WO2016192610A1 - 用于uv固化材料的酰基肟酯类化合物及其合成方法及应用 - Google Patents
用于uv固化材料的酰基肟酯类化合物及其合成方法及应用 Download PDFInfo
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- WO2016192610A1 WO2016192610A1 PCT/CN2016/083961 CN2016083961W WO2016192610A1 WO 2016192610 A1 WO2016192610 A1 WO 2016192610A1 CN 2016083961 W CN2016083961 W CN 2016083961W WO 2016192610 A1 WO2016192610 A1 WO 2016192610A1
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- Prior art keywords
- carbon atoms
- group
- alkyl
- same
- compound
- Prior art date
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- -1 ester compound Chemical class 0.000 title claims description 49
- 239000000463 material Substances 0.000 title claims description 16
- 238000001308 synthesis method Methods 0.000 title abstract 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 81
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 147
- 125000004432 carbon atom Chemical group C* 0.000 claims description 105
- 125000000217 alkyl group Chemical group 0.000 claims description 37
- 125000003545 alkoxy group Chemical group 0.000 claims description 30
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 27
- 125000002009 alkene group Chemical group 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 11
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 claims description 7
- 150000001336 alkenes Chemical group 0.000 claims description 6
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-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
- 238000005917 acylation reaction Methods 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 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
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 150000002367 halogens Chemical group 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 150000002148 esters Chemical group 0.000 abstract description 5
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- 231100000053 low toxicity Toxicity 0.000 abstract description 2
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- 239000007788 liquid Substances 0.000 description 24
- 238000002360 preparation method Methods 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 238000010992 reflux Methods 0.000 description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 21
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- 238000001723 curing Methods 0.000 description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 16
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 16
- 230000007935 neutral effect Effects 0.000 description 15
- 238000001035 drying Methods 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 10
- 238000000016 photochemical curing Methods 0.000 description 10
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- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 239000012267 brine Substances 0.000 description 9
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000011161 development Methods 0.000 description 8
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 8
- REEZZSHJLXOIHL-UHFFFAOYSA-N octanoyl chloride Chemical compound CCCCCCCC(Cl)=O REEZZSHJLXOIHL-UHFFFAOYSA-N 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 6
- 239000000976 ink Substances 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
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- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- OALNLIRHOZQOJH-UHFFFAOYSA-N 3-benzoyl-2,4,6-trimethylbenzoyl chloride Chemical compound C(C1=CC=CC=C1)(=O)C=1C(=C(C(=O)Cl)C(=CC=1C)C)C OALNLIRHOZQOJH-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
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- 239000000178 monomer Substances 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- HPQJDUGVPLQKIC-UHFFFAOYSA-N 3-benzoyl-2,4,6-trimethylbenzoic acid Chemical compound CC1=C(C(O)=O)C(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPQJDUGVPLQKIC-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical class CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
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- 0 C*(C)C(ON=C(*)C(*I)=O)=O Chemical compound C*(C)C(ON=C(*)C(*I)=O)=O 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
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- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-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
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- 125000003342 alkenyl group Chemical group 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
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- 238000005265 energy consumption 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
- 238000005286 illumination Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
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- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 description 2
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
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- AOWPVIWVMWUSBD-RNFRBKRXSA-N [(3r)-3-hydroxybutyl] (3r)-3-hydroxybutanoate Chemical compound C[C@@H](O)CCOC(=O)C[C@@H](C)O AOWPVIWVMWUSBD-RNFRBKRXSA-N 0.000 description 1
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- 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
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- 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
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- SKRDXYBATCVEMS-UHFFFAOYSA-N isopropyl nitrite Chemical compound CC(C)ON=O SKRDXYBATCVEMS-UHFFFAOYSA-N 0.000 description 1
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- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
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- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
-
- 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
- C07C323/23—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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
- 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
-
- 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 a photoinitiator, and more particularly to a photoinitiator for a UV curable material.
- UV curing Ultraviolet (UV) curing
- photocuring technology is an efficient, environmentally friendly, energy-saving, high-quality material surface treatment technology widely used in advertising, printing, high-end commodity packaging, decoration, electronics and communications, etc.
- the products are mainly in the form of UV coatings, UV inks, UV adhesives, photosensitive printing plates, photoresists, and light rapid prototyping materials.
- Photocuring is the process of illuminating a chemically active liquid material with ultraviolet light, causing it to rapidly polymerize and crosslink and cure it instantaneously.
- light curing Compared with other curing methods such as heat curing, light curing has the following advantages: 1. Fast speed, light curing products can be cured in a few seconds, which is the fastest curing speed among various inks, coatings and adhesives. 2, a wide range of applications, light curing products can be applied to a variety of substrates, especially suitable for some heat sensitive materials, such as paper, electronic components and plastics: 3. Low energy consumption, light curing products are fast at room temperature Curing, its energy consumption is only 1/10 to 1/5 of thermal curing; 4. Low pollution, photocuring products are basically free of volatile organic compounds (VOC), and are an environmentally friendly product.
- VOC volatile organic compounds
- UV wood coating can improve the wear resistance, scratch resistance and resistance of the plate.
- the UV three-dimensional coating can greatly improve the decorative effect, mainly applied to the protection of furniture and solid wood flooring.
- decoration in the printing industry, the use of UV offset inks has changed the past few problems of printing inks that need to be sprayed, and the colors are bright and saturated, and the definition is better. UV ink has become a new force for outdoor large-scale advertisements and signs.
- photoresist is an early application of light curing products, especially suitable for the production of some microelectronic products.
- a far-ultraviolet photoresist for large-scale integrated circuits is also indispensable for the fabrication of some key components in liquid crystal displays, plasma displays, and organic electroluminescent displays.
- Photocurable materials (photocurable coatings, inks, photoresists, RGB and BM) mainly composed of unsaturated resins and their monomer materials, so that they can be polymerized and cured under ultraviolet light, X-ray or laser irradiation.
- a photoinitiator or sensitizer is required.
- These added photoinitiators or sensitizers are capable of generating reactive groups under ultraviolet light, X-ray or laser irradiation of a certain wavelength, and exciting the unsaturated groups in the photocurable material to proliferate and cause curing of the photocurable material. .
- some of the traditional initiators widely used are: benzoin derivatives, benzil ketals, ⁇ , ⁇ -dialkoxyacetophenones, ⁇ -hydroxyalkylphenones, ⁇ - Aminoalkyl benzophenones, acylphosphine oxides, benzophenones/amines, methyl ketones, thioxanthone/amines, amine promoters, aromatic diazonium salts, aryl sulfonium salts and sulfonium salts, Ferrocene and ferrocene, hexaaryldiimidazole, triazazine and traditional oxime esters.
- OXE-l is the most typical ketone ester photoinitiator, which is mainly used in the manufacture of BM and RGB of large-screen LCD displays, which is expensive, and its structural formula has been applied for protection by foreign companies, Patent Publication Nos. CN99108598 and CN02811675,
- the synthetic method of the above-mentioned structural formula is cumbersome, the synthesis cost is high, the application performance of the product of the structure is not good enough, and the thermal stability is poor.
- ketoxime ester compounds having excellent photocuring application properties such as CN101565472A, which discloses a cycloalkyl-containing ketoxime ester photoinitiator which has excellent stability and solubility.
- CN101565472A discloses a cycloalkyl-containing ketoxime ester photoinitiator which has excellent stability and solubility.
- such products have been confirmed to have insufficient application performance problems, such as the safety hazard in use (decomposition to produce benzene-based highly toxic substances), photographic activity and thermal stability and other conventional properties need to be further improved.
- the present invention is directed to the insufficiency of the application performance of the existing acyl oxime ester photoinitiators, and the object of the present invention is to provide a good solubility, good thermal stability, high reactivity, low production cost, low price, and substantially no Odor, low migration, and high safety (low toxicity) acyl oxime esters.
- Another object of the present invention is to provide a process for producing the acyl oxime ester compound.
- a further object of the present invention is to provide the use of the acyl oxime ester compound in a UV curable material.
- the R 1 and R 4 are the same or different and are each independently selected from
- R 3 is selected from -H, -NO 2 , an alkyl or alkoxy group of 1 to 8 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, an alkene group of 2 to 8 carbon atoms,
- the Y 1 , Y 2 and Y 3 are the same or different and are each independently selected from -H, -CH 3 , an alkyl or alkoxy group of 2 to 8 carbon atoms, and a cycloalkyl group of 3 to 8 carbon atoms.
- the X' and Y' are the same or different and are each independently selected from -S-, -S-S-, -O-, -CO-;
- one or more of -H in the cyclic structure may be -F, -Cl, -Br, -I, -NO 2 , An alkyl or alkoxy group of 1 to 8 carbon atoms or an alkene group of 2 to 8 carbon atoms, wherein R' 1 and R' 2 are each independently selected from -H, An alkyl group of 1 to 8 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, an alkene group of 2 to 8 carbon atoms, and R' 3 is selected from -H, an alkyl group of 1 to 8 carbon atoms, 3 a cycloalkyl group of 8 to 8 carbon atoms, an alkene group of 2 to 8 carbon atoms or a carbon chain carbonyl group of 1 to 8 carbon atoms, wherein a carbonyl group of a carbon chain carbonyl group of 1 to 8 carbon atoms is located at a
- the R 2 is selected from -H, an alkyl or alkoxy group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms or an alkene group of 2 to 20 carbon atoms;
- R 2 is the same as the group represented by R 1 ,
- At least one of R 1 and R 4 represents
- one or more of -H in the cyclic structure in R 1 and R 4 may be -F, -NO 2 , -COOR' 1 , -COOR' 2 ,- OR' 3 , an alkyl or alkoxy group of 1 to 8 carbon atoms, wherein R' 1 and R' 2 are each independently selected from -H, Alkyl group having 1-8 carbon atoms, cycloalkyl of 3-8 carbon atoms, the olefin group of 2-8 carbon atoms, R '3 is selected from -H, alkyl group having 1-8 carbon atoms or a A carbon chain carbonyl group of -8 carbon atoms, wherein a carbonyl group of a carbon chain carbonyl group of 1-8 carbon atoms is at a terminal position at a bond.
- R 1 and R 4 are the same or different and are each independently selected from the group consisting of
- the R 2 is selected from -H, an alkyl or alkoxy group of 1 to 20 carbon atoms, an alkene group of 2 to 20 carbon atoms or the same as the group represented by R 1 .
- the R 2 is selected from -H, an alkyl or alkoxy group of 1 to 20 carbon atoms, an alkene group of 2 to 20 carbon atoms,
- the R 2 is selected from -H, an alkyl or alkoxy group of 1 to 15 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, 2 to 15 carbon atoms. Olefin group,
- the R 2 is selected from -H, an alkyl or alkoxy group of 1 to 15 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, 2 to 15 carbon atoms. Olefin group,
- the R 2 is selected from an alkyl or alkoxy group of 1 to 15 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, and an alkene group of 2 to 15 carbon atoms. .
- the R 3 is selected from -H, -NO 2 , an alkyl or alkoxy group of 1-8 carbon atoms, a cycloalkyl group of 3-6 carbon atoms, 2-8 Alkenyl groups of carbon atoms,
- X' and Y&apos are the same or different and are each independently selected from the group consisting of -S-, -S-S-, -O-, -CO-.
- the R 3 is selected from -H, an alkyl or alkoxy group of 1-8 carbon atoms.
- the Y 1 , Y 2 and Y 3 are the same or different and are each independently selected from -H, an alkyl group of 1-8 carbon atoms or an alkoxy group.
- R 3 represents -H.
- the Y 1 , Y 2 and Y 3 represent -CH 3 .
- the compound of Formula I is selected from the group consisting of the compounds of Formulas I-1 to I-17:
- the R 2 is selected from -H, an alkyl or alkoxy group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, an alkene group of 2 to 20 carbon atoms or a group represented by R 1 .
- the invention also provides a preparation method of the acyl oxime ester compound of the formula I, comprising the following steps:
- intermediate I-A the synthesis of intermediate I-A: starting from benzene, diphenyl sulfide or thioxanthone, and the acid halide compound containing R 2 group, in ferric chloride, aluminum trichloride or
- the intermediate I-A is synthesized by the acylation reaction under the action of zinc chloride and the like:
- acyl oxime ester photoinitiator synthesis intermediate I-B and an acid halide or anhydride containing M1 structure, in the presence of pyridine or triethylamine and other acid binding agents, in dichloromethane, dichloroethane or two
- the compound of the formula I is synthesized as a solvent such as hexacyclic or the like.
- R 1 and R 4 are the same or different and are each independently selected from Wherein R 3 is selected from -H, -NO 2 , an alkyl or alkoxy group of 1 to 8 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, an alkene group of 2 to 8 carbon atoms,
- the Y 1 , Y 2 and Y 3 are the same or different and are each independently selected from -H, -CH 3 , an alkyl or alkoxy group of 2 to 8 carbon atoms, and a cycloalkyl group of 3 to 8 carbon atoms.
- the X' and Y' are the same or different and are each independently selected from -S-, -S-S-, -O-, -CO-;
- one or more H atoms in the cyclic structure may be F, Cl, Br, I, OH, NO 2 , Alkenyl or alkoxy groups of 1-8 carbon atoms or alkene groups of 2-8 carbon atoms,
- the R 2 is selected from -H, an alkyl or alkoxy group of 1 to 8 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms or an alkene group of 2 to 8 carbon atoms
- the premise is: the R 1 is When the R 4 is not
- R 1 and R 4 represents
- X is a halogen
- the specific operation of the synthesis of the intermediate IA in the step a of the present invention is as follows: under the protection of nitrogen, the starting material (benzene, diphenyl sulfide or thioxanthone, etc.) and AlCl 3 are added to the organic solvent A, and the mixture is stirred and mixed.
- the ice brine bath is cooled to about -5 ° C, and a mixture of the R 2 group acid halide compound and the organic solvent A is added dropwise, and the temperature is controlled at -5 ° C to 5 ° C. After about 2 hours, the ice brine bath is removed. After returning to room temperature, the reaction was stirred for 2 to 3 hours, and worked up to give a white solid intermediate IA.
- the optimum molar ratio of the starting material, the acid halide compound of the AlCl 3 and R 2 groups is 1:1.1:1.05.
- the organic solvent A described in the present invention is dichloromethane, dichloroethane, chloroform or carbon tetrachloride.
- the specific operation of the synthesis of the intermediate IB in the step b described in the present invention is as follows: adding the intermediate IA to the organic solvent B, stirring uniformly, adding hydrochloric acid or hydrogen chloride at room temperature, passing methyl nitrite or adding isopropyl nitrite The ester was stirred at room temperature for 3 to 5 h, concentrated under reduced pressure and then recrystallized to afford white solid intermediate IB.
- the organic solvent B described in the present invention is tetrahydrofuran, diisopropyl ether, methyl tert-butyl ether, diethyl ether, anisole, dibutyl ether, ethylene glycol diethyl ether, dioxane or the like.
- step c acyl oxime ester photoinitiator described in the present invention is: adding the intermediate I-B and pyridine or triethylamine to the organic solvent C, stirring uniformly, and cooling to about 0 ° C in an ice brine bath.
- the mixture of the acid halide compound of the M1 group and the organic solvent C is added dropwise, and the addition is completed in about 1.5 hours, and the reaction is naturally returned to room temperature, and the reaction is stirred for about 2 hours to obtain a pale yellow oily liquid, which is represented by the general formula I of the present invention.
- An acyl oxime ester compound An acyl oxime ester compound.
- the organic solvent C described in the present invention is dichloromethane, dichloroethane, chloroform, carbon tetrachloride or dioxane.
- the molar ratio of the intermediate I-B to the acid halide or anhydride containing the M1 structure is 1:1.1.
- the invention also provides the properties of an acyl oxime ester compound of the formula I and its use in UV curable materials.
- the acyl oxime ester compound of the present invention has the same or similar ultraviolet absorption spectrum as the ultraviolet absorption spectrum of OXE-1 at the same mass concentration, wherein the acyl hydrazine of the present invention
- the thermal stability of the ester compound is significantly more stable than that of OXE-1;
- the partial structure of the acyl oxime ester compound of the present invention has a significant red shift with OXE-1 in the ultraviolet absorption spectrum, and is large at 300-365 nm.
- Absorption, LED cold light source can be used as an active light source, and the application performance (sensitivity, thermal stability, solubility) of the acyl oxime ester compound of the present invention is better than that of the existing OXE-1.
- the acyl oxime ester compound exhibits a markedly improved overall application performance (solubility, stability, developability, surface wrinkle resistance of the formed film, and safe use) as compared with the prior art products.
- the acyl oxime ester compound of the present invention has excellent storage stability and high photocuring activity, and can be cross-linked and cured at a low exposure dose, and the curing effect is excellent, and the photocuring is excellent.
- the process does not produce toxic and harmful substances and is safe to use.
- the obtained film has a flat edge without defects, no scum, good integrity of the whole pattern, no wrinkles on the surface, and the color filter produced has high optical transparency and no light leakage.
- the outstanding performance is in the odor property, storage stability, developability, surface wrinkle resistance of the formed film, use safety, and the like of the photosensitive composition.
- Figure 1 is (E)-2-((3-benzoyloxy-2,4,6-trimethylbenzoyloxy)imino)-1-(4-(phenylhydrazino)phenyl) Comparison of ultraviolet absorption lines of oct-1-one (Compound I-2-1) and OXE-1, wherein A is (E)-2-((3-benzoyloxy-2,4,6-three) Ultraviolet absorption line of methyl benzoyloxy)imino)-1-(4-(phenylhydrazo)phenyl)oct-1-one.
- Figure 2 is a nuclear magnetic ⁇ 1 >H NMR spectrum of (E)-2-((hydroxyimino)-1-(4-(phenylhydrazo)phenyl)oct-1-one (Compound I-2-1-3).
- Figure 3 is (E)-2-((3-benzoyloxy-2,4,6-trimethylbenzoyloxy)imino)-1-(4-(phenylindenyl)phenyl) Nuclear magnetic 1 H NMR spectrum of oct-1-one (Compound I-2-1).
- Figure 4 is (E)-1-(3-benzoyl-2,4,6-trimethylphenyl)-2-(hydroxyimino)oct-1-one (Compound I-7-1-3) Nuclear magnetic 1 H NMR spectrum.
- Figure 5 is (E)-1-(3-benzoyl-2,4,6-trimethylphenyl)-2-((4-(phenylphenyl)benzoyloxy)imino)octyl- Nuclear magnetic 1 H NMR spectrum of 1-ketone (Compound I-7-1).
- Figure 6 is (E)-2-(3-benzoyl-2,4,6-trimethylbenzoimido)-1-(3-benzoyl-2,4,6-tri Nuclear magnetic 1 H NMR spectrum of methylphenyl)oct-1-one (Compound I-13-1).
- Figure 7 is a nuclear magnetic ⁇ 1 >H NMR spectrum of 1-chloro-4-(2-hydroxyimino)octanoate thioxanthone (Compound I-4-1-3).
- Figure 8 is (E)-1-chloro-(2-(3-benzoyl-2,4,6-trimethylbenzoimido))-4-octanoate thioxanthone Nuclear magnetic 1 H NMR spectrum of (Compound I-4-1).
- Figure 9 is (E)-1-(3-benzoyl-2,4,6-trimethylphenyl)-2-((4-(phenylphenyl)benzoyloxy)imino)octyl- UV absorption spectrum of 1-ketone (Compound I-7-1).
- Figure 10 is (E)-2-(3-benzoyl-2,4,6-trimethylbenzoimido)-1-(3-benzoyl-2,4,6-tri UV absorption spectrum of methylphenyl)oct-1-one (Compound I-13-1).
- Figure 11 is (E)-1-chloro-(2-(3-benzoyl-2,4,6-trimethylbenzoimido))-4-octanoate thioxanthone UV absorption spectrum of (Compound I-4-1).
- the compounds of the formula I according to the invention are preferably one or more of the following compounds:
- a three-necked flask was charged with 200 ml of dichloromethane, 100 g of n-octanoic acid and 2 drops of DMF.
- a reflux condenser, a constant pressure dropping funnel, a drying tube and an alkali tail gas absorption device were placed, and the mixture was heated to reflux, and 165 g of thionyl chloride was slowly added dropwise.
- a mixture of 30 ml of methylene chloride and the mixture was refluxed for about 1 hour, and the mixture was evaporated to dryness.
- a three-necked flask was charged with 123 g (0.66 mol) of diphenyl sulfide and 350 ml of dichloromethane, cooled to -5 ° C in an ice brine bath, and passed through nitrogen, 97.1 g (0.73 mol) of anhydrous A1C1 3 was added, and a drying tube and a reflux condenser were added.
- a three-necked flask was added with 300 ml of a hydrogen chloride solution in tetrahydrofuran (containing 29 g of HCl) and 31.2 g (0.1 mol) of compound I-2-1-2, and dissolved by stirring at room temperature.
- 150 ml of a solution of methyl nitrite in tetrahydrofuran (0.12 mol) was added dropwise at room temperature.
- a three-necked flask was charged with 200 ml of dichloromethane, 100 g of n-octanoic acid and 2 drops of DMF.
- a reflux condenser, a constant pressure dropping funnel, a drying tube and an alkali tail gas absorption device were placed, and the mixture was heated to reflux, and 165 g of thionyl chloride was slowly added dropwise.
- a mixture of 30 ml of methylene chloride and the mixture was refluxed for about 1 hour, and the mixture was evaporated to dryness.
- a three-necked flask was charged with 100 g (0.45 mol) of 3-benzoyl-2,4,6-trimethylbenzene and 300 ml of dichloromethane, and the mixture was cooled to -5 ° C in an ice-bath bath, and nitrogen gas was added thereto, and 65.3 g (0.49 mol) was added.
- Anhydrous A1C1 3 add drying tube, reflux condenser and tail gas absorption, slowly drop 76.1g (0.47mol) of a mixture of n-octanoyl chloride and 50ml dichloromethane, control the temperature at -5 ⁇ 5 ° C, about 2h drop After completion, the ice brine bath was removed, and naturally returned to room temperature.
- the reaction was stirred for 2 to 3 hours, and the reaction was monitored by TLC.
- the reaction was slowly poured into 200 ml of 10% ice-dilute hydrochloric acid, stirred for 30 min, and then separated, and the aqueous phase was extracted with 100 ml of dichloromethane.
- the organic phase was combined, washed with 3 ⁇ 100 ml of water, and the solution was adjusted to neutral after 2% NaHCO 3 solution. liquid separation, washed with water 100ml 1 times, dried over anhydrous MgSO 4, filtered, and concentrated under reduced pressure, and recrystallized to give 129 g of a tan solid, that is, the compound i-7-1-2, 82% yield.
- MS: m/z 350.22.
- a three-necked flask was added with 300 ml of a solution of hydrogen chloride in tetrahydrofuran (containing 29 g of HCl) and 35.0 g (0.1 mol) of compound I-7-1-2, and dissolved by stirring at room temperature.
- 150 ml of a solution of methyl nitrite in tetrahydrofuran (0.12 mol) was added dropwise at room temperature.
- a three-necked flask was charged with 50 g (0.27 mol) of diphenyl sulfide and 200 ml of dichloromethane, cooled to -5 ° C in an ice brine bath, and passed through nitrogen, 39.4 g (0.30 mol) of anhydrous A1C1 3 was added, and a drying tube and a reflux condenser were added.
- a three-necked flask was charged with 100 g (0.45 mol) of 3-benzoyl-2,4,6-trimethylbenzene and 300 ml of dichloromethane, and the mixture was cooled to -5 ° C in an ice-bath bath, and nitrogen gas was added thereto, and 65.3 g (0.49 mol) was added.
- Anhydrous A1C1 3 add drying tube, reflux condenser and tail gas absorption, slowly drop 76.1g (0.47mol) of a mixture of n-octanoyl chloride and 50ml dichloromethane, control the temperature at -5 ⁇ 5 ° C, about 2h drop After completion, the ice brine bath was removed, and naturally returned to room temperature.
- the reaction was stirred for 2 to 3 hours, and the reaction was monitored by TLC.
- the reaction was slowly poured into 200 ml of 10% ice-dilute hydrochloric acid, stirred for 30 min, and then separated, and the aqueous phase was extracted with 100 ml of dichloromethane.
- the organic phase was combined, washed with 3 ⁇ 100 ml of water, and the solution was adjusted to neutral after 2% NaHCO 3 solution. liquid separation, washed with water 100ml 1 times, dried over anhydrous MgSO 4, filtered, and concentrated under reduced pressure, and recrystallized to give 129 g of a tan solid, that is, the compound i-13-1-2, 82% yield.
- MS: m/z 350.22.
- a three-necked flask was charged with 300 ml of a solution of hydrogen chloride in tetrahydrofuran (containing 29 g of HCl) and 35.0 g (0.1 mol) of compound I-13-1-2, dissolved at room temperature, and 150 ml of a solution of methyl nitrite in tetrahydrofuran (0.12 mol) was added dropwise at room temperature.
- a three-necked flask was charged with 200 ml of dichloromethane, 100 g of n-octanoic acid and 2 drops of DMF.
- a reflux condenser, a constant pressure dropping funnel, a drying tube and an alkali tail gas absorption device were placed, and the mixture was heated to reflux, and 165 g of thionyl chloride was slowly added dropwise.
- a mixture of 30 ml of methylene chloride and the mixture was refluxed for about 1 hour, and the mixture was evaporated to dryness.
- a three-necked flask was charged with 300 ml of a hydrogen chloride in tetrahydrofuran solution (containing 29 g of HCl) and 38.9 g (0.1 mol) of compound I-4-1-2, and dissolved by stirring at room temperature.
- 150 ml of a solution of methyl nitrite in tetrahydrofuran (0.12 mol) was added dropwise at room temperature.
- the pyrolysis properties of the compounds I-2-1, I-7-1, I-13-1 and I-4-1 were measured by a differential thermal-thermogravimetric analyzer. Heating rate: 10 ° C / min.
- the initial decomposition temperatures of the compounds I-2-1, I-7-1, I-13-1 and I-4-1 were all above 150 °C, and the thermal stability was good.
- the double bond conversion of the polymerization of hydroxyethyl methacrylate initiated by the compounds I-2-1, I-7-1, I-13-1 and I-4-1 in the examples was compared using real-time infrared testing means.
- a sample of 3% of the monomer concentration of the compound I-2-1, I-7-1, I-13-1 and I-4-1 was prepared by using acetone as a solvent, and coated on a KBr salt sheet, and then The sample was placed in a Nico-let 5700, and the sample was irradiated with an ultraviolet light source to adjust the ultraviolet light intensity of the sample surface to 30 mW/cm 2 .
- the double bond conversion rate of the monomer was collected by near-infrared real-time, and the real-time infrared parameter was set to a data acquisition interval of 0.3985 s, and each spectral scan was performed once, with a resolution of 4 cm -1 .
- the characteristic absorption peak of carbon-carbon double bond in the near-infrared spectrum is 1630 cm -1 , and the carbon-carbon double bond becomes a carbon-carbon single bond and the double-bond absorption peak as the photo-curing reaction proceeds.
- the intensity weakens as the illumination time increases, 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 the data processing software in combination with the following formula.
- Ao and A t are sample time t before and after light curing hydroxyethyl acrylate double bond character in the area of a peak absorption at 1630cm -1 methacrylic acid.
- the results showed that the compounds I-2-1, I-7-1, I-13-1 and I-4-1 could all initiate the polymerization of hydroxyethyl methacrylate. After 10 min of illumination, the double bonds of acrylic acid could be obtained. The conversion rate is over 60%.
- I-13-1 and I-4-1 adding appropriate amount of chain transfer agent and dye, and using propylene glycol methyl ether as solvent to form free radical polymerization imaging photosensitive glue 1, 2, 3, 4.
- the above glue was tested for performance as follows.
- the rotation speed of the centrifugal coater is controlled so that the coating amount (in terms of solid content) coated on the aluminum plate base is 0.5 to 2.5 g/m 2 , and after preliminary drying on a centrifugal coater, the blast is transferred to 100 ° C.
- the experimental results show that the plates of the compounds I-2-1, I-7-1, I-13-1 and I-4-1 can be displayed in the continuous adjustment of the scales when the exposure time is 40 s. Above the segment, the accuracy is 6 ⁇ or more. It can be seen that the compounds I-2-1, I-7-1, I-13-1 and I-4-1 can achieve better imaging effects under certain exposure time and exposure, and can be applied to violet lasers. In the imaging system.
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Abstract
本发明提供一种具有通式Ⅰ所示结构的新型酰基肟酯结构的化合物,所述化合物具有良好的紫外吸收效果,该化合物具有溶解性好、热稳定性和感光活性高且毒性低的特点,应用性能明显优于同类产品,本发明还提供了一种制备所述新型酰基肟酯结构的化合物的合成方法,所述合成方法具有简单高效,生产过程中不产生污染性废弃物,且产品纯度高,适用于工业化生产的优点。
Description
本发明涉及一种光引发剂,尤其涉及一种用于UV固化材料的光敏引发剂。
紫外光(UV)固化,简称光固化技术,是一种高效、环保、节能、优质的材料表面处理技术,广泛应用于广告、印刷、高档商品包装、装潢、电子及通信等领域,目前光固化产品主要以UV涂料、UV油墨、UV胶黏剂、感光性印刷版材、光刻胶、光快速成型材料等形式出现。
光固化是利用紫外光照射具有化学活性的液态材料,引发其快速聚合交联,并使其瞬间固化的过程。
光固化与热固化等其他固化方式相比,有以下优势:1.速率快,光固化产品一般在几秒内即可固化,是目前各种油墨、涂料及胶黏剂中固化速度最快的;2.应用范围广泛,光固化产品可适用于多种基材,特别适用于一些热敏感性的材质,如纸张、电子元器件及塑料等:3.能耗低,光固化产品是常温快速固化,其能耗只有热固化的1/10到1/5;4.低污染,光固化产品基本不含挥发性有机物(VOC),是一类环境友好型的产品。
在日常生活中,光固化产品无处不在,并改变着我们的生活。如在板材涂装保护及装饰行业,UV木器涂料涂装可以提高板材耐磨、抗划伤和耐抗性,通过UV立体涂装还可大大提高装饰效果,主要应用在家具、实木地板的保护及装饰上;在印刷行业,UV胶印油墨的使用一改过去印刷品印油墨不干而需喷粉的弊病,并且色彩鲜艳饱和,清晰度更佳,UV油墨已成为户外大型广告和指示牌的生力军,也是高档烟酒、保健品、化妆品和食品包装的重要印刷材料;在光电子、信息和通信工业中,光刻胶是较早应用的光固化产品,特别适用于一些微电子产品的制作。如制作大规模集成电路用的远紫外光刻胶,在液晶显示器、等离子体显示器、有机电致发光显示器中的一些关键部件的制作中也都离不开光刻胶。
1968年Bayer公司开发了第一代紫外光固化木器涂料,首先实现了光固化技术的产业化。随后光固化技术迅猛发展,应用领域不断扩大,形成了一个新的产业。上世纪70、80年代,欧美辐射固化协会成立,推动了光固化技术的研究和发
展,在北美、欧洲和日本等发达国家和地区,巴斯夫、拜耳、陶氏等跨国公司纷纷加盟光固化生产,目前已成为了具有一定市场规模的产业。我国从上世纪80年代开始发展光固化技术,由于原料和设备的限制,发展缓慢。进入90年代,紫外光固化技术和设备的引进大大推动了我国光固化产业的发展,进入21世纪,我国光固化产业获得了更加快速的发展,特别是光引发剂已成为世界上最大的生产和出口国,已初步形成一个新的高新产业。如今大力提倡可持续发展,建立和谐社会,并加大了环境的保护,这为我国光固化产业的发展提供了机遇。
主要由不饱和树脂及其单体材料组成的光固化材料(光固化涂料、油墨、光刻胶、RGB和BM),要使其能在紫外光、X射线或激光照射下发生聚合固化反应,必须光引发剂或增感剂。这些添加的光引发剂或增感剂能够在一定波长的紫外光、X射线或激光照射下,产生活性基团,激发光固化材料中的不饱和基团繁盛聚合反应,引起光固化材料的固化。
在光固化材料中,广泛应用的一些传统引发剂有:安息香衍生物、联苯酰缩酮类、α,α-二烷氧基苯乙酮类、α–羟基烷基苯酮类、α-氨基烷基苯酮类、酰基氧化膦类、二苯甲酮/胺类、米氏酮、噻吨酮/胺类、胺促进剂、芳香重氮盐、芳基腆鎓盐和硫鎓盐、二茂铁和二茂铁类、六芳基二咪唑类、三氮嗪类及传统肟酯类等。由于这些传统的光引发剂或多或少的存在着感光度低(聚合速率和转化率低)、溶解性差(透明度低和光刻残渣多)、氧气对光固化影响大及贮存稳定性差等缺点,因此它们及感光材料的使用受到了很大的限制,也极大的影响了感光材料的性能,特别是不能满足新一代大屏幕LCD关键部件BM和CF的制作要求。新型肟酯类光引发剂的出现,很大程度上解决了上述问题。肟酯类化合物的光化学特性最早出现在文献A.Wemer and A.Piguet,Ber.Dtsch.Chem.Ges.1904,37,4295中;而作为光引发剂的应用,最早则是出现在文献G.A.Delzenne,u.Laridon and H.Peeters,EuropeanPolymer Journal,1970,6,933-943中,商品名为DE-OS 179508和Agfa-Gevaert AG;曾较广泛商业应用的肟酯类光引发剂产品是Quantacure PDO。
这些传统的肟酯类光引发剂虽然光引发洁性高,但由于热稳定性差,而逐步被工业应用所淘汰;肟酯类光引发剂的”复活”最早出现在文献R.Malliviaet al,J.Photochem.Photobiol.A:Chemistry 2001,138,193和文献L.Lavalée et aI,J.Photochem.Photobiol.A:Chemistry 2002.151,27中,由于在肟酯化合物中引入了二苯硫醚或咔唑基团,这些基团中有较大的共轭体系和较强的分子内电子转移特性,因此极大的提高了这类肟酯化合物的稳定性和感光活性,目前广泛应用的两个代表性的肟酯类光引发剂是OXE-1和OXE-2,结构式如下所示:
其中OXE-l就是最典型的酮肟酯类光引发剂,它们主要应用于制造大屏幕LCD显示器的BM和RGB,价格昂贵,并且其结构式己被国外公司申请保护,专利公开号CN99108598和CN02811675,上述公布的结构式的合成方法繁琐,合成成本高,本结构的产品的应用性能不够好,热稳定性较差的问题。随后,涌现出了诸多具有优异光固化应用性能的酮肟酯类化合物的报道,如CN101565472A公开了一种含有环烷基的酮肟酯光引发剂,其具有很好的稳定性和溶解性。但是伴随着实践应用,此类产品被证实仍然存在应用性能不足的问题,如使用中存在安全隐患(分解产生苯类高毒性物质)、感光活性和热稳定性等常规性能需进一步提高。
现在入们对于光引发剂的效果及其分解产物的毒性、气味和迁移性等特性要求越来越高,开发具有良好的溶解性、低气味或无气味和低迁移性的良好特性的大分子光引发剂将成为未来发展的主要方向。但目前已商业化的大分子光引发剂大多价格昂贵或产品性能有一定缺陷,因此迫切需要价格低廉且性能好的产品来替代。
发明内容
发明目的:本发明针对现有酰基肟酯类光引发剂应用性能的不足,本发明的目的是提供一种溶解性好、热稳定性好、反应活性高、生产成本低、价格低廉、基本无气味,低迁移性,且使用安全性高(毒性低)的酰基肟酯类化合物。
本发明的另一目的是提供所述酰基肟酯类化合物的制备方法。
本发明的再一目的是提供所述酰基肟酯类化合物在UV光固化材料中的应用。
技术方案:为了达到上述发明目的,本发明提供了一种酰基肟酯类化合物,所述酰基肟酯类光化合物具有通式Ⅰ所示结构:
所述Y1、Y2及Y3相同或不同,各自独立地选自-H、-CH3、2-8个碳原子的烷基或烷氧基、3-8个碳原子的环烷基、2-8个碳原子的烯烃基;
所述X‘和Y’相同或不同,各自独立地选自-S-、-S-S-、-O-、-CO-;
上述R1和R4选择的取代基中,所述环状结构中一个或多个-H可以被-F、-Cl、-Br、-I、-NO2、1-8个碳原子的烷基或烷氧基或2-8个碳原子的烯烃基取代,其中R’1和R’2各自独立地选自-H、1-8个碳原子的烷基、3-8个碳原子的环烷基、2-8个碳原子的烯烃基,R’3选自-H、1-8个碳原子的烷基、3-8个碳原子的环烷基、2-8个碳原子的烯烃基或1-8个碳原子的碳链羰基,其中,1-8个碳原子的碳链羰基中羰基在端位,位于连接键处;
所述R2选自-H、1-20个碳原子的烷基或烷氧基、3-8个碳原子的环烷基或2-20个碳原子的烯烃基;
或者R2与R1所示基团相同,
在本发明的一些优选实施方式中,所述R1和R4中所述环状结构中一个或多个-H可以被-F、-NO2、-COOR′1、-COOR′2、-OR′3、1-8个碳原子的烷基或烷氧基,其中R’1和R’2各自独立地选自-H、
1-8个碳原子的烷基、3-8个碳原子的环烷基、2-8个碳原子的烯烃基,R’3选自-H、1-8个碳原子的烷基或1-8个碳原子的碳链羰基,其中,1-8个碳原子的碳链羰基中羰基在端位,位于连接键处。
本发明的一些优选实施方式中,所述R2选自-H、1-20个碳原子的烷基或烷氧基、2-20个碳原子的烯烃基或与R1所示基团相同。
本发明的一些实施方式中,优选地,所述R2选自1-15个碳原子的烷基或烷氧基、3-8个碳原子环烷基、2-15个碳原子的烯烃基。
在本发明的一些实施方式中,所述X‘和Y’相同或不同,各自独立地选自-S-、-S-S-、-O-、-CO-。
本发明的一些实施方式中,所述R3选自-H、1-8个碳原子的烷基或烷氧基。
本发明的一些实施方式中,所述Y1、Y2及Y3相同或不同,各自独立地选自-H、1-8个碳原子的烷基或烷氧基。
本发明的一些实施方式中,所述R3表示-H。
本发明的一些实施方式中,所述Y1、Y2及Y3表示-CH3。
本发明的一些实施方式中,通式Ⅰ的化合物选自由通式Ⅰ-1至Ⅰ-17所示化合物组成的组:
其中,
所述R2选自-H、1-20个碳原子的烷基或烷氧基、3-8个碳原子的环烷基、2-20
个碳原子的烯烃基或R1所示基团。
本发明还提供了一种通式Ⅰ所述的酰基肟酯类化合物的制备方法,包含如下步骤:
a、中间体Ⅰ-A的合成:以苯、二苯硫醚或硫杂蒽酮等为起始原料,与含有R2基团的酰卤化合物,在三氯化铁、三氯化铝或氯化锌等作用下,通过付克酰基化反应,合成中间体Ⅰ-A:
b、中间体Ⅰ-B的合成:中间体I在通有氯化氢或加盐酸的情况下与亚硝酸甲酯、***或亚硝酸异戊酯等进行氧化反应,生成酰基肟中间体Ⅰ-B:
c、酰基肟酯类光引发剂合成:中间体Ⅰ-B与含有M1结构的酰卤或酸酐,在吡啶或三乙胺等缚酸剂存在下,在二氯甲烷、二氯乙烷或二氧六环等做溶剂下合成通式Ⅰ的化合物。
其中,
所述Y1、Y2及Y3相同或不同,各自独立地选自-H、-CH3、2-8个碳原子的烷基或烷氧基、3-8个碳原子的环烷基、2-8个碳原子的烯烃基;
所述X‘和Y’相同或不同,各自独立地选自-S-、-S-S-、-O-、-CO-;
所述R2选自-H、1-8个碳原子的烷基或烷氧基、3-8个碳原子的环烷基或者2-8个碳原子的烯烃基
或者与R1所示基团相同;
X为卤素。
具体反应路线如下:
本发明中所述的步骤a中间体I-A合成的具体操作为:氮气保护下,向有机溶剂A中加入起始原料(苯、二苯硫醚或硫杂蒽酮等)、AlCl3搅拌混合,冰盐水浴冷却至-5℃左右,滴加R2基团的酰卤化合物与有机溶剂A的混合液,温度控制在-5℃~5℃,约2h滴加完毕,撤去冰盐水浴,自然恢复至室温,继续搅拌反应2~3h,后处理得到白色固体中间体I-A。起始原料、AlCl3和R2基团的酰卤化合物的最佳
摩尔比为1:1.1:1.05。
本发明中所述的有机溶剂A为二氯甲烷、二氯乙烷、氯仿或四氯化碳。
本发明中所述的步骤b中间体I-B合成的具体操作为:有机溶剂B中加入中间体I-A,搅拌均匀后,室温下加入盐酸或通氯化氢,通亚硝酸甲酯或滴加亚硝酸异戊酯,室温搅拌反应3~5h,减压浓缩,重结晶得白色固体中间体I-B。
本发明中所述的有机溶剂B为四氢呋喃、异丙醚、甲基叔丁基醚、***、苯甲醚、丁醚、乙二醇二***及二氧六环等。
本发明中所述的步骤c酰基肟酯光引发剂合成的具体操作为:向有机溶剂C中加入中间体Ⅰ-B和吡啶或三乙胺,搅拌均匀,冰盐水浴冷却至0℃左右开始滴加M1基团的酰卤化合物及有机溶剂C的混合液,1.5h左右滴加完毕,自然恢复至室温继续搅拌反应2h左右,处理得浅黄色油状液体,即为本发明通式Ⅰ所示的酰基肟酯类化合物。
本发明中所述的有机溶剂C为二氯甲烷、二氯乙烷、氯仿、四氯化碳或二氧六环。所述的中间体Ⅰ-B与含有M1结构的酰卤或酸酐的摩尔比为1:1.1。
本发明还提供了一种通式Ⅰ所述酰基肟酯类化合物性能及在UV光固化材料中的应用。
本发明的有益效果:本发明所述的酰基肟酯类化合物在质量浓度相同的情况下,其紫外吸收谱图与OXE-1的紫外吸收谱图相同或相似,其中本发明所述的酰基肟酯类化合物的热稳定性明显比OXE-1稳定;本发明所述的酰基肟酯类化合物有部分的物质结构在紫外吸收图谱中与OXE-1有明显红移,在300~365nm有较大吸收,可实现LED冷光源作为激活光源使用,本发明所述的酰基肟酯类化合物的应用性能(感光度、热稳定性、溶解性)比现有的OXE-1的应用性能好。
同时,相比于现有同类产品,所述的酰基肟酯类化合物在整体上表现出了显著改善的综合应用性能(溶解性,稳定性、显影性、成形膜的表面抗折皱性、使用安全性),另外,本发明所述的酰基肟酯类化合物还具有非常优异的储存稳定性和很高的光固化活性,在低曝光剂量下,就能交联固化且固化效果极佳,光固化过程不产生有毒、有害物质,使用安全性高。制得的膜边缘平整无缺陷,没有浮渣,整个图案完整度好,表面没有折皱,制成的彩色滤光片光学透明度高,不漏光。突出的表现在感光性组合物的气味性、存储稳定性、显影性、成形膜的表面抗折皱性、使用安全性等方面。
图1为(E)-2-((3-苯甲酰氧基-2,4,6-三甲基苯甲酰氧基)亚氨基)-1-(4-(苯巯基)苯基)辛-1-酮(化合物Ⅰ-2-1)和OXE-1的紫外吸收线比较图,其中A为(E)-2-((3-苯甲酰氧基-2,4,6-三甲基苯甲酰氧基)亚氨基)-1-(4-(苯巯基)苯基)辛-1-酮的紫外吸收线。
图2为(E)-2-((羟亚氨基)-1-(4-(苯巯基)苯基)辛-1-酮(化合物Ⅰ-2-1-3)的核磁1HNMR谱图。
图3为(E)-2-((3-苯甲酰氧基-2,4,6-三甲基苯甲酰氧基)亚氨基)-1-(4-(苯巯基)苯基)辛-1-酮(化合物Ⅰ-2-1)的核磁1HNMR谱图。
图4为(E)-1-(3-苯甲酰基-2,4,6-三甲基苯基)-2-(羟亚氨基)辛-1-酮(化合物Ⅰ-7-1-3)的核磁1HNMR谱图。
图5为(E)-1-(3-苯甲酰基-2,4,6-三甲基苯基)-2-((4-(苯巯基)苯甲酰氧基)亚氨基)辛-1-酮(化合物Ⅰ-7-1)的核磁1HNMR谱图。
图6为(E)-2-(3-苯甲酰基-2,4,6-三甲基苯甲酰亚氨酯基)-1-(3-苯甲酰基-2,4,6-三甲基苯基)辛-1-酮(化合物Ⅰ-13-1)的核磁1HNMR谱图。
图7为1-氯-4-(2-羟亚胺基)辛酸酯基硫杂蒽酮(化合物Ⅰ-4-1-3)的核磁1HNMR谱图。
图8为(E)-1-氯-(2-(3-苯甲酰基-2,4,6-三甲基苯甲酰亚氨酯基))-4-辛酸酯基硫杂蒽酮(化合物Ⅰ-4-1)的核磁1HNMR谱图。
图9为(E)-1-(3-苯甲酰基-2,4,6-三甲基苯基)-2-((4-(苯巯基)苯甲酰氧基)亚氨基)辛-1-酮(化合物Ⅰ-7-1)的UV吸收谱图。
图10为(E)-2-(3-苯甲酰基-2,4,6-三甲基苯甲酰亚氨酯基)-1-(3-苯甲酰基-2,4,6-三甲基苯基)辛-1-酮(化合物Ⅰ-13-1)的UV吸收谱图。
图11为(E)-1-氯-(2-(3-苯甲酰基-2,4,6-三甲基苯甲酰亚氨酯基))-4-辛酸酯基硫杂蒽酮(化合物Ⅰ-4-1)的UV吸收谱图。
本发明通式Ⅰ的化合物优选如下化合物中的一种或多种:
实施例1
正辛酰氯(Ⅰ-2-1-1)的制备
三口烧瓶,加入二氯甲烷200ml、正辛酸100g以及2滴DMF,搭上回流冷凝管、恒压滴液漏斗、干燥管及碱液尾气吸收装置,加热至回流,缓慢滴加165g氯化亚砜及30ml二氯甲烷混合液,约1h滴加完毕,回流2h,减压浓缩,加入新鲜二氯甲烷100ml再次减压浓缩,得浅黄色溶液114g,即为化合物Ⅰ-2-1-1。
1-(4-(苯巯基)苯基)辛-1-酮(化合物Ⅰ-2-1-2)的制备
三口烧瓶,加入123g(0.66mol)二苯硫醚和350ml二氯甲烷,冰盐水浴降温至-5℃,通氮气,加入97.1g(0.73mol)无水A1C13,加干燥管、回流冷凝管及尾气吸收,缓慢滴113g(0.69mol)的正辛酰氯和50ml二氯甲烷的混合液,控制温度在-5~5℃,约2h滴加完毕,撤去冰盐水浴,自然恢复至室温,继续搅拌反应2~3h,TLC监控反应完全。将反应物缓慢倒入200ml 10%的冰的稀盐酸中,搅拌30min后分液,100ml二氯甲烷萃取水相,合并有机相,3×100ml水洗涤,2%NaHCO3溶液调至中性后分液,100ml水洗1次,无水MgSO4干燥,过滤,减压浓缩,重结晶得白色固体175g,即为化合物Ⅰ-2-1-2,产率85%。MP:31-32℃;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-((羟亚氨基)-1-(4-(苯巯基)苯基)辛-1-酮(化合物Ⅰ-2-1-3)的制备
三口烧瓶,加入300ml氯化氢的四氢呋喃溶液(含29gHCl)和31.2g(0.1mol)化合物Ⅰ-2-1-2,室温搅拌溶解,室温下滴加150ml亚硝酸甲酯的四氢呋喃溶液(0.12mol),至反应完全后,减压浓缩,得橙红色油状液体40g,加入250ml二氯甲烷,3×100ml水洗涤,无水MgSO4干燥,过滤后减压浓缩,得红棕色油状液体34g,加入120ml石油醚,搅拌下加热溶解完全,缓慢降温至-5℃,析出白色固体,抽滤,石油醚洗滤饼,得白色固体18.7g,即为化合物Ⅰ-2-1-3,产率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),如图2所示。
3-苯甲酰基-2,4,6-三甲基苯甲酰氯(化合物Ⅰ-2-1-4)的制备
三口烧瓶,加入二氯甲烷100ml、3-苯甲酰基-2,4,6-三甲基苯甲酸26.8g(0.1mol)以及2滴DMF,搭上回流冷凝管、恒压滴液漏斗、干燥管及碱液尾气吸收装置,加热至回流,缓慢滴加36.9g(0.3mol)氯化亚砜及50ml二氯甲烷混合液,约1h滴加完毕,回流2h,减压浓缩,加入新鲜二氯甲烷100ml再次减压浓缩,得红棕色油状液体30g,即为化合物Ⅰ-2-1-4。
(E)-2-((3-苯甲酰氧基-2,4,6-三甲基苯甲酰氧基)亚氨基)-1-(4-(苯巯基)苯基)辛-1-酮(化合物Ⅰ-2-1)的制备
加入6.82g(0.02mol)化合物Ⅰ-2-1-3和50ml二氯甲烷,降温至0℃左右后加入2.37g(0.03mol)吡啶,控温滴加6.29g(0.022mol)化合物Ⅰ-2-1-4及20ml二氯甲烷,滴加完毕后自然升温反应3h,反应完毕,加入30ml H20,搅拌30min后分液,加入饱和NaHCO3溶液100ml洗至pH=10左右,水洗涤至中性,再
加入2%稀盐酸调至pH=4左右,3×100ml水洗至中性,无水MgSO4干燥,过滤,减压浓缩得橙红色油状液体8.3g,收率70%,即为化合物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),如图3所示。
实施例2
正辛酰氯(Ⅰ-7-1-1)的制备
三口烧瓶,加入二氯甲烷200ml、正辛酸100g以及2滴DMF,搭上回流冷凝管、恒压滴液漏斗、干燥管及碱液尾气吸收装置,加热至回流,缓慢滴加165g氯化亚砜及30ml二氯甲烷混合液,约1h滴加完毕,回流2h,减压浓缩,加入新鲜二氯甲烷100ml再次减压浓缩,得浅黄色溶液114g,即为化合物Ⅰ-7-1-1。
1-(3-苯甲酰基-2,4,6-三甲基苯基)辛-1-酮(Ⅰ-7-1-2)的制备
三口烧瓶,加入100g(0.45mol)3-苯甲酰基-2,4,6-三甲基苯和300ml二氯甲烷,冰盐水浴降温至-5℃,通氮气,加入65.3g(0.49mol)无水A1C13,加干燥管、回流冷凝管及尾气吸收,缓慢滴76.1g(0.47mol)的正辛酰氯和50ml二氯甲烷的混合液,控制温度在-5~5℃,约2h滴加完毕,撤去冰盐水浴,自然恢复至室温,继续搅拌反应2~3h,TLC监控反应完全。将反应物缓慢倒入200ml 10%的冰的稀盐酸中,搅拌30min后分液,100ml二氯甲烷萃取水相,合并有机相,3×100ml水洗涤,2%NaHCO3溶液调至中性后分液,100ml水洗1次,无水MgSO4干燥,过滤,减压浓缩,重结晶得棕黄色固体129g,即为化合物Ⅰ-7-1-2,产率82%。MS:m/z=350.22。
(E)-1-(3-苯甲酰基-2,4,6-三甲基苯基)-2-(羟亚氨基)辛-1-酮(Ⅰ-7-1-3)的制备
三口烧瓶,加入300ml氯化氢的四氢呋喃溶液(含29g HCl)和35.0g(0.1mol)化合物Ⅰ-7-1-2,室温搅拌溶解,室温下滴加150ml亚硝酸甲酯的四氢呋喃溶液
(0.12mol),至反应完全后,减压浓缩,得橙红色油状液体44g,加入250ml二氯甲烷,3×100ml水洗涤,无水MgSO4干燥,过滤后减压浓缩,得红棕色油状液体36g,加入120ml石油醚,搅拌下加热溶解完全,缓慢降温至-5℃,析出棕红色固体,抽滤,石油醚洗滤饼,得棕红色固体20g,即为化合物Ⅰ-7-1-3,产率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),如图4所示。
2-氯-1-(4-(苯巯基)苯基)乙酮(化合物Ⅰ-7-1-4)的制备
三口烧瓶,加入50g(0.27mol)二苯硫醚和200ml二氯甲烷,冰盐水浴降温至-5℃,通氮气,加入39.4g(0.30mol)无水A1C13,加干燥管、回流冷凝管及尾气吸收,缓慢滴31.8g(0.28mol)的氯乙酰氯和50ml二氯甲烷的混合液,控制温度在-5~5℃,约1h滴加完毕,撤去冰盐水浴,自然恢复至室温,继续搅拌反应2~3h,TLC监控反应完全。将反应液缓慢倒入10%的冰的稀盐酸中,PH=4,搅拌30min后分液,100ml二氯甲烷萃取水相,合并有机相,3×100ml水洗涤,2%NaHCO3溶液调至中性后分液,100ml水洗1次,无水MgSO4干燥,过滤,减压浓缩,重结晶后得到45g黄色固体,即为化合物Ⅰ-7-1-4,收率:64%。MS:m/z=262.7
4-苯巯基苯甲酸(化合物Ⅰ-7-1-5)的制备
在三口瓶中,加入冷却的25%NaOH溶液,NaClO溶液(10%),三甲基苄基溴化铵,控温0℃~5℃,控温缓慢滴45g(0.17mol)的2-氯-1-(4-(苯巯基)苯基)已酮(化合物Ⅰ-7-1-4)和200ml二氯甲烷的混合液,约2h滴加完毕,撤去冰盐水浴,自然恢复至室温,继续搅拌反应2~3h,TLC监控反应完全。加入亚硫酸氢钠,搅拌30min后加入200ml二氯甲烷萃和10%的盐酸,PH=3,分液,再用150ml二氯甲烷萃取水相,合并有机相,3×100ml水洗涤至中性后分液,无水MgSO4干燥,过滤,减压浓缩,重结晶后得到30g黄色固体,即为化合物Ⅰ-7-1-5,收率:76.7%。
4-(苯巯基)苯甲酰氯(化合物Ⅰ-7-1-6)的制备
三口烧瓶,加入二氯甲烷100ml、4-(苯巯基)苯甲酸21g(0.091mol)以及2滴DMF,搭上回流冷凝管、恒压滴液漏斗、干燥管及碱液尾气吸收装置,加热至回流,缓慢滴加11.2g(0.095mol)氯化亚砜及30ml二氯甲烷混合液,约0.5h滴加完毕,回流1h,减压浓缩,加入新鲜二氯甲烷100ml再次减压浓缩,得棕黄色油状液体26g,即为化合物Ⅰ-7-1-6。(与甲醇酯化后MS:m/z=244.3)
(E)-1-(3-苯甲酰基-2,4,6-三甲基苯基)-2-((4-(苯巯基)苯甲酰氧基)亚氨基)辛-1-酮(化合物Ⅰ-7-1)的制备
加入7.58g(0.02mol)化合物Ⅰ-7-1-3和50ml二氯甲烷,降温至0℃左右后加入2.37g(0.03mol)吡啶,控温滴加5.45g(0.022mol)化合物Ⅰ-7-1-6及20ml二氯甲烷,滴加完毕后自然升温反应3h,反应完毕,加入30ml H20,搅拌30min后分液,加入饱和NaHCO3溶液100ml洗至pH=10左右,水洗涤至中性,再加入2%稀盐酸调至pH=4左右,3×100ml水洗至中性,无水MgSO4干燥,过滤,减压浓缩得橙黄色极粘稠液体(近固体),乙醇重结晶得8.6g,收率73%,即为化合物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),如图5所示。
实施例3
正辛酰氯(Ⅰ-13-1-1)的制备
三口烧瓶,加入二氯甲烷200ml、正辛酸100g以及2滴DMF,搭上回流冷凝管、恒压滴液漏斗、干燥管及碱液尾气吸收装置,加热至回流,缓慢滴加165g氯化亚砜及30ml二氯甲烷混合液,约1h滴加完毕,回流2h,减压浓缩,加入
新鲜二氯甲烷100ml再次减压浓缩,得浅黄色溶液114g,即为化合物Ⅰ-13-1-1。
1-(3-苯甲酰基-2,4,6-三甲基苯基)辛-1-酮(Ⅰ-13-1-2)的制备
三口烧瓶,加入100g(0.45mol)3-苯甲酰基-2,4,6-三甲基苯和300ml二氯甲烷,冰盐水浴降温至-5℃,通氮气,加入65.3g(0.49mol)无水A1C13,加干燥管、回流冷凝管及尾气吸收,缓慢滴76.1g(0.47mol)的正辛酰氯和50ml二氯甲烷的混合液,控制温度在-5~5℃,约2h滴加完毕,撤去冰盐水浴,自然恢复至室温,继续搅拌反应2~3h,TLC监控反应完全。将反应物缓慢倒入200ml 10%的冰的稀盐酸中,搅拌30min后分液,100ml二氯甲烷萃取水相,合并有机相,3×100ml水洗涤,2%NaHCO3溶液调至中性后分液,100ml水洗1次,无水MgSO4干燥,过滤,减压浓缩,重结晶得棕黄色固体129g,即为化合物Ⅰ-13-1-2,产率82%。MS:m/z=350.22。
(E)-1-(3-苯甲酰基-2,4,6-三甲基苯基)-2-(羟亚氨基)辛-1-酮(Ⅰ-13-1-3)的制备
三口烧瓶,加入300ml氯化氢的四氢呋喃溶液(含29gHCl)和35.0g(0.1mol)化合物Ⅰ-13-1-2,室温搅拌溶解,室温下滴加150ml亚硝酸甲酯的四氢呋喃溶液(0.12mol),至反应完全后,减压浓缩,得橙红色油状液体44g,加入250ml二氯甲烷,3×100ml水洗涤,无水MgSO4干燥,过滤后减压浓缩,得红棕色油状液体36g,加入120ml石油醚,搅拌下加热溶解完全,缓慢降温至-5℃,析出棕红色固体,抽滤,石油醚洗滤饼,得棕红色固体20g,即为化合物Ⅰ-13-1-3,产率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)。
3-苯甲酰基-2,4,6-三甲基苯甲酰氯(化合物Ⅰ-13-1-4)的制备
三口烧瓶,加入二氯甲烷100ml、3-苯甲酰基-2,4,6-三甲基苯甲酸26.8g
(0.1mol)以及2滴DMF,搭上回流冷凝管、恒压滴液漏斗、干燥管及碱液尾气吸收装置,加热至回流,缓慢滴加36.9g(0.3mol)氯化亚砜及50ml二氯甲烷混合液,约1h滴加完毕,回流2h,减压浓缩,加入新鲜二氯甲烷100ml再次减压浓缩,得红棕色油状液体30g,即为化合物Ⅰ-13-1-4。
(E)-2-(3-苯甲酰基-2,4,6-三甲基苯甲酰亚氨酯基)-1-(3-苯甲酰基-2,4,6-三甲基苯基)辛-1-酮(化合物Ⅰ-13-1)的制备
加入7.8g(0.02mol)化合物Ⅰ-13-1-3和50ml二氯甲烷,降温至0℃左右后加入2.37g(0.03mol)吡啶,控温滴加6.29g(0.022mol)化合物Ⅰ-13-1-4及20ml二氯甲烷,滴加完毕后自然升温反应3h,反应完毕,加入30ml H20,搅拌30min后分液,加入饱和NaHCO3溶液100ml洗至pH=10左右,水洗涤至中性,再加入2%稀盐酸调至pH=4左右,3×100ml水洗至中性,无水MgSO4干燥,过滤,减压浓缩得浅黄色略带粘稠固体,乙醇重结晶得9.8g,收率78%,即为化合物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),如图6所示。
实施例4
正辛酰氯(化合物Ⅰ-4-1-1)的制备
三口烧瓶,加入二氯甲烷200ml、正辛酸100g以及2滴DMF,搭上回流冷凝管、恒压滴液漏斗、干燥管及碱液尾气吸收装置,加热至回流,缓慢滴加165g氯化亚砜及30ml二氯甲烷混合液,约1h滴加完毕,回流2h,减压浓缩,加入新鲜二氯甲烷100ml再次减压浓缩,得浅黄色溶液114g,即为化合物Ⅰ-4-1-1。
1-氯-4-辛酸酯基硫杂蒽酮(化合物Ⅰ-4-1-2)的制备
加入5.24g(0.02mol)化合物1-氯-4-羟基硫杂蒽酮和50ml二氯甲烷,降温至0℃左右后加入2.37g(0.03mol)吡啶,控温滴加3.56g(0.022mol)化合物Ⅰ-4-1-1及20ml二氯甲烷,滴加完毕后自然升温反应3h,TLC板跟踪至反应完毕,加入30ml H20,搅拌30min后分液,加入饱和NaHCO3溶液100ml洗至pH=10左右,水洗涤至中性,再加入2%稀盐酸调至pH=4左右,3×100ml水洗至中性,无水MgSO4干燥,过滤,减压浓缩得棕黄色固体,乙醇重结晶得6.5g,收率84%,即为化合物Ⅰ-4-1-2。
1-氯-4-(2-羟亚胺基)辛酸酯基硫杂蒽酮(Ⅰ-4-1-3)的制备
三口烧瓶,加入300ml氯化氢的四氢呋喃溶液(含29gHCl)和38.9g(0.1mol)化合物Ⅰ-4-1-2,室温搅拌溶解,室温下滴加150ml亚硝酸甲酯的四氢呋喃溶液(0.12mol),至反应完全后,减压浓缩,得橙红色油状液体49g,加入250ml二氯甲烷,3×100ml水洗涤,无水MgSO4干燥,过滤后减压浓缩,得红棕色油状液体41g,加入120ml石油醚,搅拌下加热溶解完全,缓慢降温至-5℃,析出棕土黄色固体,抽滤,石油醚洗滤饼,得土黄色固体26.7g,即为化合物Ⅰ-4-1-3,产率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=7.2Hz,1H),如图7所示。
3-苯甲酰基-2,4,6-三甲基苯甲酰氯(化合物Ⅰ-4-1-4)的制备
三口烧瓶,加入二氯甲烷100ml、3-苯甲酰基-2,4,6-三甲基苯甲酸26.8g(0.1mol)以及2滴DMF,搭上回流冷凝管、恒压滴液漏斗、干燥管及碱液尾气
吸收装置,加热至回流,缓慢滴加36.9g(0.3mol)氯化亚砜及50ml二氯甲烷混合液,约1h滴加完毕,回流2h,减压浓缩,加入新鲜二氯甲烷100ml再次减压浓缩,得红棕色油状液体30g,即为化合物Ⅰ-4-1-4。
(E)-1-氯-(2-(3-苯甲酰基-2,4,6-三甲基苯甲酰亚氨酯基))-4-辛酸酯基硫杂蒽酮(化合物Ⅰ-13-1)的制备
加入8.36g(0.02mol)化合物Ⅰ-4-1-3和50ml二氯甲烷,降温至0℃左右后加入2.37g(0.03mol)吡啶,控温滴加6.29g(0.022mol)化合物Ⅰ-4-1-4及20ml二氯甲烷,滴加完毕后自然升温反应3h,反应完毕,加入30ml H20,搅拌30min后分液,加入饱和NaHCO3溶液100ml洗至pH=10左右,水洗涤至中性,再加入2%稀盐酸调至pH=4左右,3×100ml水洗至中性,无水MgSO4干燥,过滤,减压浓缩得土黄色固体,乙醇重结晶得11.3g,收率85%,即为化合物Ⅰ-4-1。MP:140.76℃。
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),如图8所示。
应用实施例1
检测了化合物Ⅰ-2-1、Ⅰ-7-1、Ⅰ-13-1及Ⅰ-4-1在常用的有机溶剂,如乙酸乙酯、乙二醇单***、丙二醇甲醚、丙二醇甲醚醋酸酯中的溶解性。分别取四份等量的化合物Ⅰ-2-1、Ⅰ-7-1、Ⅰ-13-1及Ⅰ-4-1置于四个试样瓶中,分别用乙二醇单***、丙二醇甲醚醋酸酯溶解,通过TLC检测光引发剂在溶液中的稳定性。结果显示均具有一定的溶解性,且此类光引发剂在有机溶剂中的稳定性比较好,避光条件下在常用溶剂中均能保持20天以上不发生分解。
应用实施例2
利用差热-热重分析仪测定化合物Ⅰ-2-1、Ⅰ-7-1、Ⅰ-13-1及Ⅰ-4-1的热解性能。升温速度:10℃/min。检测了化合物Ⅰ-2-1、Ⅰ-7-1、Ⅰ-13-1及Ⅰ-4-1初始分解温度均在150℃以上,热稳定性较好。
应用实施例3
将化合物化合物Ⅰ-2-1,Ⅰ-7-1、Ⅰ-13-1及Ⅰ-4-1溶解在乙腈中,分别配成一定摩尔浓度的溶液,通过用紫外-可见分光光度计测其紫外吸收谱图,进行比较。通过检测谱图可以看出所合成的几种化合物紫外吸收谱带较宽泛,在300~365nm均有较大吸收,如图1,图9、图10、图11所示。
应用实施例4
利用实时红外测试手段,比较了实施例中化合物Ⅰ-2-1、Ⅰ-7-1、Ⅰ-13-1及Ⅰ-4-1引发甲基丙烯酸羟乙酯聚合的双键转化率。以丙酮为溶剂,配制化合物Ⅰ-2-1、Ⅰ-7-1、Ⅰ-13-1及Ⅰ-4-1的浓度为单体浓度的3%的试样,涂于KBr盐片上,然后放入Nico-let5700中,用紫外光点光源照射样品,调节样品表面的紫外光光强为30mW/cm2。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。甲基丙烯酸羟乙酯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)由数据处理软件结合下式计算得到。
DC(%)=[1-(At/Ao)]×100%
式中Ao和At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。检测结果显示化合物Ⅰ-2-1、Ⅰ-7-1、Ⅰ-13-1及Ⅰ-4-1均可以引发甲基丙烯酸羟乙酯聚合,在光照l0min之后,均能使丙烯酸双键的转化率达60%以上。
应用实施例5
用聚乙烯吡咯烷酮(MW=40000)与聚甲基丙烯酸酯树脂(Mn=50000)作成膜树脂,2-羟丁基丙烯酸酯作聚合单体,分别加入化合物Ⅰ-2-1、Ⅰ-7-1、Ⅰ-13-1及Ⅰ-4-1,加入适量的链转移剂和染料,用丙二醇甲醚作溶剂,配成自由基聚合成像感光胶液1、2、3、4。将以上胶液按以下方法进行性能测试。将感光胶液1~4用离心机旋涂在预先处理好的并满足下列条件的PS铝版基上,铝板基尺寸:1030mm×800mm;铝板基厚度:0.28~0.3mm;砂目规格:Ra=0.5~0.6μm,Rh=0.3~0.35μm;阳极氧化膜重量:3~3.5g/m2。控制离心涂布机的转速,使涂在铝版基上的涂布量(以固含量计)为0.5~2.5g/m2,在离心涂布机上初步干燥后,转移到100℃的鼓风干燥机中干燥3min,得紫激光CTP原版。将原版经紫激光曝光,用Ugra测试条做掩膜测试版材的感光性能。曝光后,用1%NaOH水溶液显影。曝光区,可光聚合化合物在引发剂存在下发生聚合反应,显影液中不溶,而非曝光区是可溶的,于是得到阴图。通过曝光显影,从得到的图像的的连续调梯尺评价感度,从微线条测试块区域评价精度,从而评价感光组合物感光性能的优劣。实验结果显示在曝光时间均为40s的情况下,化合物Ⅰ-2-1、Ⅰ-7-1、Ⅰ-13-1及Ⅰ-4-1的版材均能显到连续调梯尺的3段以上,精度在6μ以上。由此可见,化合物
Ⅰ-2-1、Ⅰ-7-1、Ⅰ-13-1及Ⅰ-4-1在一定曝光时间及曝光量下,能达到较好的成像效果,可适用于紫激光成像体系中。
以上所述,仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,虽然本发明已以较佳实施例揭露如上,然而并非用以限定本发明,任何熟悉本专业的技术人员,在不脱离本发明技术方案范围内,当可利用上述揭示的技术内容作出些许更动或修饰为等同变化的等效实施例,但凡是未脱离本发明技术方案内容,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均仍属于本发明技术方案的范围内。
Claims (10)
- 一种酰基肟酯类化合物,所述酰基肟酯类光化合物具有通式Ⅰ所示结构:其中,所述Y1、Y2及Y3相同或不同,各自独立地选自-H、-CH3、2-8个碳原子的烷基或烷氧基、3-8个碳原子的环烷基、2-8个碳原子的烯烃基;所述X‘和Y’相同或不同,各自独立地选自-S-、-S-S-、-O-、-CO-;上述R1和R4选择的取代基中,环状结构中一个或多个-H可以被-F、-Cl、-Br、-I、-NO2、-COOR′1、-CONR′2、-OR′3、1-8个碳原子的烷基或烷氧基或2-8个碳原子的烯烃基取代,其中R’1和R’2各自独立地选自-H、1-8个碳原子的烷基、3-8个碳原子的环烷基、2-8个碳原子的烯烃基,R’3选自-H、1-8个碳原子的烷基、3-8个碳原子的环烷基、2-8个碳原子的烯烃基或1-8个碳原子的碳链羰基,其中,1-8个碳原子的碳链羰基中羰基在端位,位于连接键处;所述R2选自-H、1-20个碳原子的烷基或烷氧基、3-8个碳原子的环烷基或2-20个碳原子的烯烃基;或者R2与R1所示基团相同;
- 根据权利要求1所述的酰基肟酯类化合物,其特征在于,所述R2选自-H、1-8个碳原子的烷基、烷氧基或2-8个碳原子的烯烃基或与R1所示基团相同。
- 根据权利要求1所述的酰基肟酯类化合物,其特征在于,所述Y1、Y2及Y3 相同或不同,各自独立地选自-H、-CH3、2-8个碳原子的烷基或烷氧基。
- 根据权利要求6所述的酰基肟酯类化合物,其特征在于,所述Y1、Y2及Y3相同或不同,各自独立地选自-H或-CH3。
- 一种通式Ⅰ所述的酰基肟酯类化合物的制备方法,包含如下步骤:a、中间体Ⅰ-A的合成:以苯、二苯硫醚或硫杂蒽酮为起始原料,与含有R2基团的酰卤化合物,在三氯化铁、三氯化铝或氯化锌作用下,通过付克酰基化反应,合成中间体Ⅰ-A:b、中间体Ⅰ-B的合成:中间体I在通有氯化氢或加盐酸的情况下与亚硝酸甲酯、***或亚硝酸异戊酯进行氧化反应,生成酰基肟中间体Ⅰ-B:c、酰基肟酯类光引发剂合成:中间体Ⅰ-B与含有M1结构的酰卤或酸酐,在吡啶或三乙胺缚酸剂存在下,在二氯甲烷、二氯乙烷或二氧六环溶剂下合成通式 Ⅰ的化合物。其中,所述R1和R4相同或不同,各自独立地选自 其中,所述R3选自-H、-NO2、1-8个碳原子的烷基或烷氧基、3-8个碳原子的环烷基、2-8个碳原子的烯烃基、所述Y1、Y2及Y3相同或不同,各自独立地选自-H、-CH3、2-8个碳原子的烷基或烷氧基、3-8个碳原子的环烷基、2-8个碳原子的烯烃基,所述X‘和Y’相同或不同,各自独立地选自-S-、-S-S-、-O-、-CO-;上述R1和R4选择的取代基中,环状结构中一个或多个-H可以被-F、-Cl、-Br、-I、-NO2、-COOR′1、-CONR′2、-OR′3、1-8个碳原子的烷基或烷氧基或2-8个碳原子的烯烃基取代,其中R’1和R’2各自独立地选自-H、1-8个碳原子的烷基、3-8个碳原子的环烷基、2-8个碳原子的烯烃基,R’3选自-H、1-8个碳原子的烷基、 3-8个碳原子的环烷基、2-8个碳原子的烯烃基或1-8个碳原子的碳链羰基,其中,1-8个碳原子的碳链羰基中羰基在端位,位于连接键处;所述的X为卤素;所述R2选自-H、1-8个碳原子的烷基或烷氧基、3-8个碳原子的环烷基或2-8个碳原子的烯烃基;或者R2与R1所示基团相同;
- 权利要求1-8中任一项所述酰基肟酯类化合物在UV光固化材料中的应用。
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KR20130055946A (ko) * | 2011-11-21 | 2013-05-29 | 동우 화인켐 주식회사 | 컬러필터 형성용 조성물 및 이로부터 제조되는 컬러필터 |
CN103809373A (zh) * | 2012-11-07 | 2014-05-21 | 奇美实业股份有限公司 | 感旋光性树脂组合物、其所形成的彩色滤光片及液晶显示装置 |
KR20140075449A (ko) * | 2012-12-11 | 2014-06-19 | 동우 화인켐 주식회사 | 잉크젯용 경화성 수지 조성물, 컬러필터 및 이를 구비한 화상표시장치 |
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CN110117262A (zh) * | 2019-04-30 | 2019-08-13 | 同济大学 | 2-苯乙烯基苯并恶唑或苯并噻唑基酮肟酯类化合物及其制备方法和应用 |
CN110117262B (zh) * | 2019-04-30 | 2023-04-11 | 同济大学 | 2-苯乙烯基苯并恶唑或苯并噻唑基酮肟酯类化合物及其制备方法和应用 |
CN114605380A (zh) * | 2022-04-12 | 2022-06-10 | 阜阳欣奕华材料科技有限公司 | 一种超支化大分子光引发剂及其制备方法和应用 |
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