239000000243 solution Substances 0.000 description 28
- 238000003756 stirring Methods 0.000 description 24
- 239000007787 solid Substances 0.000 description 23
- 238000010992 reflux Methods 0.000 description 20
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 19
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 17
- 238000005160 1H NMR spectroscopy Methods 0.000 description 16
- 239000007788 liquid Substances 0.000 description 16
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 16
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 14
- 238000001035 drying Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 238000001953 recrystallisation Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 7
- 230000005311 nuclear magnetism Effects 0.000 description 7
- REEZZSHJLXOIHL-UHFFFAOYSA-N octanoyl chloride Chemical compound CCCCCCCC(Cl)=O REEZZSHJLXOIHL-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 208000035126 Facies Diseases 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 150000002576 ketones Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000012544 monitoring process Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- 238000003384 imaging method Methods 0.000 description 4
- 125000001841 imino group Chemical group [H]N=* 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229960002446 octanoic acid Drugs 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000010583 slow cooling Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical group COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005034 decoration Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002633 imido ester group Chemical group 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 229940050176 methyl chloride Drugs 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- 0 C*c1c(C)c(*)c(CC(c2ccccc2)=O)c(*)c1 Chemical compound C*c1c(C)c(*)c(CC(c2ccccc2)=O)c(*)c1 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000001105 octanoic acid ester group Chemical group 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical class CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 description 2
- 238000001259 photo etching Methods 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035943 smell Effects 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- CHVNGPFOOJHLLJ-UHFFFAOYSA-N 1-chloro-4-hydroxythioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(O)=CC=C2Cl CHVNGPFOOJHLLJ-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
- PQJUJGAVDBINPI-UHFFFAOYSA-N 9H-thioxanthene Chemical compound C1=CC=C2CC3=CC=CC=C3SC2=C1 PQJUJGAVDBINPI-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- FXEGWJJILAYIOH-NUYBWQCUSA-N CCCCCC/C(/C(c1c(C)cc(C)c(C(c2ccccc2C)=O)c1C)=N)=N\O Chemical compound CCCCCC/C(/C(c1c(C)cc(C)c(C(c2ccccc2C)=O)c1C)=N)=N\O FXEGWJJILAYIOH-NUYBWQCUSA-N 0.000 description 1
- LOAYPPAXTXFSOQ-UHFFFAOYSA-N Cc(cc1)ccc1SSC1=CC=CCC1 Chemical compound Cc(cc1)ccc1SSC1=CC=CCC1 LOAYPPAXTXFSOQ-UHFFFAOYSA-N 0.000 description 1
- SYGRPSIEWATOEA-UHFFFAOYSA-N Cc1cc(C=C)c(C)c(C)c1C(c1ccccc1)=O Chemical compound Cc1cc(C=C)c(C)c(C)c1C(c1ccccc1)=O SYGRPSIEWATOEA-UHFFFAOYSA-N 0.000 description 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- 206010057040 Temperature intolerance Diseases 0.000 description 1
- 239000004837 Ultraviolet (UV) light curing adhesive Substances 0.000 description 1
- HHRFWSALGNYPHA-UHFFFAOYSA-N [N].C1CNCCN1 Chemical compound [N].C1CNCCN1 HHRFWSALGNYPHA-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical group C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- UUZYBYIOAZTMGC-UHFFFAOYSA-M benzyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=CC=C1 UUZYBYIOAZTMGC-UHFFFAOYSA-M 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000008543 heat sensitivity Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
- C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
- C07C251/68—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with at least one of the esterifying carboxyl groups bound to a carbon atom of a six-membered aromatic ring
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- 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
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- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/23—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 nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C323/46—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 nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms
- C07C323/47—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 nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms to oxygen atoms
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- C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
- C07D335/12—Thioxanthenes
- C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
- C07D335/16—Oxygen atoms, e.g. thioxanthones
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Abstract
The present invention provides the compound of a kind of novel acyl group oxime ester structure with structure shown in formula I; described compound has good ultraviolet absorption effect; this compound has that dissolubility is good, heat stability and photoreceptor activity is high and toxicity is low feature; application performance is substantially better than like product; present invention also offers the synthetic method of a kind of compound preparing described novel acyl group oxime ester structure; described synthetic method has simple efficient; production process does not produce contaminative garbage; and product purity is high, it is adaptable to the advantage of industrialized production.
Description
Technical field
The present invention relates to a kind of light trigger, particularly relate to a kind of photoinitiator for UV curing materials.
Background technology
Ultraviolet light (UV) solidifies, and is called for short photocuring technology, be a kind of efficiently, environmental protection, material surface energy-conservation, high-quality process skill
Art, is widely used in the fields such as advertisement, printing, high-grade goods packaging, decoration, electronics and communication, current photocuring product master
To occur with forms such as UV coating, UV ink, UV adhesive, photosensitive printing plate, photoresist, light rapid prototyping materials.
Photocuring is to utilize ultraviolet light to irradiate to have chemically active liquid material, causes its rapid polymerization to cross-link, and makes its moment
The process of solidification.
Compared with other curing modes such as photocuring and heat cure, there is following advantage: 1. speed is fast, and photocuring product is typically at several seconds
The most curable, it is that in current various ink, coating and adhesive, curing rate is the fastest；2. have wide range of applications, photocuring
Product is applicable to multiple base material, is particularly well-suited to the material of some heat sensitivitys, such as paper, electronic devices and components and plastics etc.: 3.
Energy consumption is low, and photocuring product is room temperature fast setting, and its energy consumption only has 1/10 to the 1/5 of heat cure；4. low stain, light is solid
Change product and be substantially free of volatile organic matter (VOC), be the environmentally friendly product of a class.
In daily life, photocuring product is ubiquitous, and changes our life.As at sheet material coating protection and decoration
Industry, UV woodwork coating application can improve that sheet material is wear-resisting, scratch resistance and resistance, also can significantly be carried by UV solid application
High decorative effect, is mainly used on furniture, the protection of solid wooden floor board and decoration；In printing industry, the use of UV offset ink
The disadvantage that leaflet printing ink of changing over is not dry and need to dust, and bright in luster saturated, and more preferably, UV ink becomes definition
For outdoor large advertisement and the fresh combatants of direction board, also it is high-grade tobacco and wine, health product, cosmetics and the important printing of packaging for foodstuff
Material；In photoelectron, information and communication industry, photoresist is the photocuring product of relatively early application, is particularly well-suited to one slightly
The making of electronic product.As made the far-ultraviolet photoetching of large scale integrated circuit, show at liquid crystal display, plasma
The making of some critical components in device, display of organic electroluminescence the most all be unable to do without photoresist.
Nineteen sixty-eight Bayer, company developed first generation UV cure wood coatings, first achieved the industrialization of photocuring technology.
Photocuring technology fast development subsequently, application constantly expands, and defines a new industry.Last century 70, the eighties,
American-European radiation curing association sets up, and has promoted the research and development of photocuring technology, in North America, the developed country such as European and Japanese
And area, the multinational corporations such as BASF, Bayer, Tao Shi joins photocuring one after another and produces, the most become and had certain market
The industry of scale.China started to develop photocuring technology from the eighties in last century, due to raw material and the restriction of equipment, slower development.
Entering the nineties, the introduction of UV-curing technology and equipment has promoted the development of China's photocuring industry significantly, enters 21 century,
China's photocuring industry obtains and more quickly develops, and particularly light trigger has become production maximum in the world and exported country,
Preliminarily form a new high technology industry.Advocate sustainable development the most energetically, build a Harmonious Society, and increase environment
Protection, this is that the development of China's photocuring industry provides opportunity.
Main photo-curing material (photocureable coating, ink, photoresist, the RGB being made up of unsaturated-resin and monomer material thereof
And BM), under ultraviolet light, X-ray or laser irradiate, polymerization curing reaction, it is necessary to light trigger or sensitizing
Agent.These light triggers added or sensitizer can produce and live under the ultraviolet light of certain wavelength, X-ray or laser irradiate
Property group, the unsaturated group in exciting light curing materials grows prosperity polyreaction, causes the solidification of photo-curing material.
In photo-curing material, more wide variety of conventional initiator have: Benzoin derivative, dibenzoyl ketal class, α, α-
Dialkoxy acetophenones class, α hydroxyalkylphenones class, alpha-aminoalkyl benzophenone class, acylphosphine oxide class, benzophenones/amines class,
Michaelis ketone, thioxanthones/amines class, amine promoter, aromatic diazo salt, the sumptuous salt of aryl and sulfosalt, ferrocene and ferrocene class,
Hexaarylbisimidazolecompounds, three nitrogen piperazine classes and tradition oxime esters etc..Due to these traditional light triggers more or less there is sense
Luminosity low (rate of polymerization and conversion ratio are low), dissolubility poor (transparency is low and photoetching residue is many), oxygen big and storage on photocuring impact
Deposit the shortcomings such as poor stability, therefore the use of they and sensitive material is limited by very large, also the photosensitive material of strong influence
The performance of material, particularly can not meet the making requirement of a new generation giant-screen LCD critical component BM and CF.Novel oxime esters
The appearance of light trigger, largely solves the problems referred to above.The photochemical properties of oxime ester compound occurs in document the earliest
A.Wemer and A.Piguet, in Ber.Dtsch.Chem.Ges.1904,37,4295；And as the application of light trigger, the earliest
Then occur from document G.A.Delzenne, u.Laridon and H.Peeters, EuropeanPolymer Journal, 1970,6,
In 933-943, trade name DE-OS 179508 and Agfa-Gevaert AG；The oxime esters of the most wide business application is light-initiated
Agent product is Quantacure PDO.
Although the light-initiated clean property of these traditional oxime ester lightlike initiating agents is high, but due to poor heat stability, and progressively it is in industrial applications
Eliminated；" resurrection " of oxime ester lightlike initiating agent occurs in document R.Malliviaet al, J.Photochem. the earliest
Photobiol.A:Chemistry 2001,138,193 and document L.Laval é e et aI, J.Photochem.
Photobiol.A:Chemistry 2002.151, in 27, owing to introducing diphenyl sulfide or carbazole group in oxime ester compound,
These groups have bigger conjugated system and stronger cyclic voltammetry method characteristic, therefore greatly improves the esterification of this kind of oxime
The stability of compound and photoreceptor activity, two the representational oxime ester lightlike initiating agents being widely used at present are OXE-1 and OXE-2,
Structural formula is as follows:
Wherein OXE-l is exactly most typical ketoxime ester photoinitiator, and they are mainly used in and manufacture giant-screen LCD display
BM and RGB, expensive, and its structural formula oneself by offshore company application protection, patent publication No. CN99108598 and
CN02811675, the synthetic method of the structural formula of above-mentioned announcement is loaded down with trivial details, and synthesis cost is high, and the application performance of the product of this structure is not
Reach, the problem that heat stability is poor.Subsequently, many ketoxime ester chemical combination with excellent photocuring application performance has been emerged
The report of thing, as CN101565472A discloses a kind of ketoxime ester initiators containing cycloalkyl, it has good stability
And dissolubility.But being accompanied by practical application, this series products is proved and yet suffers from the problem that application performance is not enough, in using
There is the traditional performances such as potential safety hazard (decompose and produce benzene class high toxic material), photoreceptor activity and heat stability need to improve further.
Enter now more and more higher for effect and the characteristic requirements such as the toxicity of catabolite, abnormal smells from the patient and animal migration thereof of light trigger,
The macromolecular photoinitiator of the superperformance that exploitation has good dissolubility, low abnormal smells from the patient or odorlessness and low migration will become not
The Main way developed.But the macromolecular photoinitiator having been commercialized at present is the most expensive or properties of product have certain defect,
Therefore substitute in the urgent need to cheap and that performance is good product.
Summary of the invention
Goal of the invention: the present invention is directed to the deficiency of existing acyl group oxime ester lightlike initiating agent application performance, it is an object of the invention to provide
A kind of dissolubility is good, Heat stability is good, reactivity high, production cost odorlessness low, cheap, basic, low migration,
And the acyl group oxime ester compound of (toxicity is low) safe to use.
It is a further object of the present invention to provide the preparation method of described acyl group oxime ester compound.
Another object of the present invention is to provide the application in UV photo-curing material of the described acyl group oxime ester compound.
Technical scheme: in order to reach foregoing invention purpose, the invention provides a kind of acyl group oxime ester compound, described acyl group oxime
Esters optical compounds has a structure shown in formula I:
Described R1And R4Identical or different, it is each independently selected from
Wherein, described R3Selected from-H ,-NO2, the alkyl of 1-8 carbon atom or alkoxyl, the cycloalkyl of 3-8 carbon atom, 2-8
The alkylene of individual carbon atom,
Described Y1、Y2And Y3Identical or different, it is each independently selected from-H ,-CH3, the alkyl of 2-8 carbon atom or alkoxyl,
The cycloalkyl of 3-8 carbon atom, the alkylene of 2-8 carbon atom；
Described X ' and Y ' is identical or different, is each independently selected from-S-,-S-S-,-O-,-CO-；
Above-mentioned R1And R4In the substituent group selected, in described circulus, one or more-H can be by-F ,-Cl ,-Br ,-I ,-NO2、
-COOR′1、-CONR′2、-OR′3、The alkyl of 1-8 carbon atom or alkoxyl or
The alkylene of 2-8 carbon atom replaces, wherein R '1And R '2Be each independently selected from-H, The alkyl of 1-8 carbon atom, the cycloalkyl of 3-8 carbon atom, 2-8 carbon atom
Alkylene, R '3Selected from-H, the alkyl of 1-8 carbon atom, the cycloalkyl of 3-8 carbon atom, the alkylene of 2-8 carbon atom or 1-8
The carbochain carbonyl of individual carbon atom, wherein, in the carbochain carbonyl of 1-8 carbon atom, carbonyl is in end position, is positioned at connecting key；
Described R2Selected from-H, the alkyl of 1-20 carbon atom or alkoxyl, the cycloalkyl of 3-8 carbon atom or 2-20 carbon atom
Alkylene；
Or R2With R1Shown group is identical,
Premise is: described R1And R4In at least one represent
In some preferred implementations of the present invention, described R1And R4In at least one represent
In some preferred implementations of the present invention, described R1And R4Described in circulus one or more-H can by-F,
-NO2、-COOR′1、-CONR′2、-OR′3, the alkyl of 1-8 carbon atom or alkoxyl, wherein R '1And R '2Select independently of one another
From-H,The alkyl of 1-8 carbon atom, 3-8
The cycloalkyl of individual carbon atom, the alkylene of 2-8 carbon atom, R '3Selected from-H, the alkyl of 1-8 carbon atom or 1-8 carbon atom
Carbochain carbonyl, wherein, in the carbochain carbonyl of 1-8 carbon atom, carbonyl is in end position, is positioned at connecting key.
In some preferred implementations of the present invention, it is preferable that described R1And R4Identical or different, it is each independently selected from
In some preferred implementations of the present invention, described R2Individual selected from-H, the alkyl of 1-20 carbon atom or alkoxyl, 2-20
The alkylene of carbon atom or and R1Shown group is identical.
In some embodiments of the present invention, it is preferable that described R2Selected from-H, the alkyl of 1-20 carbon atom or alkoxyl, 2-20
The alkylene of individual carbon atom,
In some embodiments of the present invention, it is preferable that described R2Selected from-H, the alkyl of 1-15 carbon atom or alkoxyl, 3-8
Individual carbon atom cycloalkyl, the alkylene of 2-15 carbon atom,
In some embodiments of the present invention, it is preferable that described R2Selected from-H, the alkyl of 1-15 carbon atom or alkoxyl, 3-8
Individual carbon atom cycloalkyl, the alkylene of 2-15 carbon atom,
In some embodiments of the present invention, it is preferable that described R2Alkyl or alkoxyl, 3-8 carbon selected from 1-15 carbon atom
Atom cycloalkyl, the alkylene of 2-15 carbon atom.
In certain embodiments of the present invention, described R3Selected from-H ,-NO2, the alkyl of 1-8 carbon atom or alkoxyl, 3-6
The cycloalkyl of individual carbon atom, the alkylene of 2-8 carbon atom,
In certain embodiments of the present invention, described X ' and Y ' is identical or different, be each independently selected from-S-,-S-S-,-O-,
-CO-。
In some embodiments of the present invention, described R3Selected from-H, the alkyl of 1-8 carbon atom or alkoxyl.
In some embodiments of the present invention, described Y1、Y2And Y3Identical or different, it is each independently selected from-H, 1-8 carbon former
The alkyl of son or alkoxyl.
In some embodiments of the present invention, described R3Expression-H.
In some embodiments of the present invention, described Y1、Y2And Y3Expression-CH3。
In some embodiments of the present invention, compound choosing free formula I-1 to the compound shown in I-17 of formula I forms
Group:
And
Wherein,
Described R2Selected from-H, the alkyl of 1-20 carbon atom or alkoxyl, the cycloalkyl of 3-8 carbon atom, 2-20 carbon atom
Alkylene or R1Shown group.
Present invention also offers the preparation method of acyl group oxime ester compound described in a kind of formula I, comprise the steps of:
A, the synthesis of intermediate I-A: with benzene, diphenyl sulfide or thioxanthone etc. as initiation material, and containing R2The carboxylic acid halides of group
Compound, under the effect such as ferric chloride, aluminum chloride or zinc chloride, by F-K reaction, synthetic intermediate I-A:
B, the synthesis of intermediate I-B: intermediate compound I in the case of being connected with hydrogen chloride or adding hydrochloric acid with methyl nitrite, nitrous acid
Ethyl ester or amyl nitrite etc. carry out oxidation reaction, generation acyl group oxime intermediate I-B:
C, acyl group oxime ester lightlike initiating agent synthesize: intermediate I-B and the carboxylic acid halides containing M1 structure or anhydride, in pyridine or three second
In the presence of the acid binding agents such as amine, do the compound synthesizing formula I under solvent at dichloromethane, dichloroethanes or dioxane etc..
Wherein,
Described R1And R4Identical or different, it is each independently selected from Wherein, institute
State R3Selected from-H ,-NO2, the alkyl of 1-8 carbon atom or alkoxyl, the cycloalkyl of 3-8 carbon atom, the alkene of 2-8 carbon atom
Alkyl,
Described Y1、Y2And Y3Identical or different, it is each independently selected from-H ,-CH3, the alkyl of 2-8 carbon atom or alkoxyl,
The cycloalkyl of 3-8 carbon atom, the alkylene of 2-8 carbon atom；
Described X ' and Y ' is identical or different, is each independently selected from-S-,-S-S-,-O-,-CO-；
Above-mentioned R1And R4Select substituent group in, in described circulus one or more H atom can by F, Cl, Br, I,
OH、NO2、The alkyl of 1-8 carbon atom or alkoxyl or the alkene of 2-8 carbon atom
Alkyl replaces,
Described R2Selected from-H, the alkyl of 1-8 carbon atom or alkoxyl, the cycloalkyl of 3-8 carbon atom or 2-8 carbon atom
Alkylene
Or with R1Shown group is identical；
Premise is: described R1ForTime, described R4It is not
And described R1And R4In at least one represent
X is halogen.
Concrete reaction scheme is as follows:
The concrete operations of heretofore described step a intermediate compound I-A synthesis are: under nitrogen protection, add in organic solvent A
Beginning raw material (benzene, diphenyl sulfide or thioxanthone etc.), AlCl3Stirring mixing, ice salt bath is cooled to about-5 DEG C, drips R2
The acetyl halide compound of group and the mixed liquor of organic solvent A, temperature controls at-5 DEG C～5 DEG C, and about 2h dropping is complete, removes brine ice
Bath, clear-cutting forestland to room temperature, continue stirring reaction 2～3h, post processing obtains white solid intermediate compound I-A.Initiation material, AlCl3
And R2The optimum mole ratio of the acetyl halide compound of group is 1:1.1:1.05.
Heretofore described organic solvent A is dichloromethane, dichloroethanes, chloroform or carbon tetrachloride.
The concrete operations of heretofore described step b intermediate compound I-B synthesis are: add intermediate compound I-A, stirring in organic solvent B
After Jun Yun, add hydrochloric acid or logical hydrogen chloride, logical methyl nitrite or dropping amyl nitrite under room temperature, reaction 3～5h be stirred at room temperature,
Concentrating under reduced pressure, recrystallization obtains white solid intermediate compound I-B.
Heretofore described organic solvent B be oxolane, diisopropyl ether, methyl tertiary butyl ether(MTBE), ether, methyl phenyl ethers anisole, butyl ether,
Ethylene glycol diethyl ether and dioxane etc..
The concrete operations of heretofore described step c acyl group oxime ester photoinitiator synthesis are: add intermediate in organic solvent C
I-B and pyridine or triethylamine, stir, ice salt bath be cooled to about the 0 DEG C acetyl halide compound starting to drip M1 group and
The mixed liquor of organic solvent C, about 1.5h drips complete, and clear-cutting forestland to room temperature continues stirring reaction about 2h, processes pale yellow
Color oily liquids, is the acyl group oxime ester compound shown in formula I of the present invention.
Heretofore described organic solvent C is dichloromethane, dichloroethanes, chloroform, carbon tetrachloride or dioxane.Described
The mol ratio of intermediate I-B and carboxylic acid halides containing M1 structure or anhydride be 1:1.1.
Present invention also offers acyl group oxime ester compound performance described in a kind of formula I and the application in UV photo-curing material.
Beneficial effects of the present invention: acyl group oxime ester compound of the present invention in the case of mass concentration is identical, its ultraviolet
Absorbing spectrogram same or similar with the uv absorption spectrogram of OXE-1, the heat of acyl group oxime ester compound the most of the present invention is steady
Qualitative substantially stable than OXE-1；Acyl group oxime ester compound of the present invention has the structure of matter of part at ultraviolet absorpting spectrum
In have obvious red shift with OXE-1, have bigger absorption 300～365nm, LED cold light source can be realized and use as activating light source, this
The application performance (light sensitivitys, heat stability, dissolubility) of the acyl group oxime ester compound described in invention is than existing OXE-1's
Application performance is good.
Meanwhile, compared to existing like product, described acyl group oxime ester compound show on the whole significantly improve combine
Close application performance (dissolubility, stability, developability, the surface anti-crease property of formed film, safety in utilization), it addition, this
Acyl group oxime ester compound described in invention also has the most excellent storage stability and the highest photocuring activity, in low exposure
Under dosage, just energy crosslinking curing and solidification effect are splendid, and Light Curing does not produce poisonous and harmful substances, safe to use.
The smooth zero defect of film edge prepared, does not has scum silica frost, and whole pattern integrity is good, and surface does not has wrinkle, the colorized optical filtering made
Sheet optical clarity is high, not light leak.Prominent odor profiles, storage stability, developability, the one-tenth that show photosensitive composite
The aspects such as the surface anti-crease property of shape film, safety in utilization.
Accompanying drawing explanation
Fig. 1 is (E)-2-((3-benzoyloxy-2,4,6-trimethylbenzoyl epoxide) imino group)-1-(4-(benzene sulfydryl) phenyl) octyl-1-ketone
The uv absorption line comparison diagram of (compounds I-2-1) and OXE-1, wherein A is (E)-2-((3-benzoyloxy-2,4,6-trimethyls
Benzoyloxy) imino group) the uv absorption line of-1-(4-(benzene sulfydryl) phenyl) octyl-1-ketone.
Fig. 2 is (E)-2-(nuclear-magnetism of (oximino)-1-(4-(benzene sulfydryl) phenyl) octyl-1-ketone (compounds I-2-1-3)1HNMR composes
Figure.
Fig. 3 is (E)-2-((3-benzoyloxy-2,4,6-trimethylbenzoyl epoxide) imino group)-1-(4-(benzene sulfydryl) phenyl) octyl-1-ketone
The nuclear-magnetism of (compounds I-2-1)1HNMR spectrogram.
Fig. 4 is (E)-1-(3-benzoyl-2,4,6-trimethylphenyl)-2-(oximino) octyl-1-ketone (compounds I-7-1-3)
Nuclear-magnetism1HNMR spectrogram.
Fig. 5 is (E)-1-(3-benzoyl-2,4,6-trimethylphenyl)-2-((4-(benzene sulfydryl) benzoyloxy) imino group) octyl-1-
The nuclear-magnetism of ketone (compounds I-7-1)1HNMR spectrogram.
Fig. 6 is (E)-2-(3-benzoyl-2,4,6-trimethylbenzoyl imido ester group)-1-(3-benzoyl-2,4,6-trimethyl
Phenyl) nuclear-magnetism of octyl-1-ketone (compounds I-13-1)1HNMR spectrogram.
Fig. 7 is the nuclear-magnetism of the chloro-4-of 1-(2-hydroxyl imido grpup) octanoic acid ester group thioxanthone (compounds I-4-1-3)1HNMR spectrogram.
Fig. 8 is (E)-1-chloro-(2-(3-benzoyl-2,4,6-trimethylbenzoyl imido ester group))-4-octanoic acid ester group thioxanthone
The nuclear-magnetism of (compounds I-4-1)1HNMR spectrogram.
Fig. 9 is (E)-1-(3-benzoyl-2,4,6-trimethylphenyl)-2-((4-(benzene sulfydryl) benzoyloxy) imino group) octyl-1-
The UV of ketone (compounds I-7-1) absorbs spectrogram.
Figure 10 is (E)-2-(3-benzoyl-2,4,6-trimethylbenzoyl imido ester group)-1-(3-benzoyl-2,4,6-trimethyl
Phenyl) octyl-1-ketone (compounds I-13-1) UV absorb spectrogram.
Figure 11 is (E)-1-chloro-(2-(3-benzoyl-2,4,6-trimethylbenzoyl imido ester group))-4-octanoic acid ester group thioxanthene
The UV of ketone (compounds I-4-1) absorbs spectrogram.
Detailed description of the invention
The compound of formula I of the present invention is preferably as follows one or more in compound:
Embodiment 1
The preparation of positive caprylyl chloride (I-2-1-1)
There-necked flask, adds dichloromethane 200ml, caprylic acid 100g and 2 DMF, costs reflux condensing tube, constant voltage
Dropping funnel, drying tube and alkali liquor device for absorbing tail gas, be heated to backflow, be slowly added dropwise 165g thionyl chloride and 30ml dichloro
Methane blended liquid, about 1h dropping is complete, and reflux 2h, and concentrating under reduced pressure adds fresh methylene chloride 100ml concentrating under reduced pressure again,
Obtain pale yellow solution 114g, be compounds I-2-1-1.
The preparation of 1-(4-(benzene sulfydryl) phenyl) octyl-1-ketone (compounds I-2-1-2)
There-necked flask, adds 123g (0.66mol) diphenyl sulfide and 350ml dichloromethane, and ice salt bath is cooled to-5 DEG C, logical nitrogen
Gas, adds 97.1g (0.73mol) anhydrous A1C13, add drying tube, reflux condensing tube and tail gas absorption, slowly drip 113g (0.69mol)
Positive caprylyl chloride and the mixed liquor of 50ml dichloromethane, control temperature at-5～5 DEG C, about 2h dropping complete, remove ice salt bath,
Clear-cutting forestland, to room temperature, continues stirring reaction 2～3h, and TLC monitoring reaction is completely.Reactant is poured slowly into 200ml 10%
Ice dilute hydrochloric acid in, stirring 30min after separatory, 100ml dichloromethane aqueous phase extracted, merge organic facies, 3 × 100ml water
Washing, 2%NaHCO3Solution is adjusted to separatory after neutrality, and 100ml washes 1 time, anhydrous MgSO4It is dried, filters, reduce pressure dense
Contracting, recrystallization obtains white solid 175g, is compounds I-2-1-2, productivity 85%.MP:31-32 DEG C；MS:m/z=312.15.
1HNMR (300MHz, CDCl3), δ=0.87 (t, J=6.8Hz, 3H), 1.26～1.35 (m, 8H), 1.70 (m, 2H),
2.89 (t, J=7.4Hz, 2H), 7.21 (d, J=8.3Hz, 2H), 7.38～7.42 (m, 3H), 7.47～7.52 (m, 2H), 7.82 (d,
J=8.3Hz, 2H)
(E)-2-(preparation of (oximino)-1-(4-(benzene sulfydryl) phenyl) octyl-1-ketone (compounds I-2-1-3)
There-necked flask, adds tetrahydrofuran solution (containing 29gHCl) and 31.2g (0.1mol) compounds I of 300ml hydrogen chloride
-2-1-2, is stirred at room temperature dissolving, drips the tetrahydrofuran solution (0.12mol) of 150ml methyl nitrite, to having reacted under room temperature
Quan Hou, concentrating under reduced pressure, obtain orange/red oil 40g, add 250ml dichloromethane, 3 × 100ml water washs, anhydrous MgSO4
Being dried, concentrating under reduced pressure after filtration, obtain rufous oily liquids 34g, add 120ml petroleum ether, the lower heating for dissolving of stirring is complete,
Slow cooling, to-5 DEG C, separates out white solid, sucking filtration, petroleum ether filter wash cake, obtains white solid 18.7g, be compounds I-2-1-3,
Productivity 55%.
1HNMR (300MHz, CDCl3), 0.88 (t, J=6.6Hz, 3H), 2.73 (t, J=7.5Hz, 2H), 1.29～1.36 (m,
6H), 1.50～1.58 (m, 2H), 8.73 (br, 1H), 7.18～7.28 (d, J=4.2Hz, 2H), 7.39～7.44 (m, 3H),
7.50～7.53 (m, 2H), 7.78-7.87 (d, J=8.7Hz, 2H), as shown in Figure 2.
The preparation of 3-benzoyl-2,4,6-tri-methyl chloride (compounds I-2-1-4)
There-necked flask, adds dichloromethane 100ml, 3-benzoyl-mesitylene carboxylic acid 26.8g (0.1mol) and 2
Drip DMF, cost reflux condensing tube, constant pressure funnel, drying tube and alkali liquor device for absorbing tail gas, be heated to backflow, slowly
Dropping 36.9g (0.3mol) thionyl chloride and 50ml dichloromethane mixed liquor, about 1h dropping is complete, and reflux 2h, concentrating under reduced pressure,
Add fresh methylene chloride 100ml concentrating under reduced pressure again, obtain rufous oily liquids 30g, be compounds I-2-1-4.
(E)-2-((3-benzoyloxy-2,4,6-trimethylbenzoyl epoxide) imino group)-1-(4-(benzene sulfydryl) phenyl) octyl-1-ketone (chemical combination
Thing I-2-1) preparation
Add 6.82g (0.02mol) compounds I-2-1-3 and 50ml dichloromethane, add after being cooled to about 0 DEG C
2.37g (0.03mol) pyridine, temperature control dropping 6.29g (0.022mol) compounds I-2-1-4 and 20ml dichloromethane, drip complete
Rear natural temperature reaction 3h, reacts complete, adds 30ml H20, separatory after stirring 30min, add saturated NaHCO3Molten
Liquid 100ml is washed till about pH=10, and water washing, to neutral, add 2% dilute hydrochloric acid and is adjusted to about pH=4,3 × 100ml water
It is washed till neutrality, anhydrous MgSO4Being dried, filter, concentrating under reduced pressure obtains orange/red oil 8.3g, yield 70%, is chemical combination
Thing I-2-1.
1HNMR (300MHz, CDCl3), 0.81～0.89 (t, J=6.0Hz, 3H), 2.76～2.81 (t, J=8.7Hz, 2H),
1.22～1.32 (m, 4H), 1.47-1.57 (m, 4H), 2.13～2.15 (m, 6H), 2.36～2.42 (t, J=5.8Hz, 3H), 7.03
(s, J=7.8Hz, 1H), 7.20～7.45 (d, J=4.2Hz, 2H), 7.50～7.54 (m, 5H), 7.55～7.56 (m, 2H),
7.73 (s, J=5.7Hz, 1H), 7.83～7.89 (d, J=8.3Hz, 2H), 7.98～8.01 (m, 2H), as shown in Figure 3.
Embodiment 2
The preparation of positive caprylyl chloride (I-7-1-1)
There-necked flask, adds dichloromethane 200ml, caprylic acid 100g and 2 DMF, costs reflux condensing tube, constant voltage
Dropping funnel, drying tube and alkali liquor device for absorbing tail gas, be heated to backflow, be slowly added dropwise 165g thionyl chloride and 30ml dichloro
Methane blended liquid, about 1h dropping is complete, and reflux 2h, and concentrating under reduced pressure adds fresh methylene chloride 100ml concentrating under reduced pressure again,
Obtain pale yellow solution 114g, be compounds I-7-1-1.
The preparation of 1-(3-benzoyl-2,4,6-trimethylphenyl) octyl-1-ketone (I-7-1-2)
There-necked flask, adds 100g (0.45mol) 3-benzoyl-2,4,6-trimethylbenzenes and 300ml dichloromethane, ice salt bath
It is cooled to-5 DEG C, logical nitrogen, add 65.3g (0.49mol) anhydrous A1C13, add drying tube, reflux condensing tube and tail gas absorption,
Slowly dripping positive caprylyl chloride and the mixed liquor of 50ml dichloromethane of 76.1g (0.47mol), control temperature is at-5～5 DEG C, and about 2h drips
Complete, remove ice salt bath, clear-cutting forestland to room temperature, continue stirring reaction 2～3h, TLC monitoring reaction is completely.By reactant
In the dilute hydrochloric acid of the ice being poured slowly into 200ml 10%, separatory after stirring 30min, 100ml dichloromethane aqueous phase extracted, merge
Organic facies, 3 × 100ml water washs, 2%NaHCO3Solution is adjusted to separatory after neutrality, and 100ml washes 1 time, anhydrous MgSO4
Being dried, filter, concentrating under reduced pressure, recrystallization obtains yellow-brown solid 129g, is compounds I-7-1-2, productivity 82%.MS:
M/z=350.22.
(E) preparation of-1-(3-benzoyl-2,4,6-trimethylphenyl)-2-(oximino) octyl-1-ketone (I-7-1-3)
There-necked flask, adds tetrahydrofuran solution (containing 29g HCl) and 35.0g (0.1mol) compounds I of 300ml hydrogen chloride
-7-1-2, is stirred at room temperature dissolving, drips the tetrahydrofuran solution (0.12mol) of 150ml methyl nitrite, to having reacted under room temperature
Quan Hou, concentrating under reduced pressure, obtain orange/red oil 44g, add 250ml dichloromethane, 3 × 100ml water washs, anhydrous MgSO4
Being dried, concentrating under reduced pressure after filtration, obtain rufous oily liquids 36g, add 120ml petroleum ether, the lower heating for dissolving of stirring is complete,
Slow cooling, to-5 DEG C, separates out brown-red solid, sucking filtration, petroleum ether filter wash cake, obtains brown-red solid 20g, be compounds I
-7-1-3, productivity 53%.
1HNMR (300MHz, CDCl3), 0.86～0.90 (t, J=6.4Hz, 3H), 2.64～2.70 (t, J=8.4Hz, 2H),
1.29～1.37 (m, 6H), 1.49～1.54 (m, 2H), 1.89 (t, J=5.7Hz, 3H), 2.01～2.16 (m, 6H), 8.99 (br,
1H), 6.95 (s, J=7.8Hz, 1H), 7.28～7.45 (m, 2H), 7.56～7.61 (m, 1H), 7.82～7.84 (d, J=6.3Hz,
2H), as shown in Figure 4.
The preparation of the chloro-1-of 2-(4-(benzene sulfydryl) phenyl) ethyl ketone (compounds I-7-1-4)
There-necked flask, adds 50g (0.27mol) diphenyl sulfide and 200ml dichloromethane, and ice salt bath is cooled to-5 DEG C, logical nitrogen,
Add 39.4g (0.30mol) anhydrous A1C13, add drying tube, reflux condensing tube and tail gas absorption, slowly drip 31.8g (0.28mol)
Chloracetyl chloride and the mixed liquor of 50ml dichloromethane, control temperature at-5～5 DEG C, about 1h dropping complete, remove ice salt bath,
Clear-cutting forestland, to room temperature, continues stirring reaction 2～3h, and TLC monitoring reaction is completely.Reactant liquor is poured slowly into the ice of 10%
In dilute hydrochloric acid, PH=4, separatory after stirring 30min, 100ml dichloromethane aqueous phase extracted, merge organic facies, 3 × 100ml water
Washing, 2%NaHCO3Solution is adjusted to separatory after neutrality, and 100ml washes 1 time, anhydrous MgSO4It is dried, filters, reduce pressure dense
Contracting, obtains 45g yellow solid, is compounds I-7-1-4, yield: 64% after recrystallization.MS:m/z=262.7
The preparation of 4-benzene mercaptobenzoic acid (compounds I-7-1-5)
In there-necked flask, add the 25%NaOH solution of cooling, NaClO solution (10%), tri-methyl benzyl ammonium bromide, control
Temperature 0 DEG C～5 DEG C, temperature control slowly drips the chloro-1-of 2-(4-(benzene sulfydryl) phenyl) ketone (compounds I-7-1-4) of 45g (0.17mol)
With the mixed liquor of 200ml dichloromethane, about 2h dropping is complete, removes ice salt bath, clear-cutting forestland to room temperature, continues stirring anti-
Answering 2～3h, TLC monitoring reaction is completely.Add sodium sulfite, after stirring 30min, add 200ml dichloromethane extraction and 10%
Hydrochloric acid, PH=3, separatory, then by 150ml dichloromethane aqueous phase extracted, merge organic facies, the washing of 3 × 100ml water is to neutral
Rear separatory, anhydrous MgSO4It is dried, filters, concentrating under reduced pressure, obtain 30g yellow solid after recrystallization, be compounds I-7-1-5,
Yield: 76.7%.
The preparation of 4-(benzene sulfydryl) Benzenecarbonyl chloride. (compounds I-7-1-6)
There-necked flask, adds dichloromethane 100ml, 4-(benzene sulfydryl) benzoic acid 21g (0.091mol) and 2 DMF,
Cost reflux condensing tube, constant pressure funnel, drying tube and alkali liquor device for absorbing tail gas, be heated to backflow, be slowly added dropwise 11.2g
(0.095mol) thionyl chloride and 30ml dichloromethane mixed liquor, about 0.5h dropping is complete, and reflux 1h, and concentrating under reduced pressure adds
Enter fresh methylene chloride 100ml concentrating under reduced pressure again, obtain brown yellow oil liquid 26g, be compounds I-7-1-6.(with first
MS:m/z=244.3 after alcohol esterification)
(E)-1-(3-benzoyl-2,4,6-trimethylphenyl)-2-((4-(benzene sulfydryl) benzoyloxy) imino group) octyl-1-ketone (chemical combination
Thing I-7-1) preparation
Add 7.58g (0.02mol) compounds I-7-1-3 and 50ml dichloromethane, after being cooled to about 0 DEG C, add 2.37g (0.03
Mol) pyridine, temperature control dropping 5.45g (0.022mol) compounds I-7-1-6 and 20ml dichloromethane, naturally rise after dropping
Temperature reaction 3h, reacts complete, adds 30ml H20, separatory after stirring 30min, add saturated NaHCO3Solution 100ml
Being washed till about pH=10, water washing, to neutral, add 2% dilute hydrochloric acid and is adjusted to about pH=4, and 3 × 100ml is washed to neutrality,
Anhydrous MgSO4Being dried, filter, concentrating under reduced pressure obtains orange-yellow very viscous liquid (nearly solid), and ethyl alcohol recrystallization obtains 8.6g, receives
Rate 73%, is compounds I-7-1.
1HNMR (300MHz, CDCl3), 0.85～0.89 (t, J=6.6Hz, 3H), 2.82～2.87 (t, J=8.7Hz, 2H),
1.30～1.32 (m, 4H), 1.45 (m, 2H), 1.60～1.65 (m, 2H), 1.97 (m, 3H), 2.12 (m, 3H), 2.24 (t,
J=5.8Hz, 3H), 6.99 (s, J=7.8Hz, 1H), 7.21～7.28 (d, J=8.9Hz, 2H), 7.43～7.62 (m, 8H),
7.90～7.93 (m, 4H), as shown in Figure 5.
Embodiment 3
The preparation of positive caprylyl chloride (I-13-1-1)
There-necked flask, adds dichloromethane 200ml, caprylic acid 100g and 2 DMF, costs reflux condensing tube, constant voltage
Dropping funnel, drying tube and alkali liquor device for absorbing tail gas, be heated to backflow, be slowly added dropwise 165g thionyl chloride and 30ml dichloro
Methane blended liquid, about 1h dropping is complete, and reflux 2h, and concentrating under reduced pressure adds fresh methylene chloride 100ml concentrating under reduced pressure again,
Obtain pale yellow solution 114g, be compounds I-13-1-1.
The preparation of 1-(3-benzoyl-2,4,6-trimethylphenyl) octyl-1-ketone (I-13-1-2)
There-necked flask, adds 100g (0.45mol) 3-benzoyl-2,4,6-trimethylbenzenes and 300ml dichloromethane, ice salt bath
It is cooled to-5 DEG C, logical nitrogen, add 65.3g (0.49mol) anhydrous A1C13, add drying tube, reflux condensing tube and tail gas absorption,
Slowly dripping positive caprylyl chloride and the mixed liquor of 50ml dichloromethane of 76.1g (0.47mol), control temperature is at-5～5 DEG C, and about 2h drips
Complete, remove ice salt bath, clear-cutting forestland to room temperature, continue stirring reaction 2～3h, TLC monitoring reaction is completely.By reactant
In the dilute hydrochloric acid of the ice being poured slowly into 200ml 10%, separatory after stirring 30min, 100ml dichloromethane aqueous phase extracted, merge
Organic facies, 3 × 100ml water washs, 2%NaHCO3Solution is adjusted to separatory after neutrality, and 100ml washes 1 time, anhydrous MgSO4
Being dried, filter, concentrating under reduced pressure, recrystallization obtains yellow-brown solid 129g, is compounds I-13-1-2, productivity 82%.MS:
M/z=350.22.
(E) preparation of-1-(3-benzoyl-2,4,6-trimethylphenyl)-2-(oximino) octyl-1-ketone (I-13-1-3)
There-necked flask, adds tetrahydrofuran solution (containing 29gHCl) and 35.0g (0.1mol) compounds I of 300ml hydrogen chloride
-13-1-2, is stirred at room temperature dissolving, drips the tetrahydrofuran solution (0.12mol) of 150ml methyl nitrite under room temperature, to reaction
After Wan Quan, concentrating under reduced pressure, obtain orange/red oil 44g, add 250ml dichloromethane, 3 × 100ml water washs, anhydrous
MgSO4It is dried, concentrating under reduced pressure after filtration, obtains rufous oily liquids 36g, add 120ml petroleum ether, under stirring, add thermosol
Solving completely, slow cooling, to-5 DEG C, separates out brown-red solid, sucking filtration, petroleum ether filter wash cake, obtains brown-red solid 20g, be
Compounds I-13-1-3, productivity 53%.
1HNMR (300MHz, CDCl3), 0.86～0.90 (t, J=6.4Hz, 3H), 2.64～2.70 (t, J=8.4Hz, 2H),
1.29～1.37 (m, 6H), 1.49～1.54 (m, 2H), 1.89 (t, J=5.7Hz, 3H), 2.01～2.16 (m, 6H), 8.99 (br,
1H), 6.95 (s, J=7.8Hz, 1H), 7.28～7.45 (m, 2H), 7.56～7.61 (m, 1H), 7.82～7.84 (d, J=6.3Hz,
2H)。
The preparation of 3-benzoyl-2,4,6-tri-methyl chloride (compounds I-13-1-4)
There-necked flask, adds dichloromethane 100ml, 3-benzoyl-mesitylene carboxylic acid 26.8g (0.1mol) and 2
Drip DMF, cost reflux condensing tube, constant pressure funnel, drying tube and alkali liquor device for absorbing tail gas, be heated to backflow, slowly
Dropping 36.9g (0.3mol) thionyl chloride and 50ml dichloromethane mixed liquor, about 1h dropping is complete, and reflux 2h, concentrating under reduced pressure,
Add fresh methylene chloride 100ml concentrating under reduced pressure again, obtain rufous oily liquids 30g, be compounds I-13-1-4.
(E)-2-(3-benzoyl-2,4,6-trimethylbenzoyl imido ester group)-1-(3-benzoyl-2,4,6-trimethylphenyl) is pungent
The preparation of-1-ketone (compounds I-13-1)
Add 7.8g (0.02mol) compounds I-13-1-3 and 50ml dichloromethane, after being cooled to about 0 DEG C, add 2.37g (0.03
Mol) pyridine, temperature control dropping 6.29g (0.022mol) compounds I-13-1-4 and 20ml dichloromethane, naturally rise after dropping
Temperature reaction 3h, reacts complete, adds 30ml H20, separatory after stirring 30min, add saturated NaHCO3Solution 100ml
Being washed till about pH=10, water washing, to neutral, add 2% dilute hydrochloric acid and is adjusted to about pH=4, and 3 × 100ml is washed to neutrality,
Anhydrous MgSO4Being dried, filter, concentrating under reduced pressure obtains light yellow slightly sticky solid, and ethyl alcohol recrystallization obtains 9.8g, yield 78%,
It is compounds I-13-1.
1HNMR (300MHz, CDCl3), 0.83～0.87 (t, J=6.6Hz, 3H), 2.72～2.77 (t, J=8.7Hz, 2H),
1.26～1.37 (m, 4H), 1.50-1.63 (m, 4H), 1.92～2.05 (m, 3H), 2.12～2.16 (t, J=12.4Hz, 3H), 2.30 (m,
6H), 2.72～2.77 (m, 6H), 6.95-6.97 (d, J=8.1Hz, 2H), 7.45～7.57 (m, 4H), 7.60-7.64 (m,
2H), 7.80～7.88 (m, 4H), as shown in Figure 6.
Embodiment 4
The preparation of positive caprylyl chloride (compounds I-4-1-1)
There-necked flask, adds dichloromethane 200ml, caprylic acid 100g and 2 DMF, costs reflux condensing tube, constant voltage
Dropping funnel, drying tube and alkali liquor device for absorbing tail gas, be heated to backflow, be slowly added dropwise 165g thionyl chloride and 30ml dichloro
Methane blended liquid, about 1h dropping is complete, and reflux 2h, and concentrating under reduced pressure adds fresh methylene chloride 100ml concentrating under reduced pressure again,
Obtain pale yellow solution 114g, be compounds I-4-1-1.
The preparation of 1-chloro-4-octanoic acid ester group thioxanthone (compounds I-4-1-2)
Add 5.24g (0.02mol) compound 1-chloro-4-hydroxyl thioxanthone and 50ml dichloromethane, after being cooled to about 0 DEG C
Add 2.37g (0.03mol) pyridine, temperature control dropping 3.56g (0.022mol) compounds I-4-1-1 and 20ml dichloromethane, dropping
After natural temperature reaction 3h, TLC plate tracks to react complete, adds 30ml H20, separatory after stirring 30min, add
Enter saturated NaHCO3Solution 100ml is washed till about pH=10, and water washing, to neutral, add 2% dilute hydrochloric acid and is adjusted to pH=4
Left and right, 3 × 100ml is washed to neutrality, anhydrous MgSO4Being dried, filter, concentrating under reduced pressure obtains yellow-brown solid, ethyl alcohol recrystallization
Obtain 6.5g, yield 84%, be compounds I-4-1-2.
The preparation of the chloro-4-of 1-(2-hydroxyl imido grpup) octanoic acid ester group thioxanthone (I-4-1-3)
There-necked flask, adds tetrahydrofuran solution (containing 29gHCl) and 38.9g (0.1mol) compounds I of 300ml hydrogen chloride
-4-1-2, is stirred at room temperature dissolving, drips the tetrahydrofuran solution (0.12mol) of 150ml methyl nitrite, to having reacted under room temperature
Quan Hou, concentrating under reduced pressure, obtain orange/red oil 49g, add 250ml dichloromethane, 3 × 100ml water washs, anhydrous MgSO4
Being dried, concentrating under reduced pressure after filtration, obtain rufous oily liquids 41g, add 120ml petroleum ether, the lower heating for dissolving of stirring is complete,
Slow cooling, to-5 DEG C, separates out umber yellow solid, sucking filtration, petroleum ether filter wash cake, obtains khaki solid 26.7g, be chemical combination
Thing I-4-1-3, productivity 64%.
1HNMR (300MHz, CDCl3), 0.85～0.88 (t, J=7.3Hz, 3H), 2.71～2.75 (t, J=9.4Hz, 2H),
1.30～1.36 (m, 6H), 1.50～1.57 (m, 2H), 11.24 (br, 1H), 7.21 (s, J=7.2Hz, 1H), 7.26～7.31 (s,
J=7.2Hz, 1H), 7.46 (s, J=8.1Hz, 1H), 7.54～7.57 (d, J=8.9Hz, 2H), 8.24-8.26 (s, J=7.2
Hz, 1H), as shown in Figure 7.
The preparation of 3-benzoyl-2,4,6-tri-methyl chloride (compounds I-4-1-4)
There-necked flask, adds dichloromethane 100ml, 3-benzoyl-mesitylene carboxylic acid 26.8g (0.1mol) and 2
Drip DMF, cost reflux condensing tube, constant pressure funnel, drying tube and alkali liquor device for absorbing tail gas, be heated to backflow, slowly
Dropping 36.9g (0.3mol) thionyl chloride and 50ml dichloromethane mixed liquor, about 1h dropping is complete, and reflux 2h, concentrating under reduced pressure,
Add fresh methylene chloride 100ml concentrating under reduced pressure again, obtain rufous oily liquids 30g, be compounds I-4-1-4.
(E)-1-chloro-(2-(3-benzoyl-2,4,6-trimethylbenzoyl imido ester group))-4-octanoic acid ester group thioxanthone (chemical combination
Thing I-13-1) preparation
Add 8.36g (0.02mol) compounds I-4-1-3 and 50ml dichloromethane, after being cooled to about 0 DEG C, add 2.37g (0.03
Mol) pyridine, temperature control dropping 6.29g (0.022mol) compounds I-4-1-4 and 20ml dichloromethane, naturally rise after dropping
Temperature reaction 3h, reacts complete, adds 30ml H20, separatory after stirring 30min, add saturated NaHCO3Solution 100ml
Being washed till about pH=10, water washing, to neutral, add 2% dilute hydrochloric acid and is adjusted to about pH=4, and 3 × 100ml is washed to neutrality,
Anhydrous MgSO4Being dried, filter, concentrating under reduced pressure obtains khaki solid, and ethyl alcohol recrystallization obtains 11.3g, yield 85%, being
Compound I-4-1.MP:140.76 DEG C.
1HNMR (300MHz, CDCl3), 0.81～0.83 (t, J=6.5Hz, 3H), 2.76～2.78 (t, J=8.5Hz, 2H),
1.21～1.26 (m, 4H), 1.47～1.52 (m, 4H), 2.13～2.15 (m, 6H), 2.42 (m, 3H), 7.23 (s, J=7.4Hz,
1H), 7.48～7.56 (m, 8H), 7.85～7.88 (m, 2H), 8.73～8.46 (s, J=8.4Hz, 1H), as shown in Figure 8.
Application Example 1
Have detected compounds I-2-1, I-7-1, I-13-1 and I-4-1 at conventional organic solvent, such as ethyl acetate, ethylene glycol
Dissolubility in single ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate.Take respectively the compounds I-2-1 of four parts of equivalent, I-7-1,
I-13-1 and I-4-1 is placed in four sample bottles, and spent glycol list ether, propylene glycol methyl ether acetate dissolve respectively, pass through TLC
Detection light trigger stability in the solution.Result shows and is respectively provided with certain dissolubility, and this photoinitiator is organic molten
Stability in agent is relatively good, all can keep more than 20 days not decomposing under the conditions of lucifuge in common solvent.
Application Example 2
Differential thermal-thermogravimetric analyzer is utilized to measure compounds I-2-1, I-7-1, I-13-1 and the pyrolysis performance of I-4-1.Programming rate:
10℃/min.Have detected compounds I-2-1, I-7-1, I-13-1 and I-4-1 temperature of initial decomposition all more than 150 DEG C, heat
Stability is preferable.
Application Example 3
Compound Compound I-2-1, I-7-1, I-13-1 and I-4-1 are dissolved in acetonitrile, are made into certain molar concentration respectively
Solution, by surveying its uv absorption spectrogram with ultraviolet-visible spectrophotometer, compare.Be can be seen that by detection spectrogram
Synthesized several compound uv absorption bands of a spectrum are broad, all have bigger absorption 300～365nm, as Fig. 1, Fig. 9, Figure 10,
Shown in Figure 11.
Application Example 4
Utilize REAL TIME INFRARED THERMAL IMAGE means of testing, compare compounds I-2-1 in embodiment, I-7-1, I-13-1 and I-4-1 and cause first
The double bond conversion rate of base 2-(Acryloyloxy)ethanol polymerization.With acetone as solvent, prepare compounds I-2-1, I-7-1, I-13-1 and I
The concentration of-4-1 is the sample of the 3% of monomer concentration, is applied on KBr salt sheet, is then placed in Nico-let5700, uses ultraviolet luminous point
Light source irradiates sample, and the ultraviolet light light intensity of regulation sample surfaces is 30mW/cm2.The double bond conversion rate near-infrared of monomer is real-time
Gathering, REAL TIME INFRARED THERMAL IMAGE parameter is set to data acquisition intervals 0.3985s, each spectral scan 1 time, and resolution is 4cm-1.Methyl
2-(Acryloyloxy)ethanol in near-infrared spectrogram the characteristic absorption peak of carbon-carbon double bond at 1630cm-1Place, along with the carrying out of photocuring reaction,
Carbon-carbon double bond becomes carbon-carbon single bond, and the absorption peak strength of double bond increases with light application time and dies down, so utilizing the spy of carbon-carbon double bond
Levy the change of absworption peak to reflect the intensity of variation of its polyreaction.Double bond conversion rate (DC) is combined following formula meter by data processing software
Obtain.
DC (%)=[1-(At/ Ao)] × 100%
Ao and A in formulatBe respectively sample before curing with illumination after t at 1630cm-1Place's hydroxyethyl methylacrylate double bond feature is inhaled
Receive the area at peak.Testing result display compounds I-2-1, I-7-1, I-13-1 and I-4-1 all can cause hydroxyethyl methacrylate
Polymerizable methacrylate, after illumination l0min, all can make the conversion ratio of acrylic double bond reach more than 60%.
Application Example 5
Film-forming resin, 2-hydroxyl butyl is made with polyvinylpyrrolidone (MW=40000) and polymethacrylate resin (Mn=50000)
Polymerization monomer made by acrylate, is separately added into compounds I-2-1, I-7-1, I-13-1 and I-4-1, adds appropriate chain tra nsfer
Agent and dyestuff, make solvent with propylene glycol monomethyl ether, is made into radical polymerization imaging photosensitive glue 1,2,3,4.Above glue is pressed
Following methods carries out performance test.Photosensitive liquid 1～4 centrifuge is spin-coated on PS that is that anticipate and that meet following condition
On aluminum substrate, aluminum plate foundation size: 1030mm × 800mm；Aluminum plate foundation thickness: 0.28～0.3mm；Grains specification: Ra=0.5～
0.6 μm, Rh=0.3～0.35 μm；Anode oxide film weight: 3～3.5g/m2.Control the rotating speed of centrifugal coating machine, make to be coated in
Coating weight (in terms of solid content) on aluminum substrate is 0.5～2.5g/m2, on centrifugal coating machine after preliminarily dried, transfer to 100 DEG C
Blast drier in be dried 3min, obtain purple laser c TP master.By master through purple laser explosure, do mask by Ugra test strip
The photosensitive property of test plate.After exposure, use 1%NaOH aqueous development.Exposure region, photopolymerizable compound is at initiator
In the presence of there is polyreaction, insoluble in developer solution, and non-exposed area is solvable, then obtains negative.By exposure imaging,
From the image obtained continuous tone step scale evaluate sensitivity, from micro-lines test block regional evaluation precision, thus evaluate photosensitive composition
The quality of thing photosensitive property.Experimental result shows in the case of time of exposure is 40s, compounds I-2-1, I-7-1, I-13-1
And I the plate of-4-1 all can show more than 3 sections of continuous tone step scale, precision is at 6 more than μ.As can be seen here, compounds I-2-1,
I-7-1, I-13-1 and I-4-1, under certain time of exposure and light exposure, can reach preferable imaging effect, are applicable to purple sharp
In photo-imaging system.
The above, be only presently preferred embodiments of the present invention, the present invention not makees any pro forma restriction, although the present invention
Disclosed above with preferred embodiment, but it is not limited to the present invention, any those skilled in the art, do not taking off
In the range of technical solution of the present invention, when the technology contents of available the disclosure above makes a little change or is modified to equivalent variations
Equivalent embodiments, as long as being without departing from technical solution of the present invention content, is made above example according to the technical spirit of the present invention
Any simple modification, equivalent variations and modification, all still fall within the range of technical solution of the present invention.
Claims (10)
1. an acyl group oxime ester compound, described acyl group oxime esters optical compounds has a structure shown in formula I:
Wherein,
Described R1And R4Identical or different, it is each independently selected from
Wherein, described R3Selected from-H ,-NO2, the alkyl of 1-8 carbon atom or alkoxyl, the cycloalkyl of 3-8 carbon atom, 2-8
The alkylene of individual carbon atom,
Described Y1、Y2And Y3Identical or different, it is each independently selected from-H ,-CH3, the alkyl of 2-8 carbon atom or alkoxyl,
The cycloalkyl of 3-8 carbon atom, the alkylene of 2-8 carbon atom；
Described X ' and Y ' is identical or different, is each independently selected from-S-,-S-S-,-O-,-CO-；
Above-mentioned R1And R4In the substituent group selected, in circulus, one or more-H can be by-F ,-Cl ,-Br ,-I ,-NO2、
-COOR′1、-CONR′2、-OR′3、The alkyl of 1-8 carbon atom or alkoxyl or
The alkylene of 2-8 carbon atom replaces, wherein R '1And R '2Be each independently selected from-H, The alkyl of 1-8 carbon atom, the cycloalkyl of 3-8 carbon atom, the alkylene of 2-8 carbon atom, R '3It is selected from
-H, the alkyl of 1-8 carbon atom, the cycloalkyl of 3-8 carbon atom, the alkylene of 2-8 carbon atom or the carbochain of 1-8 carbon atom
Carbonyl, wherein, in the carbochain carbonyl of 1-8 carbon atom, carbonyl is in end position, is positioned at connecting key；
Described R2Selected from-H, the alkyl of 1-20 carbon atom or alkoxyl, the cycloalkyl of 3-8 carbon atom or 2-20 carbon atom
Alkylene；
Or R2With R1Shown group is identical；
Premise is: above-mentioned R1And R4In at least one be
Acyl group oxime ester compound the most according to claim 1, it is characterised in that described R1And R4Identical or different, respectively
From independently selected from
Acyl group oxime ester compound the most according to claim 1, it is characterised in that described R1And R4In at least one represent
Acyl group oxime ester compound the most according to claim 1, it is characterised in that described R2Selected from-H, 1-8 carbon atom
The alkylene of alkyl, alkoxyl or 2-8 carbon atom or and R1Shown group is identical.
Acyl group oxime ester compound the most according to claim 1, it is characterised in that described R3Selected from-H ,-NO2、1-8
The alkyl of individual carbon atom or alkoxyl, the cycloalkyl of 3-8 carbon atom, the alkylene of 2-8 carbon atom,
Acyl group oxime ester compound the most according to claim 1, it is characterised in that described Y1、Y2And Y3It is identical or different,
It is each independently selected from-H ,-CH3, the alkyl of 2-8 carbon atom or alkoxyl.
Acyl group oxime ester compound the most according to claim 6, it is characterised in that described Y1、Y2And Y3It is identical or different,
It is each independently selected from-H or-CH3。
8. the acyl group oxime ester compound according to claim 1, according to any one of 2,3,5-7, it is characterised in that described
The group that the compound free formula I-1 of choosing of formula I forms to compound shown in I-17:
Wherein,
Described R2Selected from-H, the alkyl of 1-20 carbon atom or alkoxyl, the cycloalkyl of 3-8 carbon atom, 2-20 carbon atom
Alkylene or R1Shown group.
9. a preparation method for the acyl group oxime ester compound described in formula I, comprises the steps of:
A, the synthesis of intermediate I-A: with benzene, diphenyl sulfide or thioxanthone as initiation material, and containing R2The carboxylic acid halides of group
Compound, under ferric chloride, aluminum chloride or zinc chloride effect, by F-K reaction, synthetic intermediate I-A:
B, the synthesis of intermediate I-B: intermediate compound I in the case of being connected with hydrogen chloride or adding hydrochloric acid with methyl nitrite, nitrous acid
Ethyl ester or amyl nitrite carry out oxidation reaction, generation acyl group oxime intermediate I-B:
C, acyl group oxime ester lightlike initiating agent synthesize: intermediate I-B and the carboxylic acid halides containing M1 structure or anhydride, in pyridine or three second
In the presence of amine acid binding agent, under dichloromethane, dichloroethanes or dioxane solvent, synthesize the compound of formula I.
Wherein,
Described R1And R4Identical or different, it is each independently selected from
Wherein, described R3Selected from-H ,-NO2、
The alkyl of 1-8 carbon atom or alkoxyl, the cycloalkyl of 3-8 carbon atom, the alkylene of 2-8 carbon atom, Described Y1、Y2And Y3Identical or different, it is each independently selected from-H ,-CH3、
The alkyl of 2-8 carbon atom or alkoxyl, the cycloalkyl of 3-8 carbon atom, the alkylene of 2-8 carbon atom, described X ' and Y ' phase
Same or different, it is each independently selected from-S-,-S-S-,-O-,-CO-；
Above-mentioned R1And R4In the substituent group selected, in circulus, one or more-H can be by-F ,-Cl ,-Br ,-I ,-NO2、
-COOR′1、-CONR′2、-OR′3、The alkyl of 1-8 carbon atom or alkoxyl or
The alkylene of 2-8 carbon atom replaces, wherein R '1And R '2Be each independently selected from-H, The alkyl of 1-8 carbon atom, the cycloalkyl of 3-8 carbon atom, the alkylene of 2-8 carbon atom, R '3It is selected from
-H, the alkyl of 1-8 carbon atom, the cycloalkyl of 3-8 carbon atom, the alkylene of 2-8 carbon atom or the carbochain of 1-8 carbon atom
Carbonyl, wherein, in the carbochain carbonyl of 1-8 carbon atom, carbonyl is in end position, is positioned at connecting key；
Described X is halogen；
Described R2Selected from-H, the alkyl of 1-8 carbon atom or alkoxyl, the cycloalkyl of 3-8 carbon atom or the alkene of 2-8 carbon atom
Alkyl；
Or R2With R1Shown group is identical；
Premise is: described R1And R4In at least one represent
10. acyl group oxime ester compound application in UV photo-curing material according to any one of claim 1-8.
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| PCT/CN2016/083961 WO2016192610A1 (en) | 2015-06-03 | 2016-05-30 | Acyloxime ester compound used for uv curing material, synthesis method of same, and application of same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110776866A (en) * | 2018-07-27 | 2020-02-11 | 日本化药株式会社 | Sealing agent for electronic component, and liquid crystal display unit |
| CN115996959A (en) * | 2020-09-30 | 2023-04-21 | 积水化学工业株式会社 | Thioxanthone compound, photopolymerization initiator, curable resin composition, composition for display element, sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| WO2024041569A1 (en) * | 2022-08-24 | 2024-02-29 | 湖北固润科技股份有限公司 | Acyloxyphosphine oxime ester compound suitable for deep curing of uv-vis led light sources, method for preparing same, and use thereof |
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|---|---|---|---|---|
| CN110117262B (en) * | 2019-04-30 | 2023-04-11 | 同济大学 | 2-styryl benzoxazole or benzothiazolyl ketoxime ester compound and preparation method and application thereof |
| CN114605380A (en) * | 2022-04-12 | 2022-06-10 | 阜阳欣奕华材料科技有限公司 | Hyperbranched macromolecular photoinitiator and preparation method and application thereof |
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| CN115996959A (en) * | 2020-09-30 | 2023-04-21 | 积水化学工业株式会社 | Thioxanthone compound, photopolymerization initiator, curable resin composition, composition for display element, sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| WO2024041569A1 (en) * | 2022-08-24 | 2024-02-29 | 湖北固润科技股份有限公司 | Acyloxyphosphine oxime ester compound suitable for deep curing of uv-vis led light sources, method for preparing same, and use thereof |
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| CN106278967B (en) | 2020-08-07 |
| WO2016192610A1 (en) | 2016-12-08 |
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