CN101724099B - Aromatic ketone compound and photoinitiator with same - Google Patents
Aromatic ketone compound and photoinitiator with same Download PDFInfo
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- CN101724099B CN101724099B CN200910188985A CN200910188985A CN101724099B CN 101724099 B CN101724099 B CN 101724099B CN 200910188985 A CN200910188985 A CN 200910188985A CN 200910188985 A CN200910188985 A CN 200910188985A CN 101724099 B CN101724099 B CN 101724099B
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- Prior art keywords
- compound
- alkyl
- straight
- ketone
- xenyl
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- -1 Aromatic ketone compound Chemical class 0.000 title claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 62
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- 239000011574 phosphorus Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 49
- 125000000217 alkyl group Chemical group 0.000 claims description 35
- 125000003118 aryl group Chemical group 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 7
- 235000010290 biphenyl Nutrition 0.000 abstract description 4
- 239000004305 biphenyl Substances 0.000 abstract description 4
- 125000005842 heteroatom Chemical group 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 150000008365 aromatic ketones Chemical class 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- 125000006267 biphenyl group Chemical group 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 46
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 42
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 22
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 22
- 241000720974 Protium Species 0.000 description 22
- 229910052799 carbon Inorganic materials 0.000 description 22
- 230000006837 decompression Effects 0.000 description 18
- 239000012074 organic phase Substances 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 14
- 239000003480 eluent Substances 0.000 description 14
- 239000012046 mixed solvent Substances 0.000 description 14
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 11
- 238000004587 chromatography analysis Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000010898 silica gel chromatography Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000010992 reflux Methods 0.000 description 8
- 238000004809 thin layer chromatography Methods 0.000 description 8
- 239000012855 volatile organic compound Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 238000003810 ethyl acetate extraction Methods 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 7
- 238000000605 extraction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- HEQOJEGTZCTHCF-UHFFFAOYSA-N 2-amino-1-phenylethanone Chemical class NCC(=O)C1=CC=CC=C1 HEQOJEGTZCTHCF-UHFFFAOYSA-N 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 4
- 125000001246 bromo group Chemical class Br* 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- ZWVMLYRJXORSEP-LURJTMIESA-N (2s)-hexane-1,2,6-triol Chemical compound OCCCC[C@H](O)CO ZWVMLYRJXORSEP-LURJTMIESA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 150000002780 morpholines Chemical class 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- 0 CC(*)(C(c(cc1)ccc1-c1ccccc1)=O)OP(c1ccccc1)c1ccccc1 Chemical compound CC(*)(C(c(cc1)ccc1-c1ccccc1)=O)OP(c1ccccc1)c1ccccc1 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical class Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- DGMOBVGABMBZSB-UHFFFAOYSA-N 2-methylpropanoyl chloride Chemical class CC(C)C(Cl)=O DGMOBVGABMBZSB-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- GPTJVDAFFWFOKK-UHFFFAOYSA-N CC(C)(C(c(cc1)ccc1-c1ccccc1)=O)OP(c1ccccc1)(c1ccccc1)=O Chemical compound CC(C)(C(c(cc1)ccc1-c1ccccc1)=O)OP(c1ccccc1)(c1ccccc1)=O GPTJVDAFFWFOKK-UHFFFAOYSA-N 0.000 description 1
- FBLAQPBGEXKUNY-UHFFFAOYSA-N CC(C)(C(c(cc1)ccc1-c1ccccc1)=O)P(c1ccccc1)(c1ccccc1)=O Chemical compound CC(C)(C(c(cc1)ccc1-c1ccccc1)=O)P(c1ccccc1)(c1ccccc1)=O FBLAQPBGEXKUNY-UHFFFAOYSA-N 0.000 description 1
- XMTHCHWBRUQHBC-UHFFFAOYSA-N CC(CC(C(OC)=O)C(OC)=O)(C(c(cc1)ccc1-c1ccccc1)=O)O Chemical compound CC(CC(C(OC)=O)C(OC)=O)(C(c(cc1)ccc1-c1ccccc1)=O)O XMTHCHWBRUQHBC-UHFFFAOYSA-N 0.000 description 1
- GHQMPHYJVMFLML-UHFFFAOYSA-N CC(CN(c1ccccc1)c1ccccc1)(C(c(cc1)ccc1-c1ccccc1)=O)O Chemical compound CC(CN(c1ccccc1)c1ccccc1)(C(c(cc1)ccc1-c1ccccc1)=O)O GHQMPHYJVMFLML-UHFFFAOYSA-N 0.000 description 1
- SMWLPOPFUIYNEW-YWEYNIOJSA-N CC(COC(/C=C\C)=C)(C(c(cc1)ccc1C1=CC=CCC1)=O)O Chemical compound CC(COC(/C=C\C)=C)(C(c(cc1)ccc1C1=CC=CCC1)=O)O SMWLPOPFUIYNEW-YWEYNIOJSA-N 0.000 description 1
- ROYYSDVQCVKDBP-UHFFFAOYSA-N CC(COc1ccccc1)(C(c(cc1)ccc1-c1ccccc1)=O)O Chemical compound CC(COc1ccccc1)(C(c(cc1)ccc1-c1ccccc1)=O)O ROYYSDVQCVKDBP-UHFFFAOYSA-N 0.000 description 1
- TWGKEAJKHQBUJX-UHFFFAOYSA-N CC(CP(c1ccccc1)(c1ccccc1)=O)(C(c(cc1)ccc1-c1ccccc1)=O)O Chemical compound CC(CP(c1ccccc1)(c1ccccc1)=O)(C(c(cc1)ccc1-c1ccccc1)=O)O TWGKEAJKHQBUJX-UHFFFAOYSA-N 0.000 description 1
- FSNNHMGELYSJIN-UHFFFAOYSA-N CC(CP(c1ccccc1)c1ccccc1)(C(c(cc1)ccc1-c1ccccc1)=O)O Chemical compound CC(CP(c1ccccc1)c1ccccc1)(C(c(cc1)ccc1-c1ccccc1)=O)O FSNNHMGELYSJIN-UHFFFAOYSA-N 0.000 description 1
- RZVCUYJVNFIBHZ-UHFFFAOYSA-N CC(Cc1ccccc1)(C(c(cc1)ccc1-c1ccccc1)=O)N(c1ccccc1)O Chemical compound CC(Cc1ccccc1)(C(c(cc1)ccc1-c1ccccc1)=O)N(c1ccccc1)O RZVCUYJVNFIBHZ-UHFFFAOYSA-N 0.000 description 1
- JXAWEKGYRGKGOK-UHFFFAOYSA-N CC(Cc1ccccc1)(C(c(cc1)ccc1-c1ccccc1)=O)ONc1ccccc1 Chemical compound CC(Cc1ccccc1)(C(c(cc1)ccc1-c1ccccc1)=O)ONc1ccccc1 JXAWEKGYRGKGOK-UHFFFAOYSA-N 0.000 description 1
- ZVFASFWRIXFILT-UHFFFAOYSA-N COc(cc1)ccc1P(C(CCCC1)C1(C(c(cc1)ccc1-c1ccccc1)=O)O)(c(cc1)ccc1OC)=O Chemical compound COc(cc1)ccc1P(C(CCCC1)C1(C(c(cc1)ccc1-c1ccccc1)=O)O)(c(cc1)ccc1OC)=O ZVFASFWRIXFILT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- CJKOYHIJFXXCBB-UHFFFAOYSA-N [N+](=O)([O-])CC.[Na] Chemical compound [N+](=O)([O-])CC.[Na] CJKOYHIJFXXCBB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- KGNDCEVUMONOKF-UGPLYTSKSA-N benzyl n-[(2r)-1-[(2s,4r)-2-[[(2s)-6-amino-1-(1,3-benzoxazol-2-yl)-1,1-dihydroxyhexan-2-yl]carbamoyl]-4-[(4-methylphenyl)methoxy]pyrrolidin-1-yl]-1-oxo-4-phenylbutan-2-yl]carbamate Chemical compound C1=CC(C)=CC=C1CO[C@H]1CN(C(=O)[C@@H](CCC=2C=CC=CC=2)NC(=O)OCC=2C=CC=CC=2)[C@H](C(=O)N[C@@H](CCCCN)C(O)(O)C=2OC3=CC=CC=C3N=2)C1 KGNDCEVUMONOKF-UGPLYTSKSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 229940125833 compound 23 Drugs 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- OVEHNNQXLPJPPL-UHFFFAOYSA-N lithium;n-propan-2-ylpropan-2-amine Chemical compound [Li].CC(C)NC(C)C OVEHNNQXLPJPPL-UHFFFAOYSA-N 0.000 description 1
- 208000030208 low-grade fever Diseases 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- NLRKCXQQSUWLCH-UHFFFAOYSA-N nitrosobenzene Chemical compound O=NC1=CC=CC=C1 NLRKCXQQSUWLCH-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an environmentally friendly photoinitiator without sulfur. The photoinitiator contains biphenyl substituted aromatic ketone compound with hetero atoms or a composite with the compound. The compound is a substituted aromatic ketone which uses one or more biphenyl groups as key substituted groups and contains one or more hetero atoms (oxygen, nitrogen, phosphorus, silicon and other elements). The compound of the invention can be used as the photoinitiator of the photopolymerization of the unsaturated alkene compound or the mixture with same and the compound of the invention can also be combined with another photoinitiator and/or with other additives in use.
Description
[technical field]
The invention belongs to aromatic ketone compounds; Relate in particular to the substituted heteroatoms that contains of a kind of xenyl and (comprise oxygen; Nitrogen, phosphorus, elements such as silicon; But do not comprise element sulphur) aromatic ketone compounds, and be used for the light trigger that comprises this type of aromatic ketone compounds as unsaturated allyl compound system photopolymerization reaction.
[background technology]
At present, the light trigger of radical photopolymerization reaction commonly used is Alpha-hydroxy methyl phenyl ketone and alpha-aminoacetophenone compounds.This compounds has been disclosed in the various patent documentations, and for example international publication number is PCT patented claim, the USP 4,582,862,4,992,547,5,541,308,5,077,402 and Japanese Patent 2009203299A of 2008122504A1.
International publication number is that the PCT patented claim of 2005014515A2 and 2008084853A1 disclosed respectively with phenyl ether and carbazole is the bifunctional Alpha-hydroxy methyl phenyl ketone and the alpha-aminoacetophenone of skeleton.
USP 4,559,371 and 4,739,052 has disclosed Sauerstoffatom substituted aroma ketone deutero-mono-functionalized and bifunctional Alpha-hydroxy methyl phenyl ketone and alpha-aminoacetophenone.
Chinese patent is open/and notification number is that the patented claim of 1668648A, 1871200A, 1942424A and 101104582A has disclosed some mono-functionalized and bifunctional Alpha-hydroxy methyl phenyl ketone and alpha-aminoacetophenone.
Chinese patent is open/and notification number is that 1184117A and 101031543A have disclosed sulfydryl (SH), single sulphur, and two sulphur (S-S-) substituted mono-functionalized and bifunctional Alpha-hydroxy methyl phenyl ketone and alpha-aminoacetophenone.
Light trigger commonly used usually produces carinogenicity aromatic hydrocarbon in use; Effusion volatile organic compounds (Volatile Organic Compounds; Be called for short VOC), or produce unpleasant chemicals smell (particularly some sulfur-bearing light triggers), or problem such as compound migration takes place.Therefore, the significant problem of these environmental protection and healthy aspect is promoting the continuous research and development to the eco-friendly light trigger of a new generation.
[summary of the invention]
For this reason, the present invention's first technical problem that will solve provides a kind of eco-friendly light trigger that does not comprise sulphur.
Second technical problem that the present invention solves provides the some kinds of aromatic ketone compounds that can be applicable to light trigger.
For solving first technical problem; The present invention provides a kind of light trigger that is used for as unsaturated allyl compound system photopolymerization reaction; It comprises in the compound that following general formula I-IV representes one of at least or the arbitrary composition formed of the compound represented of following general formula I-IV, wherein:
The compound of general formula I is:
Wherein, X and Y are hydroxyl (OH), amine alkyl (NR
2, NRR ', NHR), nitro (NO
2), alkyl (R), alkoxyl group (OR), azyloxy (NROH, ONHR), siloyl group (SiR
3, SiR
2R '), siloxanes (OSiR
3, OSiR
2R '), phosphine alkyl (PR
2, PRR '), or phosphine oxyalkyl (O=PR
2, O=PRR '), R and R ' they are C
1-C
12The alkyl of straight or branched, or aryl; R
1Be C
1-C
12The straight or branched alkyl;
The compound of general formula I I is:
Wherein, X and X ' are hydroxyl (OH), amine alkyl (NR
2, NRR ', NHR), nitro (NO
2), alkyl (R), alkoxyl group (OR), azyloxy (NROH, ONHR), siloyl group (SiR
3, SiR
2R '), siloxanes (OSiR
3, OSiR
2R '), phosphine alkyl (PR
2, PRR '), or phosphine oxyalkyl (O=PR
2, O=PRR '), R and R ' they are C
1-C
12The alkyl of straight or branched, or aryl; Z contains aerobic, nitrogen, phosphorus, the divalence of elements such as silicon, trivalent or quaternary groups; R
1Be C
1-C
12The straight or branched alkyl;
The compound of general formula III is:
Wherein, Z contains aerobic, nitrogen, phosphorus, the divalence of elements such as silicon, trivalent or quaternary groups; R
1And R
2Be C
1-C
12The straight or branched alkyl; And
The compound of general formula I V is:
Wherein, X and X ' are hydroxyl (OH), amine alkyl (NR
2, NRR ', NHR), nitro (NO
2), alkyl (R), alkoxyl group (OR), azyloxy (NROH, ONHR), siloyl group (SiR
3, SiR
2R '), siloxanes (OSiR
3, OSiR
2R '), phosphine alkyl (PR
2, PRR '), or phosphine oxyalkyl (O=PR
2, O=PRR '), R and R ' they are C
1-C
12The alkyl of straight or branched, or aryl; R
2Be C
1-C
12The straight or branched alkyl; R
3Be R
4Be C
1-C
8Alkylidene group.
For solving second technical problem, the present invention provides a kind of compound of general formula I:
Wherein, X and Y are hydroxyl (OH), amine alkyl (NR
2, NRR ', NHR), nitro (NO
2), alkyl (R), alkoxyl group (OR), azyloxy (NROH, ONHR), siloyl group (SiR
3, SiR
2R '), siloxanes (OSiR
3, OSiR
2R '), phosphine alkyl (PR
2, PRR '), or phosphine oxyalkyl (O=PR
2, O=PRR '), R or R ' they are C
1-C
12The alkyl of straight or branched, or aryl; R
1Be C
1-C
12The straight or branched alkyl.
The present invention also provides the compound of a kind of general formula I I:
Wherein, X and X ' are hydroxyl (OH), amine alkyl (NR
2, NRR ', NHR), nitro (NO
2), alkyl (R), alkoxyl group (OR), azyloxy (NROH, ONHR), siloyl group (SiR
3, SiR
2R '), siloxanes (OSiR
3, OSiR
2R '), phosphine alkyl (PR
2, PRR '), or phosphine oxyalkyl (O=PR
2, O=PRR '), R or R ' they are C
1-C
12The alkyl of straight or branched, or aryl; Z contains aerobic, nitrogen, phosphorus, the divalence of elements such as silicon, trivalent or quaternary groups; R
1Be C
1-C
12The straight or branched alkyl.
The present invention also provides a kind of compound of general formula III:
Wherein, Z contains aerobic, nitrogen, phosphorus, the divalence of elements such as silicon, trivalent or quaternary groups; R
1And R
2Be C
1-C
12The straight or branched alkyl.
The present invention also provides the compound of a kind of general formula I V:
Wherein, X and X ' are hydroxyl (OH), amine alkyl (NR
2, NRR ', NHR), nitro (NO
2), alkyl (R), alkoxyl group (OR), azyloxy (NROH, ONHR), siloyl group (SiR
3, SiR
2R '), siloxanes (OSiR
3, OSiR
2R '), phosphine alkyl (PR
2, PRR '), or phosphine oxyalkyl (O=PR
2, O=PRR '), R or R ' they are C
1-C
12The alkyl of straight or branched, or aryl; R
2Be C
1-C
12The straight or branched alkyl; R
3Be R
4Be C
1-C
8Alkylidene group.
To be that the xenyl of I-IV is substituted contain the heteroatoms aromatic ketone compounds and compsn can make an addition in the unsaturated allyl compound system to general formula of the present invention, causes this unsaturated allyl compound system generation photopolymerization reaction and solidify through suitable wavelength light source irradiation.
And above-claimed cpd is to serve as crucial to replace group with one or more biphenyl, and contains the substituted aromatic ketone of one or more heteroatomss (oxygen, nitrogen, phosphorus, elements such as silicon).This compound does not contain any element sulphur, is a kind of environment friendly light trigger, has avoided the volatile organic compounds of overflowing in the reaction, or has produced unpleasant chemicals smell, or problem such as compound migration takes place.
[embodiment]
The present invention has disclosed the substituted aroma ketone compounds that following general formula is I-IV.
Wherein, X, X ' and Y are hydroxyl (OH), amine alkyl (NR
2, NRR ', NHR), nitro (NO
2), alkyl (R), alkoxyl group (OR), azyloxy (NROH, ONHR), siloyl group (SiR
3, SiR
2R '), siloxanes (OSiR
3, OSiR
2R '), phosphine alkyl (PR
2, PRR '), or phosphine oxyalkyl (O=PR
2, O=PRR '); R or R ' are C
1-C
12The alkyl of straight or branched, or aryl.
Z contains aerobic, nitrogen, phosphorus, the divalence of elements such as silicon, trivalent or quaternary groups.
R
1And R
2Be C
1-C
12The straight or branched alkyl.
R
3Be R
4Be C
1-C
8Alkylidene group.
Contain compsn and these compounds of above-claimed cpd or the light trigger that compsn can be used as unsaturated allyl compound system light polymerization.By the polymeric unsaturated allyl compound can be monomer, the compound of oligomeric or poly, and its nonsaturation can be embodied in and contain one or more alkene double bonds.
This compounds comprises but is not limited to following example: vinyl cyanide, acrylic amide, vinyl-acetic ester, vinylchlorid; Vinylbenzene, methyl acrylate, Bing Xisuandingzhi, vinylformic acid 2-hydroxy methyl; The silicon Acrylote oxyalkyl ester, ethyl methacrylate, isobutyl vinyl ether, N-V-Pyrol RC etc.
Wherein, the compound of general molecular formula I comprises but is not limited to following example structure:
The compound of general molecular formula II comprises but is not limited to following example structure:
The compound of general molecular formula III comprises but is not limited to following example structure:
The compound of general molecular formula IV comprises but is not limited to following example structure:
Compound of the present invention can be used as unsaturated allyl compound or contain the light trigger of light polymerization of the mixture of this compound, and these compounds also can be used in combination with another kind of light trigger and/or with other additive.
Further specify the present invention with exemplary embodiment below:
Embodiment one
1-(xenyl-4-yl)-2-methyl-2-morpholinyl propane-1-ketone:
The first step: under the nitrogen protection, after 23.5 gram biphenyl dissolved with 150 milliliters of methylene dichloride, the ice-water bath cooling added 29.2 gram aluminum chlorides, drips 19.1 milliliters of isobutyryl chlorides then.Stirred 2 hours in the ice-water bath, move to room temperature restir reaction 2 hours.Above-mentioned reaction solution is poured in 100 milliliters of 5N hydrochloric acid,, merged organic phase with equal-volume dichloromethane extraction three times; Anhydrous sodium sulfate drying; Filter, decompression is revolved dried, gets compound bullion 34 grams; Available silica gel column chromatogram chromatography method is that the eluent purifying obtains midbody 1-(xenyl-4-yl)-2-methylpropane-1-ketone with the hexane/ethyl acetate mixed solvent.
Second step: after getting 17 gram above-claimed cpds and dissolving with 150 milliliters of methylene dichloride; Drip 0.5 milliliter of bromine, have gas to emerge after, then slowly drip 3.7 milliliters of bromines again; Stirring at room 3 hours is with thin-layer chromatography or hydrogen nuclear magnetic resonance spectroscopy tracking monitor reaction end.The reaction solution decompression is revolved dried, gets compound 23 grams.This compound is suspended in 150 milliliters of absolute ethyl alcohols, adds 14 milliliters of morpholines, reflux 24 hours is with thin-layer chromatography or hydrogen nuclear magnetic resonance spectroscopy tracking monitor reaction end.It is dried that reaction solution decompression is revolved, and adds 100 milliliters of 1N sodium hydroxide solutions, with equal-volume dichloromethane extraction three times, merges organic phase, and anhydrous sodium sulfate drying filters, and decompression is revolved dried, and the compound bullion use the absolute ethyl alcohol recrystallization, gets faint yellow solid powder-product 19 and restrains.
1-(xenyl-4-yl)-2-methyl-2-morpholinyl propane-1-ketone:
Molecular formula: C
20H
23NO
2
Theoretical value: carbon element content 77.64%, protium content 7.49%;
Measured value: carbon element content 77.21%, protium content 7.43%.
Embodiment two
1-(xenyl-4-yl)-2-hydroxy-2-methyl-morpholinyl propane-1-ketone:
The first step: embodiment one the first step products obtained therefrom 1-(xenyl-4-yl)-2-methylpropane-1-ketone 20 is restrained with after 160 milliliters of methylene dichloride dissolvings; Slowly drip 4.9 milliliters of bromines; Stirring at room 3 hours is with thin-layer chromatography or hydrogen nuclear magnetic resonance spectroscopy tracking monitor reaction end.The reaction solution decompression is revolved dried, and resistates mixes with 120 milliliter of 30% sodium hydroxide solution, reflux 5 hours.Reaction solution is cooled to room temperature, adds the salt acid for adjusting pH value to 8-9, with equal-volume dichloromethane extraction three times; Merge organic phase; Anhydrous magnesium sulfate drying filters, and decompression is revolved dried; The compound bullion is used the silica gel column chromatography chromatography, is that the eluent purifying obtains midbody 1-(xenyl-4-yl)-2-methyl-propyl-2-alkene-1-ketone 14 grams with the hexane/ethyl acetate mixed solvent.
Second step: get 13 gram 1-(xenyl-4-yl)-2-methyl-propyl-2-alkene-1-ketone and place the methanol solution of 150 milliliters of 1N sodium hydroxide, add 65 milliliter 30% superoxol.The airtight back of reaction system is 50 ℃ of reacting by heating, and reacting to terminal with the tlc tracking monitor, postcooling adds saturated ammonium chloride and regulates the pH value to neutrality to room temperature; With equal-volume dichloromethane extraction three times, merge organic phase, anhydrous magnesium sulfate drying; Filter; Decompression is revolved dried, and the compound bullion is used the silica gel column chromatography chromatography, is that the eluent purifying obtains midbody xenyl-4-base-(2-methyl oxirane-2-yl)-ketone 9.2 grams with the hexane/ethyl acetate mixed solvent.
The 3rd step: get 9 gram xenyl-4-base-(2-methyl oxirane-2-yl)-ketones and 30 gram morpholine and 20 milliliters of N, dinethylformamide mixes, reflux; React to terminal postcooling to room temperature with the tlc tracking monitor, with 100 ml water dilute reaction solutions, then with equal-volume ethyl acetate extraction three times; Merge organic phase; Anhydrous sodium sulfate drying filters, and decompression is revolved dried; The compound bullion is used the silica gel column chromatography chromatography, is that the eluent purifying obtains the finished product 1-(xenyl-4-yl)-2-hydroxy-2-methyl-morpholinyl propane-1-ketone 11 grams with the hexane/ethyl acetate mixed solvent.
1-(xenyl-4-yl)-2-hydroxy-2-methyl-morpholinyl propane-1-ketone:
Molecular formula: C
20H
23NO
3
Theoretical value: carbon element content 73.82%, protium content 7.12%;
Measured value: carbon element content 73.31%, protium content 7.76%.
Embodiment three
1-(xenyl-4-yl)-2-hydroxy-2-methyl-3-phenylol propane-1-ketone:
Get 6 gram the foregoing descriptions, 2 second steps obtained compound xenyl-4-base-(2-methyl oxirane-2-yl)-ketone and 3.5 gram sodium phenylate and 40 milliliters of N, dinethylformamide mixes, reflux; React to terminal postcooling to room temperature with the tlc tracking monitor, with 120 ml water dilute reaction solutions, then with equal-volume ethyl acetate extraction three times; Merge organic phase; Anhydrous sodium sulfate drying filters, and decompression is revolved dried; The compound bullion is used the silica gel column chromatography chromatography, is that the eluent purifying obtains the finished product 1-(xenyl-4-yl)-2-hydroxy-2-methyl-3-phenylol propane-1-ketone 7.8 grams with the hexane/ethyl acetate mixed solvent.
1-(xenyl-4-yl)-2-hydroxy-2-methyl-3-phenylol propane-1-ketone:
Molecular formula: C
22H
20O
3
Theoretical value: carbon element content 79.50%, protium content 6.06%;
Measured value: carbon element content 79.89%, protium content 6.53%.
Embodiment four:
1-(xenyl-4-yl)-2-hydroxy-2-methyl-4-nitrobutane-1-ketone:
Get 6 gram the foregoing descriptions, 2 second steps obtained compound xenyl-4-base-(2-methyl oxirane-2-yl)-ketone and 2.5 grams nitroethane sodium salt and 25 milliliters of N of preparation in advance; Dinethylformamide mixes, and reflux is reacted to terminal postcooling to room temperature with the tlc tracking monitor; With 120 ml water dilute reaction solutions; With equal-volume ethyl acetate extraction three times, merge organic phase, anhydrous sodium sulfate drying then; Filter; Decompression is revolved dried, and the compound bullion is used the silica gel column chromatography chromatography, is that the eluent purifying obtains the finished product 1-(xenyl-4-yl)-2-hydroxy-2-methyl-4-nitrobutane-1-ketone 7.3 grams with the hexane/ethyl acetate mixed solvent.
1-(xenyl-4-yl)-2-hydroxy-2-methyl-4-nitrobutane-1-ketone:
Molecular formula: C
17H
17NO
4
Theoretical value: carbon element content 68.21%, protium content 5.72%;
Measured value: carbon element content 68.91%, protium content 5.96%.
Embodiment five:
1-(xenyl-4-yl)-3-(3,5-dimethylphenyl is silica-based)-2-hydroxy-2-methyl propane-1-ketone:
Get 6 gram the foregoing descriptions 2 second step obtained compound xenyl-4-base-(2-methyl oxirane-2-yl)-ketones and 5.4 grams the dimethylphenylsilaneand lithium salts of preparation [notes: by the dimethylphenylsilaneand of equivalent and diisopropylamine lithium in the anhydrous tetrahydro furan made acid-stable in situ] and 25 milliliters of N in advance; Dinethylformamide mixes, and reflux is reacted to terminal postcooling to room temperature with the tlc tracking monitor; With 120 ml water dilute reaction solutions; With equal-volume ethyl acetate extraction three times, merge organic phase, anhydrous sodium sulfate drying then; Filter; Decompression is revolved dried, and the compound bullion is used the silica gel column chromatography chromatography, is that the eluent purifying obtains the finished product 1-(xenyl-4-yl)-3-(3,5-dimethylphenyl is silica-based)-2-hydroxy-2-methyl propane-1-ketone 8.7 grams with the hexane/ethyl acetate mixed solvent.
1-(xenyl-4-yl)-3-(3,5-dimethylphenyl is silica-based)-2-hydroxy-2-methyl propane-1-ketone:
Molecular formula: C
24H
26SiO
2
Theoretical value: carbon element content 76.96%, protium content 7.00%;
Measured value: carbon element content 77.11%, protium content 7.13%.
Embodiment six:
1-(xenyl-4-yl)-2-(hydroxy phenyl amido)-2-methylpropane-1-ketone:
Getting the 8 gram obtained midbody 1-of the foregoing description one the first step (xenyl-4-yl)-2-methylpropane-1-ketone under the nitrogen protection is dissolved in 100 milliliters of anhydrous tetrahydro furans; Be cooled to-20 ℃; The anhydrous tetrahydrofuran solution that slowly adds 1.2 equivalent diisopropylamine lithiums finished stirring reaction 1 hour; Slowly add 5.8 gram exsiccant nitrosobenzene liquid then, reaction solution is back to room temperature and continues stirring reaction, with the reaction of tlc tracking monitor to terminal.The concentration of reaction solution volume dilutes with 250 ml waters to half the, then with equal-volume ethyl acetate extraction three times; Merge organic phase; Anhydrous sodium sulfate drying filters, and decompression is revolved dried; The compound bullion is used the silica gel column chromatography chromatography, is that the eluent purifying obtains the finished product 1-(xenyl-4-yl)-2-(hydroxy phenyl amido)-2-methylpropane-1-ketone 9.5 grams with the hexane/ethyl acetate mixed solvent.
1-(xenyl-4-yl)-2-(hydroxy phenyl amido)-2-methylpropane-1-ketone:
Molecular formula: C
22H
21NO
2
Theoretical value: carbon element content 79.73%, protium content 6.39%;
Measured value: carbon element content 80.08%, protium content 6.79%.
Embodiment seven
3,3 '-(piperazine-1,4-two bases) two (1-(xenyl-4-yl))-2-hydroxy-2-methyl propane-1-ketone:
Get 5 gram the foregoing descriptions 2 second step obtained compound xenyl-4-base-(2-methyl oxirane-2-yl)-ketones and 0.9 and restrain piperazine and be mixed in the withstand voltage tube sealing of glass, 120 ℃ of reacting by heating 14 hours.Reaction solution is cooled to room temperature; Reaction solution directly obtains the finished product 3 with the hexane/ethyl acetate mixed solvent as the eluent purifying after using the dissolving of 100 amount of ethyl acetate on silica gel chromatographic column; 3 '-(piperazine-1,4-two bases) two (1-(xenyl-4-yl))-2-hydroxy-2-methyl propane-1-ketone 4.3 grams.
3,3 '-(piperazine-1,4-two bases) two (1-(xenyl-4-yl))-2-hydroxy-2-methyl propane-1-ketone:
Molecular formula: C
36H
38N
2O
4
Theoretical value: carbon element content 76.84%, protium content 6.81%;
Measured value: carbon element content 77.02%, protium content 7.01%.
Embodiment eight
3,3 '-(1,4-phenyl thiazolinyl dioxygen) two (1-(xenyl-4-yl))-2-hydroxy-2-methyl propane-1-ketone:
Get 5 gram the foregoing descriptions 2 second step obtained compound xenyl-4-base-(2-methyl oxirane-2-yl)-ketones and 1.6 and restrain the Resorcinol double sodium salts and be mixed in 5 milliliters of N, in the dinethylformamide, back flow reaction is 20 hours in the withstand voltage tube sealing of glass.Reaction solution is cooled to room temperature, with 50 ml waters dilutions, then with equal-volume ethyl acetate extraction three times; Merge organic phase, anhydrous sodium sulfate drying filters; Decompression is revolved dried, and the compound bullion is used the silica gel column chromatography chromatography, is that the eluent purifying obtains the finished product 3 with the hexane/ethyl acetate mixed solvent; 3 '-(1,4-phenyl thiazolinyl dioxygen) two (1-(xenyl-4-yl))-2-hydroxy-2-methyl propane-1-ketone 3.1 grams.
3,3 '-(1,4-phenyl thiazolinyl dioxygen) two (1-(xenyl-4-yl))-2-hydroxy-2-methyl propane-1-ketone:
Molecular formula: C
38H
34O
6
Theoretical value: carbon element content 77.80%, protium content 5.84%;
Measured value: carbon element content 77.92%, protium content 6.01%.
Embodiment nine
2,2 '-(piperazine-1,4-two bases) two (1-(xenyl-4-yl))-2-methylpropane-1-ketone:
The first step: after getting 17 gram the foregoing descriptions one the first step gained midbody 1-(xenyl-4-yl)-2-methylpropane-1-ketone and dissolving with 150 milliliters of methylene dichloride; Drip 4.2 milliliters of bromines; Stirring at room 3 hours is with thin-layer chromatography or hydrogen nuclear magnetic resonance spectroscopy tracking monitor reaction end.The reaction solution decompression is revolved dried, and the gained compound dissolution slowly is added dropwise to the methanol solution of 30% sodium methylate of 16 grams in 120 milliliters of toluene.Reaction solution stirring reaction 16 hours under 35 ℃ of low-grade fevers is cooled to room temperature, filters insolubles; Filtered liq is concentrated into half and filters once more; Filtrating is concentrated into dried midbody 2-(xenyl-4-the yl)-2-methoxyl group-3 that obtains, 3-dimethyl ethylene oxide, step reaction under not purified can directly being used for.
Second step: get 15 gram above-mentioned midbody 2-(xenyl-4-yl)-2-methoxyl groups-3,3-dimethyl ethylene oxide and 40 gram morpholines mix, and stirring reaction also steams the methyl alcohol of generation slowly under the heating reflux reaction condition.After the reaction to terminal of tlc tracking monitor; The reaction solution vacuum concentration; Crude product is that the eluent purifying obtains product 2 with the hexane/ethyl acetate mixed solvent directly on silica gel chromatographic column, 2 '-(piperazine-1,4-two bases) two (1-(xenyl-4-yl))-2-methylpropanes-1-ketone 13.3 grams.
2,2 '-(piperazine-1,4-two bases) two (1-(xenyl-4-yl))-2-methylpropane-1-ketone:
Molecular formula: C
36H
38N
2O
2
Theoretical value: carbon element content 81.47%, protium content 7.22%;
Measured value: carbon element content 81.68%, protium content 7.50%.
Embodiment ten
(1,4-dihydroxyl hexanaphthene-1,4-two bases) two (xenyls-4-base-ketone):
The first step: under the nitrogen protection, after 50 gram biphenyl dissolved with 230 milliliters of methylene dichloride, the ice-water bath cooling added 62 gram aluminum chlorides, drips 34 grams 1 then, 4-hexanaphthene diacid chloride.Drip the reaction of Bi Yizhi stirring at room, with thin-layer chromatography or hydrogen nuclear magnetic resonance spectroscopy tracking monitor reaction end.Above-mentioned reaction solution is poured in 300 milliliters of 5N hydrochloric acid,, merged organic phase with equal-volume dichloromethane extraction three times; Anhydrous sodium sulfate drying; Filter, decompression is revolved dried, and the compound bullion that obtains is used the silica gel column chromatography chromatography; With the hexane/ethyl acetate mixed solvent is that the eluent purifying obtains midbody hexanaphthene-1,4-two bases-two (xenyl-4-base-ketone) 60 grams.
Second step: get 44 gram above-claimed cpd and 12 milliliters of tetracol phenixin, 6 gram Tetrabutyl amonium bromides, 200 milliliter of 20% sodium hydroxide solution mixes, in the 600C reaction, with thin-layer chromatography tracking monitor reaction end.Reacted postcooling, then reaction solution has been diluted with 100 ml waters, told organic phase, water merges organic phase with 100 milliliters of ethyl acetate extractions 3 times, and organic phase is neutral with equal-volume washing 3 times to water.Organic phase with anhydrous sodium sulfate drying after, filtering and concentrating, crude product is that the eluent purifying obtains product (1,4-dihydroxyl hexanaphthene-1,4-two bases) two (xenyl-4-base-ketone) 37 gram with the hexane/ethyl acetate mixed solvent on silica gel chromatographic column.
(1,4-dihydroxyl hexanaphthene-1,4-two bases) two (xenyls-4-base-ketone):
Molecular formula: C
32H
28O
4
Theoretical value: carbon element content 80.65%, protium content 5.92%;
Measured value: carbon element content 81.01%, protium content 6.11%.
Embodiment 11
(1,4-dimorpholine basic ring hexane-1,4-two bases) two (xenyls-4-base-ketone):
Under the nitrogen protection; Get 17 gram previous embodiment, ten the first steps obtained hexanaphthene-1; After 4-two bases-two (xenyl-4-base-ketone) dissolve with 150 milliliters of methylene dichloride; Slowly drip 4.2 milliliters of bromines, stirring at room 3 hours is with thin-layer chromatography or hydrogen nuclear magnetic resonance spectroscopy tracking monitor reaction end.The reaction solution decompression is revolved dried, and gained compound bullion directly is suspended in 90 milliliters of morpholines, and heating reflux reaction is with thin-layer chromatography or hydrogen nuclear magnetic resonance spectroscopy tracking monitor reaction end.The reaction solution decompression is revolved dried, adds the jolting of 150 milliliters of 1N sodium hydroxide solutions, with 200 milliliters of dichloromethane extraction secondaries; Merge organic phase, anhydrous sodium sulfate drying filters; Decompression is revolved dried; The compound bullion gets pure article (1,4-dimorpholine basic ring hexane-1,4-two bases) two (xenyl-4-base-ketone) 9 grams with the absolute ethyl alcohol recrystallization.Mother liquor reclaim to concentrate, and on silica gel chromatographic column, is eluent purifying product 4.2 grams of getting back with the hexane/ethyl acetate mixed solvent.
(1,4-dimorpholine basic ring hexane-1,4-two bases) two (xenyls-4-base-ketone):
Molecular formula: C
40H
42N
2O
4
Theoretical value: carbon element content 78.65%, protium content 6.89%;
Measured value: carbon element content 78.58%, protium content 6.44%.
Need to prove; Above-mentioned explanation only is the detailed description to preferred embodiment of the present invention; Narration is merely explanation realizability of the present invention and outstanding effect thereof; Concrete characteristic can not be used as the restriction to technical scheme of the present invention, and protection scope of the present invention should be as the criterion with appended claims of the present invention.
The compounds of this invention discharges benzene and other each item VOC data in the light-initiated test:
In the photocuring test of epoxy acrylate system, be initiator with following example compound, detect following each item VOC data (seeing the following form):
Table one: the some compounds of the present invention produce benzene during as light trigger and each item VOC detects data.
Table one (continuing): the some compounds of the present invention produce benzene during as light trigger and each item VOC detects data.
Claims (5)
1. light trigger that is used for as unsaturated allyl compound system photopolymerization reaction, the characteristic of described light trigger be its comprise in the compound that following general formula I-IV representes one of at least, wherein,
The compound of general formula I is:
Wherein, X and Y are OH, NR
2, NO
2, NHR, R, OR, NROH, ONHR, SiR
3, OSiR
3, PR
2, or O=PR
2, R is C
1-C
12The alkyl of straight or branched, or aryl; R
IBe C
1-C
12The straight or branched alkyl;
The compound of general formula I I is:
Wherein, X and X ' are OH, NR
2, NO
2, NHR, R, OR, NROH, ONHR, SiR
3, OSiR
3, PR
2, or O=PR
2, R is C
1-C
12The alkyl of straight or branched, or aryl; Z contains aerobic, nitrogen, phosphorus, the divalence of element silicon, trivalent or quaternary groups; R
IBe C
1-C
12The straight or branched alkyl;
The compound of general formula III is:
Wherein, Z contains aerobic, nitrogen, phosphorus, the divalence of element silicon, trivalent or quaternary groups; R
IAnd R
IIBe C
1-C
12The straight or branched alkyl; With
The compound of general formula I V is:
Wherein, X and X ' are OH, NR
2, NO
2, NHR, R, OR, NROH, ONHR, SiR
3, OSiR
3, PR
2, or O=PR
2, R is C
1-C
12The alkyl of straight or branched, or aryl; R
IIIAnd R
IVBe C
1-C
8Alkylidene group.
2. the compound of following general formula I:
Wherein, X and Y are OH, NR
2, NO
2, NHR, R, OR, NROH, ONHR, SiR
3, OSiR
3, PR
2, or O=PR
2, R is C
1-C
12The alkyl of straight or branched, or aryl; R
IBe C
1-C
12The straight or branched alkyl.
3. the compound of following general formula I I:
Wherein, X and X ' are OH, NR
2, NO
2, NHR, R, OR, NROH, ONHR, SiR
3, OSiR
3, PR
2, or O=PR
2, R is C
1-C
12The alkyl of straight or branched, or aryl; Z contains aerobic, nitrogen, phosphorus, the divalence of element silicon, trivalent or quaternary groups; R
IBe C
1-C
12The straight or branched alkyl.
4. the compound of following general formula I II:
Wherein, Z contains aerobic, nitrogen, phosphorus, the divalence of element silicon, trivalent or quaternary groups; R
IAnd R
IIBe C
1-C
12The straight or branched alkyl.
5. the compound of following general formula I V:
Wherein, X and X ' are OH, NR
2, NO
2, NHR, R, OR, NROH, ONHR, SiR
3, OSiR
3, PR
2, or O=PR
2, R is C
1-C
12The alkyl of straight or branched, or aryl; R
IIIAnd R
IVBe C
1-C
8Alkylidene group.
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| CN102924630A (en) * | 2011-08-09 | 2013-02-13 | 陈婷 | UV light curing application system containing amino ketone compound 1-([1,1'-biphenyl]-4-yl)-2-methyl-2-morpholinopropan-1-one |
| CN102417553B (en) * | 2011-09-29 | 2013-04-10 | 长沙新宇高分子科技有限公司 | Hydroxyalkyl aryl ketone photoinitiator capable of reducing volatile organic compound (VOC) discharge until elimination of VOC discharge |
| CN102504054B (en) * | 2011-11-01 | 2014-07-02 | 长沙新宇高分子科技有限公司 | Hydroxy-ketone photoinitiator containing multiple functional groups for reducing and eliminating VOC (volatile organic compounds) emission |
| CN102993123B (en) * | 2012-12-21 | 2015-07-29 | 天津久日化学股份有限公司 | A kind of polymer polyfunctional alpha-amine alkylacetophenone light trigger |
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