CN103709036A - Novel bifunctional benzoyl formic acid hydroxy ketone ester compounds and photoinitiators containing the compounds - Google Patents
Novel bifunctional benzoyl formic acid hydroxy ketone ester compounds and photoinitiators containing the compounds Download PDFInfo
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- CN103709036A CN103709036A CN201310648695.XA CN201310648695A CN103709036A CN 103709036 A CN103709036 A CN 103709036A CN 201310648695 A CN201310648695 A CN 201310648695A CN 103709036 A CN103709036 A CN 103709036A
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- Prior art keywords
- formic acid
- compounds
- benzoyl
- ether
- formula
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 60
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 21
- VCURKOZLHQTIKD-UHFFFAOYSA-N OC(=O)O.C(C1=CC=CC=C1)(=O)C(=O)O Chemical compound OC(=O)O.C(C1=CC=CC=C1)(=O)C(=O)O VCURKOZLHQTIKD-UHFFFAOYSA-N 0.000 title abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 69
- -1 benzoyl formic acid hydroxyketone ester compound Chemical class 0.000 claims description 45
- 229910052736 halogen Inorganic materials 0.000 claims description 16
- FAQJJMHZNSSFSM-UHFFFAOYSA-N phenylglyoxylic acid Chemical compound OC(=O)C(=O)C1=CC=CC=C1 FAQJJMHZNSSFSM-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 230000032050 esterification Effects 0.000 claims description 11
- 238000005886 esterification reaction Methods 0.000 claims description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- VTESCYNPUGSWKG-UHFFFAOYSA-N (4-tert-butylphenyl)hydrazine;hydrochloride Chemical compound [Cl-].CC(C)(C)C1=CC=C(N[NH3+])C=C1 VTESCYNPUGSWKG-UHFFFAOYSA-N 0.000 claims description 8
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 claims description 7
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 7
- 238000005809 transesterification reaction Methods 0.000 claims description 6
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 150000001555 benzenes Chemical group 0.000 claims description 3
- 125000002837 carbocyclic group Chemical group 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 3
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 claims description 2
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical class OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 claims 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims 1
- 238000006266 etherification reaction Methods 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 125000001424 substituent group Chemical group 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 50
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 30
- 239000000047 product Substances 0.000 description 28
- 238000002360 preparation method Methods 0.000 description 26
- 238000001556 precipitation Methods 0.000 description 25
- 239000007791 liquid phase Substances 0.000 description 21
- 238000012544 monitoring process Methods 0.000 description 21
- 238000003756 stirring Methods 0.000 description 21
- 238000004809 thin layer chromatography Methods 0.000 description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 13
- 238000001035 drying Methods 0.000 description 13
- 238000009413 insulation Methods 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 12
- 241000720974 Protium Species 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 12
- 239000012074 organic phase Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 238000004128 high performance liquid chromatography Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000000543 intermediate Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000013019 agitation Methods 0.000 description 7
- 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 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000003480 eluent Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 235000015320 potassium carbonate Nutrition 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229960001866 silicon dioxide Drugs 0.000 description 6
- DTZKVZKYSZUBAG-UHFFFAOYSA-N 2-chloro-2-methylpropanoyl chloride Chemical compound CC(C)(Cl)C(Cl)=O DTZKVZKYSZUBAG-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 5
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 5
- 230000031709 bromination Effects 0.000 description 5
- 238000005893 bromination reaction Methods 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 5
- 125000005425 toluyl group Chemical group 0.000 description 5
- BNGOFPJWZUXKNR-UHFFFAOYSA-N 2-oxo-2-phenylacetyl chloride Chemical compound ClC(=O)C(=O)C1=CC=CC=C1 BNGOFPJWZUXKNR-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000012230 colorless oil Substances 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- WIDYZOXBOLTJJB-UHFFFAOYSA-N phenyl 2-oxo-2-phenylacetate Chemical compound C=1C=CC=CC=1C(=O)C(=O)OC1=CC=CC=C1 WIDYZOXBOLTJJB-UHFFFAOYSA-N 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 2
- FIOCEWASVZHBTK-UHFFFAOYSA-N 2-[2-(2-oxo-2-phenylacetyl)oxyethoxy]ethyl 2-oxo-2-phenylacetate Chemical compound C=1C=CC=CC=1C(=O)C(=O)OCCOCCOC(=O)C(=O)C1=CC=CC=C1 FIOCEWASVZHBTK-UHFFFAOYSA-N 0.000 description 2
- 125000003816 2-hydroxybenzoyl group Chemical group OC1=C(C(=O)*)C=CC=C1 0.000 description 2
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229940043232 butyl acetate Drugs 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 125000006331 halo benzoyl group Chemical group 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 2
- 229940057847 polyethylene glycol 600 Drugs 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- JMCWGWFQDBATEA-UHFFFAOYSA-N C(=O)Cl.C1(=CC=CC=C1)C(C(=O)O)=O Chemical compound C(=O)Cl.C1(=CC=CC=C1)C(C(=O)O)=O JMCWGWFQDBATEA-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical class C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- GJQBHOAJJGIPRH-UHFFFAOYSA-N benzoyl cyanide Chemical compound N#CC(=O)C1=CC=CC=C1 GJQBHOAJJGIPRH-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/04—End-capping
Abstract
The invention relates to a class of novel bifunctional benzoyl formic acid hydroxy ketone ester compounds and photoinitiators containing the compounds. The general formula I and II of the compounds are shown in the specification, wherein n is 0-90, R1 and R2 are selected from hydrogen, alkane or aryl groups with C1-C12 straight chains or branched chains and cyclic structures containing C5-C12 carbocycles, Ar is selected from phenyl rings or substituted phenyl rings wherein the substituent is one or more R, OR and halogen atom, and R is selected from alkyl, phenyl ring or benzyl with C1-C12 straight chains or branched chains. The compounds are suitable as photoinitiators of olefinic unsaturated compounds or mixtures containing the compounds for photopolymerization. The compounds can also be used with combination of another photoinitiator and/or other additives.
Description
Technical field
The present invention describes the preparation method of series of new bifunctional benzoyl formic acid hydroxyl ketone ester class aromatic ketone compounds and this compounds and the light trigger that comprises this compounds that is used as alefinically unsaturated compounds system photopolymerization reaction.
Background technology
Benzoyl formate compounds and alpha-hydroxy ketones are the known efficient not free radical photo-initiations of xanthochromia of two classes, and there are some compounds to realize commercialization: methyl benzoylformate (Darocur MBF), hydroxyphenyl acetic acid-2-(2-oxygen base-2-phenyl-acetic acid base-oxyethyl group)-ethyl ester and hydroxyphenyl acetic acid-2-(2-oxygen base-2-oxyethyl group)-ethyl ester mixture (Irgacure754), 2-hydroxy-2-methyl-1-phenyl-acetone (Darocur1173), 1-hydroxy-cyclohexyl phenyl ketone (Irgacure184), 2-hydroxyl-4 '-(2-hydroxy ethoxy)-2-methyl phenyl ketone (Irgacure2959).
Irgacure754 is Ciba company on to the basis of benzoyl formic acid structural modification, is in succession proposing following structure A(CN1157359) and structure B(CN1307207) basis on the light trigger of the more excellent performance just released.And to the photochemistry mechanism of this photoinitiator study also comparison system (J.Org.Chem.1997,62:7827, J.Photochem.Photobio.A.Chem.1998,118:75, Macromolecules, 2000,33:4030).
The alpha-hydroxy ketones of simple function group is disclosed (EP0003002) by vapour Bagong department very early, releases again on this basis that activity is higher, the better Irgacure127 of performance.Bifunctional alpha-hydroxy ketones (CN1582267, CN101812142), polyfunctional alpha-alcohol ketone compounds (CN103073658) and macromole class bifunctional alpha-hydroxy ketones (CN102020726), macromole class polyfunctional alpha-alcohol ketone compounds (CN101333263) are also disclosed successively.
Shenzhen promising chemical technology company limited will obtain two or trifunctional benzoyl formic acid hydroxyketone lipoid substance structure C and structure D(CN201010112324.6 together with the structure composite of benzoyl formate compounds and alpha-hydroxy ketones first), this compounds can be used as alefinically unsaturated compounds or containing the light trigger of the light polymerization of the mixture of this compounds.
If we find benzoyl formate class chemical combination and alpha-hydroxy ketones to form composite structure; and in molecule, retain benzoyl formate and the original functional group of alpha-hydroxy ketones simultaneously; the compound obtaining has good light-cured performance, and this compounds is not also in the news.This compounds not only can overcome compound before shortcoming separately, after compound, can also keep even surpassing original activity, and the obvious increase of compound rear molecular weight overcome again the shortcomings such as small molecules volatility, scent of, transport property, there is preferably the prospect as the light trigger of alefinically unsaturated compounds system photopolymerization reaction.
Summary of the invention
The invention provides a kind of novel bifunctional benzoyl formic acid hydroxyketone ester compound and as the light trigger that comprises this compounds of alefinically unsaturated compounds system photopolymerization reaction, its comprise in the compound that following formula I and II represent one of at least or the arbitrary composition that forms of the compound that represents of following formula I and II:
Wherein,
n=0-90；
R
1and R
2be selected from hydrogen, C
1-C
12the alkane of straight or branched or aryl, contain C
5-C
12the ring texture of carbocyclic ring;
Ar is selected from phenyl ring, substituted benzene ring, and wherein substituting group is herein one or more R, OR, halogen atom, and R is selected from C
1-C
12the alkyl of straight or branched, phenyl ring or benzyl.
The novel bifunctional benzoyl of formula I of the present invention formic acid hydroxyketone ester compound, is characterized in that: n=0-90, R
1and R
2be selected from methyl, cyclohexyl.
The novel bifunctional benzoyl of formula I of the present invention formic acid hydroxyketone ester compound, is characterized in that: n=1-90, R
1and R
2be selected from methyl.
The novel bifunctional benzoyl of formula I of the present invention formic acid hydroxyketone ester compound, is characterized in that: n=1, R
1and R
2be selected from methyl, cyclohexyl.
The novel bifunctional benzoyl of general formula II of the present invention formic acid hydroxyketone ester compound, is characterized in that: n=0.
Compound formula I provided by the invention and II can be used as alefinically unsaturated compounds or contain the light trigger of the mixed light polymerization of this compounds, and these compounds also can mix with another one or more light trigger use.
Formula I and II compound are including, but not limited to following exemplary configurations:
The invention provides the method for preparing I-II formula compound, can conveniently by esterification or transesterify, prepare, also can prepare by esterification, acylations, hydrolysis.Many benzoyl formic acid compounds (formula III) or the benzoyl formate compounds (formula IV) that the present invention relates to can have been bought from market, also can be by the conveniently preparation of method of bibliographical information, as chemical intermediate [J], 2010,04:49-54 is disclosed take benzoyl nitrile as raw material, adopt " one kettle way " synthetic, under the vitriol oil and catalyst action, reaction obtains intermediate product formula III; Synthesis[J], 2012,44:238-289 discloses take various substituted acetophenones as raw material, reacts conveniently obtain various benzoyl formate compounds after two bromo-reactions with correspondent alcohol.
Wherein R ' is selected from C
1-C
12the alkyl of straight or branched, phenyl ring or benzyl; Ar defines as above-mentioned.
The invention provides the method for preparing compound (formula I and II) can obtain by benzoyl formic acid compounds (formula III) or benzoyl formate compounds (formula IV) and 'alpha '-hydroxylation compound (formula V or VI) esterification or transesterification reaction under acid catalysis.Compound V part can have been bought from market, also can the disclosed preparation method of referenced patent CN201210311169.X.
N=0-90 wherein, Ar, R ', R
1, R
2as above-mentioned, define, R ' is preferably methyl, ethyl.
The invention provides prepare the method for compound (formula I and II) can also be by structure III or IV and hydroxyl; ether (formula VII or VIII) carries out esterification or transesterification reaction obtains ester compound; then react then and react and obtain halo benzoyl formate ketone compounds intermediate at carbonyl alpha-position halo or with alpha-halogen acyl chlorides (formula IX) with acyl chlorides (formula X), intermediate is hydrolyzed and can obtains target product.Compound IX can easily be prepared (Chinese patent CN201110139077.3).
N=0-90 wherein, X=Cl, Br, Ar, R ', R
1, R
2as above-mentioned, define, R ' is preferably methyl, ethyl.
The invention provides prepare compound (formula I and II) method can also by structure III or IV and polyoxyethylene glycol (formula XI) carries out esterification or transesterification reaction obtains ester compound, the hydroxy ester compounds obtaining reacts with phosphorus pentachloride or thionyl chloride or reacts with methylsulfonyl chloride or react with Tosyl chloride (PTSC) intermediate preparing is respectively E
1, E
2, E
3, then reacting with phenol or diphenyl-carbinol and obtain ether-ether compounds intermediate, intermediate reacts and obtains halo benzoyl formate ketone compounds intermediate with alpha-halogen acyl chlorides (formula IX), and halogenated intermediates is hydrolyzed and can obtains target product.
N=1-90 wherein, Ar, R ', R
1, R
2as above-mentioned, define, R ' is preferably methyl, ethyl.When n=0, benzoyl formic acid or benzoyl formate and phenol or diphenyl-carbinol carry out esterification or transesterify, obtain ether-ether compounds; Ether-ether compounds reacts and prepares alpha-halogen midbody compound with alpha-halogen acyl chlorides (formula IX) again; Alpha-halogen midbody compound is hydrolyzed to react and obtains target product under alkaline condition.
According to the present invention, at alefinically unsaturated compounds or comprise that in the photopolymerization of mixture of this compounds, the compound of formula I and II can be used as light trigger.Can use separately one or more also can be combined with other kind of photoinitiator and (or) other additive.
The present invention relates to photopolymerisable compositions, said composition comprises:
(a) the unsaturated photopolymerization compound of at least one olefinic and,
(b) as light trigger, the compound of at least one formula I or II,
Except component (b), composition also can comprise other light trigger and (or) other additive.
Specific embodiment:
In order to be illustrated more clearly in the present invention, hereinafter take indefiniteness embodiment to further illustrate.
Embodiment 1:4-(2-hydroxy-2-methyl propionyl) preparation of phenyl benzoyl formiate (compound 1)
By 2-hydroxy-2-methyl-1-(4-hydroxy phenyl)-1-acetone (22.5g, 0.125mol) be dissolved in 50ml methylene dichloride, add triethylamine (19.0g, 0.188mol), under agitation condition, be heated to 60 ℃, drip methyl benzoylformate (20.5g, 0.125mol), drip complete insulation reaction, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, be down to room temperature, with equal-volume washing, dry, precipitation, after gained resistates dissolves with methylene dichloride, on silicagel column, by petrol ether/ethyl acetate, be that eluent is purified and obtained light yellow product.
Ultimate analysis: molecular formula C
18h
16o
5
Theoretical content: carbon element content 69.22%; Protium content 5.16%
Actual measurement content: carbon element content 69.11%; Protium content 5.18%
Embodiment 2:4-(2-hydroxy-2-methyl propionyl) preparation of phenyl benzoyl formiate (compound 1)
1) preparation of benzoyl formyl chloride
Benzoyl formic acid (30.0g, 0.2mol) and 50ml thionyl chloride are joined in reaction vessel, and stirring and refluxing reaction, reclaims excessive thionyl chloride after 2h, and remaining raffinate can be by underpressure distillation directly next step reaction that proposes also can not purify.
2) preparation of benzoyl formic acid phenyl ester
The above-mentioned benzoyl formyl chloride without purifying preparing is dissolved in the methylene dichloride of 120ml, adds phenol (20.6g, 0.22mol) and 30ml triethylamine stirring reaction at ambient temperature, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, add equal-volume water washing, separate organic phase, with anhydrous sodium sulfate drying, precipitation, underpressure distillation (3mmHg), the cut while collecting 145 ℃, obtain 40.7g benzoyl formic acid phenyl ester, yield 90%.
3) the 4-(2-chloro-2-methyl propionyl) preparation of phenyl benzoyl formiate
100mL methylene dichloride is cooled to 5 ℃ with ice-water bath, add 16.8g(0.126mol) aluminum chloride, slowly add 16.0g(0.113mol) 2-chloro-2-methyl propionyl chloride 20min, slowly drip 20.6g(0.091mol) benzoyl formic acid phenyl ester (being dissolved in 20ml methylene dichloride) 30min.Be heated to 50 ℃, stir 3h.Reaction solution is cooled to 20 ℃, joins in the technical hydrochloric acid of 120mL10% and stir 1h.Standing, branch vibration layer, organic phase is washed with water to neutrality, anhydrous sodium sulfate drying, precipitation, obtains 4-(2-chloro-2-methyl propionyl) phenyl benzoyl formiate 27.2g, yield 90.3%, purity 95.5%.
4) the 4-(2-hydroxy-2-methyl propionyl) preparation of phenyl benzoyl formiate
By 16.5g(0.05mol) 4-(2-chloro-2-methyl propionyl) phenyl benzoyl formiate, 6.5g sodium formiate and 70ml acetonitrile join in reaction vessel, keep 5 ℃ of mixture temperatures, under agitation condition, add again 0.2g tertiary butyl bromination ammonium, 9.5g sodium bicarbonate, 60ml water, then be warmed up to 60 ℃, insulation reaction 20h left and right, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, be down to room temperature, separate acetonitrile phase, washing precipitation, after gained resistates dissolves with methylene dichloride, on silicagel column, by petrol ether/ethyl acetate, be that eluent is purified and obtained light yellow product.
Ultimate analysis: molecular formula C
18h
16o
5
Theoretical content: carbon element content 69.22%; Protium content 5.16%
Actual measurement content: carbon element content 69.41%; Protium content 5.23%
Embodiment 3:2-(4-(2-hydroxy-2-methyl propionyl) phenoxy group) preparation of ethylbenzoyl manthanoate (compound 2)
Methyl benzoylformate (16.4g, 0.1mol) is dissolved in 50ml toluene, adds pyridine (15.8g, 0.2mol), under agitation condition, be heated to 70 ℃, add Irgacure2959(22.4g, 0.1mol), drip complete insulation reaction 20h left and right, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, be cooled to room temperature, with equal-volume washing, dry, precipitation, after gained resistates dissolves with methylene dichloride, on silicagel column, by petrol ether/ethyl acetate, be that eluent is purified and obtained light yellow product.
Ultimate analysis: molecular formula C
20h
20o
6
Theoretical content: carbon element content 67.41%; Protium content 5.66%
Actual measurement content: carbon element content 67.23%; Protium content 5.60%
Embodiment 4:2-(4-(2-hydroxy-2-methyl propionyl) phenoxy group) preparation of ethylbenzoyl manthanoate (compound 2)
1) preparation of 2-phenoxyethyl alcohol
By phenol (94.0g, 1.0mol), ethylene chlorhydrin (322.0g, 4.0mol), salt of wormwood (276.0g, 2.0mol) join in 2000ml reaction flask with 800ml ethanol, stir and be heated to 70 ℃, insulation reaction 16h left and right, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, be cooled to room temperature, filter unreacted salt of wormwood, filtrate precipitation, 2000ml methylene dichloride dilution for residue, 1000ml washing, with anhydrous sodium sulfate drying, precipitation, underpressure distillation is purified, collect 100-105 ℃ (4mmHg), obtain colorless oil 127.0g, yield 92.0%, purity 99.2%.
2) preparation of 2-phenoxy group ethylbenzoyl manthanoate
By methyl benzoylformate (16.4g, 0.1mol), 2-phenoxyethyl alcohol (13.8g, 0.1mol), 0.26g Lithium Acetate and 50ml methylene dichloride join in 250ml reaction flask, be stirred and heated to 60 ℃, insulation reaction, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, slough the methyl alcohol that solvent and reaction produce, in residue, add 50ml water, with 100ml toluene extraction 2 times, merge organic phase, with anhydrous sodium sulfate drying, precipitation had both obtained product, by NMR spectrogram and HPLC, confirmed structure.
3) the 2-(4-(2-chloro-2-methyl propionyl) phenoxy group) preparation of ethylbenzoyl manthanoate
100mL methylene dichloride is cooled to 5 ℃ with ice-water bath, add 16.8g(0.126mol) aluminum chloride, slowly add 16.0g(0.113mol) 2-chloro-2-methyl propionyl chloride 20min, slowly drip 24.6g(0.091mol) 2-phenoxy group ethylbenzoyl manthanoate (being dissolved in 20ml methylene dichloride) 30min.Be heated to 50 ℃, stirring reaction, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, is cooled to 20 ℃ by reaction solution, joins in the technical hydrochloric acid of 120mL10% and stirs 1h.Standing, branch vibration layer, organic phase is with being washed with water to respectively neutrality, anhydrous sodium sulfate drying, precipitation, obtains 2-(4-(2-chloro-2-methyl propionyl) phenoxy group) ethylbenzoyl manthanoate, by NMR spectrogram and HPLC, confirm structure.
4) the 2-(4-(2-hydroxy-2-methyl propionyl) phenoxy group) preparation of ethylbenzoyl manthanoate
By 18.7g(0.05mol) 2-(4-(2-chloro-2-methyl propionyl) phenoxy group) ethylbenzoyl manthanoate, 6.5g sodium formiate and 70ml acetonitrile join in reaction vessel, keep 5 ℃ of mixture temperatures, under agitation condition, add again 0.2g tertiary butyl bromination ammonium, 9.5g sodium bicarbonate, 60ml water, then be warmed up to 60 ℃, insulation reaction 20h, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, be down to room temperature, separate acetonitrile phase, washing precipitation, after gained resistates dissolves with methylene dichloride, on silicagel column, by petrol ether/ethyl acetate, be that eluent is purified and obtained light yellow product, by NMR spectrogram and HPLC, confirm structure.
Ultimate analysis: molecular formula C
20h
20o
6
Theoretical content: carbon element content 67.41%; Protium content 5.66%
Actual measurement content: carbon element content 67.37%; Protium content 5.69%
Embodiment 5:
1) take Tetraglycol 99 as raw material preparation
By Tetraglycol 99 (38.8g, 0.2mol) be dissolved in 80ml pyridine, stir and be cooled to 10 ℃, slowly drip benzoyl formyl chloride (33.8g, 0.2mol), 40min drips complete, and then mixing solutions rises to room temperature, at room temperature stirring reaction 4h left and right, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, reaction solution is poured in 200g frozen water, used CHCl
3(3*100ml) extraction, merge organic phase, with HCl and the saturated sodium hydrogen carbonate solution of 100ml of 100ml6mol/L, wash respectively, organic phase anhydrous sodium sulfate drying, precipitation, after gained resistates dissolves with methylene dichloride, is that eluent is purified and obtained colorless oil product 43.1g by ethyl acetate on silicagel column, this product is confirmed structure by NMR spectrogram and HPLC, and structure is
Get the above-mentioned (2-hydroxybenzoyl) manthanoate (16.3g making, 0.05mol) be dissolved in 30ml methylene dichloride, drip phosphorus trichloride (2.3g, 0.02mol), be stirred and heated to 40 ℃, insulation reaction 3h left and right, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, with the extraction of 3*20ml toluene, precipitation obtains chloro benzoyl formiate 16.0g(liquid content 93%).
By phenol (16.9g, 0.18mol), chloro benzoyl formiate (20.3g, 0.046mol), salt of wormwood (49.8g, 0.36mol) join in 250ml reaction flask with 120ml ethanol, stir and be heated to 70 ℃, insulation reaction 16h left and right, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, be cooled to room temperature, filter unreacted salt of wormwood, filtrate precipitation, 120ml methylene dichloride dilution for residue, 120ml washing, with anhydrous sodium sulfate drying, precipitation obtains product 17.6g, this product is confirmed structure by NMR spectrogram and HPLC, and structure is
120mL methylene dichloride is cooled to 5 ℃ with ice-water bath, add 7.6g(0.057mol) aluminum chloride, slowly add 7.3g(0.052mol) 2-chloro-2-methyl propionyl chloride 20min, slowly drip 17.3g(0.043mol) benzoyl formiate (being dissolved in the 20ml methylene dichloride) 30min of above-mentioned preparation.Be heated to 50 ℃, stirring reaction, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, is cooled to 20 ℃ by reaction solution, joins in the technical hydrochloric acid of 100mL10% and stirs 1h.Standing, branch vibration layer, organic phase is washed with water to neutrality, anhydrous sodium sulfate drying, precipitation, obtains product 20.7g, and this product is confirmed structure by NMR spectrogram and HPLC, and structure is
By 19.8g(0.039mol) the above-mentioned alpha-chloro product making, 5.1g sodium formiate and 60ml acetonitrile join in reaction vessel, keep 5 ℃ of mixture temperatures, under agitation condition, add again 0.2g tertiary butyl bromination ammonium, 7.4g sodium bicarbonate, 50ml water, be then warmed up to 60 ℃, insulation reaction 20h, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, be down to room temperature, separate acetonitrile phase, washing precipitation, obtain light yellow product, structure is that this product is confirmed structure by NMR spectrogram and HPLC.
Ultimate analysis: molecular formula C
26h
32o
9
Theoretical content: carbon element content 63.92%; Protium content 6.60%
Actual measurement content: carbon element content 63.89%; Protium content 6.63%
Structure is:
(compound 3).
2) take Polyethylene Glycol-600 as raw material preparation
By Polyethylene Glycol-600 (60g, 0.1mol) be dissolved in 40ml pyridine, stir and be cooled to 10 ℃, slowly drip benzoyl formyl chloride (16.9g, 0.1mol), 40min drips complete, and then mixing solutions rises to room temperature, at room temperature stirring reaction 4h left and right, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, reaction solution is poured in 100g frozen water, used CHCl
3(3*50ml) extraction, merges organic phase, with HCl and the saturated sodium hydrogen carbonate solution of 50ml of 80ml6mol/L, washes respectively, and organic phase anhydrous sodium sulfate drying, precipitation, obtains colorless oil product 43.9g, and the molecular-weight average of this product is 732, and structure is
N(mean value)=13.2
Get the above-mentioned (2-hydroxybenzoyl) manthanoate (22.0g making, 0.03mol) be dissolved in 30ml methylene dichloride, drip phosphorus trichloride (1.4g, 0.01mol), be stirred and heated to 40 ℃, insulation reaction 3h left and right, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, with the extraction of 3*20ml toluene, precipitation obtains chloro benzoyl formiate 20.3g.
By phenol (10.3g, 0.11mol), the above-mentioned chloro benzoyl formiate (20.3g making, 0.027mol), salt of wormwood (30.4g, 0.22mol) join in 250ml reaction flask with 60ml ethanol, stir and be heated to 70 ℃, insulation reaction 16h left and right, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, be cooled to room temperature, filter unreacted salt of wormwood, filtrate precipitation, 60ml methylene dichloride dilution for residue, 60ml washing, with anhydrous sodium sulfate drying, precipitation obtains product 20.1g, product molecular-weight average is 808, and structure is
N(mean value)=13.2
60mL methylene dichloride is cooled to 5 ℃ with ice-water bath, add 4.5g(0.034mol) aluminum chloride, slowly add 4.4g(0.031mol) 2-chloro-2-methyl propionyl chloride 20min, slowly drip 20.1g(0.025mol) 2-phenoxy group ethylbenzoyl manthanoate (being dissolved in 20ml methylene dichloride) 30min.Be heated to 50 ℃, stirring reaction, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, is cooled to 20 ℃ by reaction solution, joins in the technical hydrochloric acid of 70mL10% and stirs 1h.Standing, branch vibration layer, organic phase is washed with water to neutrality, anhydrous sodium sulfate drying, precipitation, obtains product 21.5g, and product molecular-weight average is 912.5, and structure is
N(mean value)=13.2
By 20.1g(0.022mol) the above-mentioned alpha-chloro product making, 2.9g sodium formiate and 40ml acetonitrile join in reaction vessel, keep 5 ℃ of mixture temperatures, under agitation condition, add again 0.2g tertiary butyl bromination ammonium, 4.2g sodium bicarbonate, 35ml water, be then warmed up to 60 ℃, insulation reaction 20h, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, be down to room temperature, separate acetonitrile phase, washing precipitation, obtain light yellow product, product molecular-weight average is 894, and structure is
N(mean value)=13.2
(compound 4).
Embodiment 6: the preparation of two [4-(2-hydroxy-2-methyl propionyl) phenyl] toluyl manthanoate (compound 5)
1) preparation of diphenyl methyl benzoyl formiate
Benzoyl formic acid formyl chloride (the 33.7g preparing by embodiment 2 methods, 0.2mol) be dissolved in the methylene dichloride of 120ml, add diphenyl-carbinol (40.5g, 0.22mol) and 30ml triethylamine stirring reaction at ambient temperature, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, add equal-volume water washing, separate organic phase, with anhydrous sodium sulfate drying, precipitation had both obtained product, by NMR spectrogram and HPLC, confirmed structure.
2) preparation of two [4-(2-chloro-2-methyl propionyl) phenyl] toluyl manthanoate
100mL methylene dichloride is cooled to 5 ℃ with ice-water bath, add 16.8g(0.126mol) aluminum chloride, slowly add 16.0g(0.113mol) 2-chloro-2-methyl propionyl chloride 20min, slowly drip 28.8g(0.091mol) diphenyl methyl-2-oxygen base benzoyl formiate (being dissolved in 20ml methylene dichloride) 30min.Be heated to 50 ℃, stirring reaction, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, is cooled to 20 ℃ by reaction solution, joins in the technical hydrochloric acid of 120mL10% and stirs 1h.Standing, branch vibration layer, organic phase is washed with water to neutrality, anhydrous sodium sulfate drying, precipitation, obtains two [4-(2-chloro-2-methyl propionyl) phenyl] toluyl manthanoate, by NMR spectrogram and HPLC, confirms structure.
3) preparation of two [4-(2-hydroxy-2-methyl propionyl) phenyl] toluyl manthanoate
By 26.3g(0.05mol) two [4-(2-chloro-2-methyl propionyl) phenyl] toluyl manthanoate, 6.5g sodium formiate and 70ml acetonitrile join in reaction vessel, keep 5 ℃ of mixture temperatures, under agitation condition, add again 0.2g tertiary butyl bromination ammonium, 9.5g sodium bicarbonate, 60ml water, then be warmed up to 60 ℃, insulation reaction 20h, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, be down to room temperature, separate acetonitrile phase, washing precipitation, after gained resistates dissolves with methylene dichloride, on silicagel column, by petrol ether/ethyl acetate, be that eluent is purified and obtained light yellow product, by NMR spectrogram and HPLC, confirm structure.
Ultimate analysis: molecular formula C
29h
28o
7
Theoretical content: carbon element content 71.30%; Protium content 5.78%
Actual measurement content: carbon element content 71.37%; Protium content 5.70%
Embodiment 7-11:
The following preparation of Preparation Example 7-11:
The polyacrylic ester of component A:11.38 part hydroxyl is 70% in butylacetate
21.23 parts of pentaerythritol triacrylates are 75% in butylacetate
0.55 part of trolamine
32.03 part methyl alcohol
B component: containing the urethane acrylate (with providing in scale 1) of isocyanate groups
The light trigger that will test with the concentration shown in table 1 under stirring joins component A, then adds B component, after mixing, with squeegee, on sheet glass, films, and then under room temperature, steams solvent, and the curing of film irradiated with standard mercury(vapor)lamp.Get 20cm
2the above-mentioned sheet glass that is prepared into, puts into watch-glass, adds 1 gram of gac, and the baking oven of putting into 120 ℃ heats 20 minutes, cooling, removes sample, with tetrahydrofuran (THF), extracts gac, and the light trigger being prepared into the quantitative embodiment of high performance liquid chromatography, the results are shown in Table 1.
The volatile research of light trigger prepared by table 1 embodiment
| Embodiment | 7 | 8 | 9 | 10 | 11 |
| Component A | 65.19 | 65.19 | 65.19 | 65.19 | 65.19 |
| B component | 31.07 | 31.07 | 31.07 | 31.07 | 31.07 |
| Compound 1 light trigger | 3.00 | ? | ? | ? | ? |
| Compound 2 light triggers | ? | 1.55 | ? | ? | ? |
| Compound 3 light triggers | ? | ? | 2.05 | ? | ? |
| Compound 4 light triggers | ? | ? | ? | 2.00 | ? |
| Compound 5 light triggers | ? | ? | ? | ? | 1.66 |
| Volatility (mg/m 2） | 0.01 | 0 | 0 | 0 | 0 |
The result of table 1 shows that all samples light trigger in heat-processed seldom or not overflows from preparation.
The light trigger that method prepares above experimental results show that through photocuring reaction; all there is good Photoinitiation Property; but also there is low volatility, low migration, low smell, the advantage such as xanthochromia not, can be used as the novel bifunctional benzoyl of class formic acid hydroxyketone ester lightlike initiating agent and be applied in industrial production.
Claims (10)
1. a novel bifunctional benzoyl formic acid hydroxyketone ester compound, is characterized in that: logical formula I is expressed as:
Wherein:
n=0-90；
R
1and R
2be selected from hydrogen, C
1-C
12the alkane of straight or branched or aryl, contain C
5-C
12the ring texture of carbocyclic ring;
Ar is selected from phenyl ring, substituted benzene ring, and wherein substituting group is herein one or more R, OR, halogen atom, and R is selected from C
1-C
12the alkyl of straight or branched, phenyl ring or benzyl.
2. a novel bifunctional benzoyl formic acid hydroxyketone ester compound, is characterized in that: logical formula I is expressed as:
Wherein:
n=0-90；
Ar is selected from phenyl ring, substituted benzene ring, and wherein substituting group is herein one or more R, OR, halogen atom, and R is selected from C
1-C
12the alkyl of straight or branched, phenyl ring or benzyl.
3. novel bifunctional benzoyl formic acid hydroxyketone ester compound according to claim 1, is characterized in that: n=0-90, R
1and R
2be selected from methyl, cyclohexyl.
4. novel bifunctional benzoyl formic acid hydroxyketone ester compound according to claim 1, is characterized in that: n=1-90, R
1and R
2be selected from methyl.
5. novel bifunctional benzoyl formic acid hydroxyketone ester compound according to claim 1, is characterized in that: n=1, R
1and R
2be selected from methyl, cyclohexyl.
6. novel bifunctional benzoyl formic acid hydroxyketone ester compound according to claim 2, is characterized in that: n=0.
7. a method of preparing novel bifunctional benzoyl formic acid hydroxyketone ester compound, the method: directly by benzoyl formic acid or benzoyl formate and formula V or VI is carried out esterification or prepared by transesterification reaction,
Wherein:
n=0-90；
R
1and R
2be selected from hydrogen, C
1-C
12the alkane of straight or branched or aryl, contain C
5-C
12the ring texture of carbocyclic ring.
8. a method of preparing novel bifunctional benzoyl formic acid hydroxyketone ester compound, the method comprises the following steps:
(a) by benzoyl formic acid or benzoyl formate and formula XI is carried out esterification or transesterification reaction is prepared hydroxy ester;
(b) obtain hydroxy ester and react with phosphorus trichloride or sulfur oxychloride, react with methylsulfonyl chloride or react with Tosyl chloride and prepare chloro ester or sulphonate, then react and prepare ether-ether compounds with phenol or diphenyl-carbinol;
(c) ether-ether compounds obtained above reacts and prepares alpha-halogen midbody compound with alpha-halogen acyl chlorides (formula IX) again;
(d) alpha-halogen midbody compound is hydrolyzed to react and obtains target product under alkaline condition;
When n=0, by benzoyl formic acid or benzoyl formate and phenol or diphenyl-carbinol, carry out esterification or transesterify, obtain ether-ether compounds; Ether-ether compounds reacts and prepares alpha-halogen midbody compound with alpha-halogen acyl chlorides (formula IX) again; Alpha-halogen midbody compound is hydrolyzed to react and obtains target product under alkaline condition.
9. a method of preparing novel bifunctional benzoyl formic acid hydroxyketone ester compound, the method comprises the following steps:
(a) by phenol or diphenyl-carbinol and formula XI, carry out etherification reaction and obtain hydroxy ethers compounds;
(b) benzoyl formic acid or benzoyl formate and hydroxy ethers compounds carry out esterification or transesterification reaction, obtain ether-ether compounds;
(c) ether-ether compounds reacts and prepares alpha-halogen midbody compound with alpha-halogen acyl chlorides (formula IX);
(d) alpha-halogen midbody compound is hydrolyzed to react and obtains target product under alkaline condition;
When n=0, directly by phenol or diphenyl-carbinol and benzoyl formic acid or benzoyl formate, carry out esterification or transesterify, obtain ether-ether compounds; Ether-ether compounds reacts and prepares alpha-halogen midbody compound with alpha-halogen acyl chlorides (formula IX); The reaction that is finally hydrolyzed under alkaline condition obtains target product.
10. a photopolymerisable compositions, comprising:
(a) the unsaturated photopolymerization compound of at least one olefinic;
(b) as at least one of photoinitiator according to the formula I of claim 1 or II compound.
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| CN104292445A (en) * | 2014-09-03 | 2015-01-21 | 山东久日化学科技有限公司 | Preparation method for macromolecular p-dimethylamino benzoate compound |
| JP2015536923A (en) * | 2012-10-19 | 2015-12-24 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Hybrid photoinitiator |
| CN105885028A (en) * | 2016-06-17 | 2016-08-24 | 华东理工大学 | Polyether alcohol ester compound and application thereof |
| CN108947803A (en) * | 2018-03-19 | 2018-12-07 | 山东润博生物科技有限公司 | A kind of preparation method of phenoxy carboxylic acid substance |
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| JP2015536923A (en) * | 2012-10-19 | 2015-12-24 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Hybrid photoinitiator |
| US9701762B2 (en) | 2012-10-19 | 2017-07-11 | Basf Se | Hybrid photoinitiators |
| CN104292445A (en) * | 2014-09-03 | 2015-01-21 | 山东久日化学科技有限公司 | Preparation method for macromolecular p-dimethylamino benzoate compound |
| CN105885028A (en) * | 2016-06-17 | 2016-08-24 | 华东理工大学 | Polyether alcohol ester compound and application thereof |
| CN105885028B (en) * | 2016-06-17 | 2020-09-04 | 华东理工大学 | Polyether alcohol ester compound and application thereof |
| CN108947803A (en) * | 2018-03-19 | 2018-12-07 | 山东润博生物科技有限公司 | A kind of preparation method of phenoxy carboxylic acid substance |
| CN113583212A (en) * | 2021-08-05 | 2021-11-02 | 明光科迪新材料有限公司 | Polyurethane modified epoxy acrylate UV resin containing double-type photo-initiation group |
| CN113583212B (en) * | 2021-08-05 | 2022-06-17 | 明光科迪新材料有限公司 | Polyurethane modified epoxy acrylate UV resin containing double-type photo-initiation group |
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