CN106967027A - Novel coumarin compound and its application - Google Patents
Novel coumarin compound and its application Download PDFInfo
- Publication number
- CN106967027A CN106967027A CN201710152011.5A CN201710152011A CN106967027A CN 106967027 A CN106967027 A CN 106967027A CN 201710152011 A CN201710152011 A CN 201710152011A CN 106967027 A CN106967027 A CN 106967027A
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- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- -1 coumarin compound Chemical class 0.000 title claims description 22
- 229960000956 coumarin Drugs 0.000 title claims description 10
- 235000001671 coumarin Nutrition 0.000 title claims description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 238000003847 radiation curing Methods 0.000 claims abstract description 9
- 230000001235 sensitizing effect Effects 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- PQMOXTJVIYEOQL-UHFFFAOYSA-N Cumarin Natural products CC(C)=CCC1=C(O)C(C(=O)C(C)CC)=C(O)C2=C1OC(=O)C=C2CCC PQMOXTJVIYEOQL-UHFFFAOYSA-N 0.000 claims abstract description 5
- FSOGIJPGPZWNGO-UHFFFAOYSA-N Meomammein Natural products CCC(C)C(=O)C1=C(O)C(CC=C(C)C)=C(O)C2=C1OC(=O)C=C2CCC FSOGIJPGPZWNGO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000009472 formulation Methods 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 239000004593 Epoxy Chemical group 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910001868 water Inorganic materials 0.000 claims description 15
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 11
- 239000005977 Ethylene Substances 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 150000003384 small molecules Chemical class 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000005864 Sulphur Substances 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 230000032050 esterification Effects 0.000 claims description 5
- 238000005886 esterification reaction Methods 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 238000010538 cationic polymerization reaction Methods 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 150000002431 hydrogen Chemical group 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000004437 phosphorous atom Chemical group 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000007259 addition reaction Methods 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000007142 ring opening reaction Methods 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- 238000010464 Blanc reaction Methods 0.000 claims description 2
- 239000007848 Bronsted acid Substances 0.000 claims description 2
- 125000006519 CCH3 Chemical group 0.000 claims description 2
- 238000007341 Heck reaction Methods 0.000 claims description 2
- RMRFFCXPLWYOOY-UHFFFAOYSA-N allyl radical Chemical compound [CH2]C=C RMRFFCXPLWYOOY-UHFFFAOYSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000006267 biphenyl group Chemical group 0.000 claims description 2
- 125000002837 carbocyclic group Chemical group 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 230000017858 demethylation Effects 0.000 claims description 2
- 238000010520 demethylation reaction Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 235000003642 hunger Nutrition 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 2
- 125000006850 spacer group Chemical group 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 2
- 229920000642 polymer Polymers 0.000 claims 2
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 claims 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 239000011230 binding agent Substances 0.000 claims 1
- 239000004305 biphenyl Substances 0.000 claims 1
- 235000010290 biphenyl Nutrition 0.000 claims 1
- 239000013538 functional additive Substances 0.000 claims 1
- 230000026030 halogenation Effects 0.000 claims 1
- 238000005658 halogenation reaction Methods 0.000 claims 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- 239000000543 intermediate Substances 0.000 claims 1
- 239000011159 matrix material Substances 0.000 claims 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 230000005855 radiation Effects 0.000 abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 230000000269 nucleophilic effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000003504 photosensitizing agent Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002027 dichloromethane extract Substances 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- LIIALPBMIOVAHH-UHFFFAOYSA-N herniarin Chemical compound C1=CC(=O)OC2=CC(OC)=CC=C21 LIIALPBMIOVAHH-UHFFFAOYSA-N 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- RADLTTWFPYPHIV-UHFFFAOYSA-N (2-sulfanylphenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1S RADLTTWFPYPHIV-UHFFFAOYSA-N 0.000 description 1
- VOAAEKKFGLPLLU-UHFFFAOYSA-N (4-methoxyphenyl)boronic acid Chemical class COC1=CC=C(B(O)O)C=C1 VOAAEKKFGLPLLU-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical class [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- FLTZDSVIFBIENN-UHFFFAOYSA-N 7-methoxy-3-(4-methoxyphenyl)chromen-2-one Chemical compound C1=CC(OC)=CC=C1C1=CC2=CC=C(OC)C=C2OC1=O FLTZDSVIFBIENN-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 101710094902 Legumin Proteins 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
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- VLGSRJCUNKGJCE-UHFFFAOYSA-N boric acid 1,3,5-trimethylbenzene Chemical compound B(O)(O)O.CC1=CC(=CC(=C1)C)C VLGSRJCUNKGJCE-UHFFFAOYSA-N 0.000 description 1
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
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- 238000012544 monitoring process Methods 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
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- 239000011591 potassium Substances 0.000 description 1
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- 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
- 238000000746 purification Methods 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to new material organic chemicals technical field, more particularly to using cumarin as the noval chemical compound of core texture shown in formula (I), its chemical preparating process technology, its as radiation curing sensitising agent purposes, and it is in radiation curable formulation product, photocureable coating or ink that particularly UV Vis LED can be excited, wait the application purpose of many occasions.
Description
【Technical field】
The present invention relates to new material organic chemicals technical field, the new change containing tonka bean camphor structure of a more particularly to class
Compound, its chemical preparating process technology, it is as the purposes of radiation curing sensitising agent, and it is in radiation curable formulation product,
Particularly in UV-Vis-LED photocureable coating or ink, the application purpose of many occasions is waited.
【Background technology】
Photosensitizer compounds are the important Fine Organic Chemical product materials of a class.With ultraviolet light or visible (UV) light or
LED (i.e. Light-Emitting Diode) is the radiation curing technology field of light source, can be sensitized triggering under light radiation parameter
It is to induce containing the unsaturated system of alkene or enter containing epoxy systems that agent, which generates free radical activity species or the photosensitizer compounds of cation,
The key species of the efficient photopolymerization reaction of row, therefore be one of important radiation curable formulation component.Known numerous photosensitive
In agent product, coumarin kind compound occupies consequence due to good sensitization effect and preferable solubility, such as fragrant
Legumin ketone, related patent such as CN104603121A and CN104755507A.
On the other hand, photocuring light source is usually using mercury lamp, and mercuryvapour does not meet world's energy-conserving and environment-protective industry development
Strategic new trend, thus LED/light source obtains increasingly extensive attention and quickly development, and LED light solidification skill in recent years
The application of art considerably reduces energy resource consumption and ozone generation, industry sustainable growth powerful.For the solidification of LED systems,
It is also required to both have the light-initiated of sensitive absorption for LED longwave transmissions wavelength (365-420 nanometers, particularly 395-405 nanometer)
System.Therefore, design, research and development, and the new photosensitizer compounds of industrialization, it is that the key technique that current this area is faced is chosen
War problem.The scope of the absorption spectrum of coumarin kind compound is a feasible approach known to further red shift.
For above-mentioned technological challenge, the present invention is it has been unexpectedly discovered that some are via containing that novel synthesis is obtained
There is the coumarin compound of appropriate functional group, possess the absorbing wavelength matched very much with LED, sensitization effect well can be played
Really, such technology is to the green application of woodenware, environmental printing, inkjet printing, and the field such as energy-saving material possesses far-reaching influence.
【The content of the invention】
This application discloses the novel coumarin class compound shown in below formula (I)：
In above-mentioned logical formula (I) compound structure：
X-R0And R2- Q is containing R independently of one another3, R4, R5, R6, R7Substituted aryl (as shown in formula), or R8, R9, R10
Substituted tertiary alkyl, wherein R3, R4, R5, R6, R7Independent of each other is hydrogen, halogen atom, R, OR, SR, NRR ', CH2OH,
CH2OR, or CH2NRR ', wherein R or R ' independent of each other are (to be labeled as-C containing 1-24 carbon atom1-C24, similarly hereinafter) straight chain
Or the alkyl of side chain or-C6-C121-6 discrete oxygen, nitrogen, or element sulphur, R and R ' can be contained in aryl, R or R ' structures
The ring system structure of a 3-6 member can also be formed in the presence of simultaneously therebetween.R8, R9, R10Independent of each other is among R, three
The carbocyclic ring structure of a 3-6 member can also be formed both any.It is preferred that, R3=R5=R7=CH3And R4=R6=H, or R3=R4
=R6=R7=H and R5=CH3, or R4=R5=OCH3And R3=R6=R7=H, or R3=R5=R7=CH3And R4=R6=
CH2OH, or R3=R5=R6=R7=H and R4=SCH3, or R3=R4=R6=R7=H and R5=SCH3, or R3=R5=R7=CH3
And R4=R6=CH2OC (O) R, or R3=R5=R7=CH3And R4=CH2OH and R6=H, or R3=R5=R7=CH3And R4=R6
=CH2OR, or R3=R5=R7=CH3And R4=R6=CH2NRR ', or R3=R5=R7=CH3And R4=CH2OH and R6=
CH2NRR’.It is preferred that, R8=R9=R10=H, or R8=R9=CH3, R10=H, or R8=R9=R10=CH2CH3, or R8=CH3
And R9-R10It is cyclohexane structure；
Y is CH=CH, or oxygen element, or Y is not present；
Integer between n values 1-1000, it is preferred that the integer between n values 1-100, it is furthermore preferred that n values 1-10
Between integer；
R1It is R or-C (O)-R0, R preferably1It is CH3, CH2CH3, CH (CH3)2, C6H5, p-CH3OC6H4, CH2CH=CH2,
CH2Ph, C (O) CEt3, C (O) CMe3, xenyl,；
As n=1, X-R0And R2- Q structures are hydrogen, the C containing 0-4 substituent6-C24(preferably phenyl, joins aryl
Phenyl, naphthyl), CH3, CH2CH3, CH (CH3)2, OR, CH2OH, CH2OR, CH2OC (O) R, CH2NRR ', CHR (OH), CRR '
(OH), CCH3(CH2OH) OH, C (CH2OH)2OH, CH2CH2OH, CH2CHMeOH, CHMeCH2OH, CH2CHPhOH, CH2C (O) R,
CH2CO2H or its metal salt or amine salt, CH2CH2CO2H or its metal salt or amine salt, CH2CH2C(O)OCH2CH2OH, CH2CHMeC
(O)OCH2CH2OH, CH2CH2C(O)OCH2CH2OCH2CH2OH, CH2CH2C (O) OZ, CH2OC (O)-NHZ, or CH2CH2OC(O)
NHZ, Z is one containing 2-6 C=C double bonds-C here2-C36Group, preferably Z are one containing 2-6 acrylate list
- the C of member2-C36Group, preferred Z is one of following shown group：
When n values 2 or the integer more than 2, X and Q structures are a n member spacer groups；X or Q are preferably-CH2- ,-
CH2CH2- ,-CH2CH(OH)CH2- ,-CH2CH(OR)CH2- ,-CH2CH(OC(O)R)CH2- ,-CH2CH2C(O)OCH2CH2- ,-
CH2CH(Me)C(O)OCH2CH2- ,-CH2CH2C(O)OCH2CH2OCH2CH2- ,-CH2CH2C(O)OCH2CH2CH2- ,-CH2CH2C
(O)OCH2CH2CH2CH2-, and the small molecule or polymeric groups of X or Q to be one have 2 or more-NHC (O) O- units,
And X or Q are preferably following groups：
Or, X or Q, which are one, has the small molecule or polymeric groups of 2 or more-C (O) O- units, and X or Q are excellent
Choosing is following groups (wherein R11It is hydrogen or R)：
It is apparent that for this specialty working technical staff, it will therefore be readily appreciated that the polynary isocyanide in above-mentioned X or Q structures
Acid esters【-NHC(O)O-】Unit or polyester【-C(O)O-】Unit is derived from R0Or R2Hydroxyl OH in structure with it is corresponding polynary
Polyurethane NCO group or polyacid or multi-anhydride or polynary carboxylic acid halides carry out esterification and got, therefore above-mentioned preferred X or Q knots
Structure is merely illustrative and non-restrictive structure, and every X or Q structures for meeting the substantive main idea of above-mentioned chemical reaction belong to the present invention
Disclose scope.
Or, when n values 2 or the integer more than 2 and work as R1When being R, X or Q structures are one and contain n members-CH2CH2C
(O) O- ,-CH2CH (Me) C (O) O- ,-CH2CH2C (O) C (O) O- ,-CH2CH (Me) C (O) C (O) O- ,-CH2CH2C(O)C
(O)-,-CH2CH (Me) C (O) C (O)-,-CH2CH2C (O) C (O) NH- ,-CH2CH (Me) C (O) C (O) NH- ,-CH2CH2C
(O)-,-CH2CH (Me) C (O)-,-CH2CH2C (O) NH- ,-CH2CH (Me) C (O) NH- ,-CH2CH2C (O) NR- ,-CH2CH(Me)
C (O) NR- ,-CH2CH2SO2- ,-CH2CH(Me)SO2- ,-CH2CH2S (O) R-, or-CH2The small molecule of CH (Me) S (O) R- units
Or polymeric groups, it is preferred that X or Q are following groups：
It is apparent that for this specialty working technical staff, it will therefore be readily appreciated that-the CH in above-mentioned X or Q structures2CH2C
(O) O- ,-CH2CH (Me) C (O) O- ,-CH2CH2C (O) C (O) O- ,-CH2CH (Me) C (O) C (O) O- ,-CH2CH2C(O)C
(O)-,-CH2CH (Me) C (O) C (O)-,-CH2CH2C (O) C (O) NH- ,-CH2CH (Me) C (O) C (O) NH- ,-CH2CH2C
(O)-,-CH2CH (Me) C (O)-,-CH2CH2C (O) NH- ,-CH2CH (Me) C (O) NH- ,-CH2CH2C (O) NR- ,-CH2CH
(Me) C (O) NR- ,-CH2CH2SO2- ,-CH2CH(Me)SO2- ,-CH2CH2S (O) R-, or-CH2The equal source of CH (Me) S (O) R- units
The intermediate of nucleophilic (nucleophilic) characteristic is come with to corresponding beta-unsaturated esters, unsaturated amides, unsaturated sulfone or sulfoxide
Deng Michael addition reaction prepare.Therefore above-mentioned preferred X or Q structures are merely illustrative and non-restrictive structure, every to meet
The small molecule or polymer-type X or Q structure of the substantive main idea of above-mentioned chemical reaction belong to present disclosure scope.
Or, when n values 2 or the integer more than 2, X or Q structures are one and contain n members-CH2CH (OH)-, or-CH2CH
(OR) small molecule or polymeric groups of-unit, it is preferred that X or Q are following groups：
It is apparent that for those of ordinary skills, it will therefore be readily appreciated that-the CH in above-mentioned X or Q structures2CH
(OH)-or-CH2CH (OR)-unit is derived from the intermediate with nucleophilic (nucleophilic) characteristic to corresponding epoxy compound
It is prepared by the ring-opening reaction of thing.Therefore above-mentioned preferred X or Q structures are merely illustrative and non-restrictive structure, every to meet above-mentionedization
The small molecule or polymer-type X or Q structure for learning the substantive main idea of reaction belong to present disclosure scope.
One of universality preparation method of logical formula (I) compound is shown below, from monosubstituted or disubstituted organic halogen
Change cumarin (Hal is halogen) set out, via known references method, such as Suzuki and Heck reaction, formed biphenyl group or
The substitution of person's styrene group, that is, obtain partial Formula (I) product；Or, on the basis of product prepared by demethylation to carry hydroxyl
The intermediate of base, then carries out into ether, epoxy ring opening reaction, isocyanates addition reaction (esterification), and Michael's conjugation adds
Into reaction, esterification etc., obtain another part and lead to formula (I) product.
The preparation method of above-mentioned logical formula (I) compound we will do further exemplary illustration by son in conjunction with the embodiments.
Meeting the preparation method of another part compound of above-mentioned logical formula (I) is, via a class of the formula of a starting
Coumarin compound (I)-A, so-called Blanc reactions occur under acid and formaldehyde collective effect, corresponding halide is obtained
(I)-B (wherein r values 1 or 2), acid is Louis or Bronsted acid here, and preferred acid is alchlor, alchlor, hydrochloric acid,
Hydrobromic acid, acetic acid, or above-mentioned sour appropriate mixture；Hal represents halogen atom, and Hal preferably is chlorine.Key intermediate (I)-
Under suitable nucleopilic reagent HNu effects nucleophilic substitution occurs for B, that is, prepares target compound (I)-C.It is preferred that parent
Core reagent HNu is the species for containing aerobic, nitrogen, sulphur, or phosphorus atoms, and particularly preferred HNu is water, NR3, HNRR ', H2NR, HSR,
RSSR ', HP (O) RR ', or the heterocycle containing aerobic, nitrogen, sulphur, or phosphorus atoms.
The exemplary compounds for meeting logical formula (I) structure are listed below：
The present invention further disclose it is a kind of it is containing above-mentioned logical formula (I) compound, can via light (ultraviolet or visible ray or
LED light or equal lamp-house) radiation curing mixture, and this kind of formula materials system is in inkjet printing, paper printing, bonding
Agent, woodwork coating, plastic coating, painting dressing automobiles, packaging material, flexible electronic, the application in the field such as photovoltaic material.
This kind of light radiation curing formula system is characterized in：
(1) contain the compound described by least one logical formula (I) as light sensitising agent, draw simultaneously containing at least one light
Send out agent；
(2) containing it is at least one containing ethylene linkage (C=C) unsaturated compound or containing at least one compound containing epoxy or
Both mixtures.
Calculated with the every 100 parts of weight of insatiable hunger containing ethylene linkage in system and/or epoxy component total amount, the logical formula (I) compound contained
Suitable amount be 0.01-30 parts by weight, preferred 0.5-10 parts by weight.The appropriate radiation curing system that this application is disclosed is included
The radical polymerization that can be by double bond of polymerizable unsaturated component or epoxy component or both the mixture containing ethylene linkage it is anti-
Should or epoxy bond the compound that is crosslinked of cationic polymerization or mixture, this unsaturated component containing ethylene linkage can be single
Body, oligomer or prepolymer, or their mixture or copolymer, or said components water-borne dispersions, it is this contain ring
Oxygen component can be monomer, oligomer or prepolymer, or their mixture or copolymer.
Appropriate radiation curing system described above inorganic or organic can be filled out containing what is added according to actual needs
Fill agent and/or colouring agent (such as pigment or dyestuff), and other additives (such as ultra-violet absorber, light stabilizer, resistance
Fire agent, levelling agent, or defoamer etc.) and any condition such as solvent.
The monomer of suitable radical polymerization is such as polymerisable monomer containing ethylene linkage, includes but is not limited to (methyl) acrylic acid
Ester, methacrylaldehyde, alkene, conjugated diolefin, styrene, maleic anhydride, fumaric acid anhydride, vinyl acetate, vinyl pyrrolidone,
Vinyl imidazole, (methyl) acrylic acid, (methyl) acrylic acid derivative such as (methyl) acrylamide, vinyl halide is sub-
Vinyl halide etc..The monomer of suitable cationic polymerization is such as polymerisable monomer containing epoxy, includes but is not limited to (first
Base) glycidyl acrylate, allyl glycidyl ether, epoxyalkane etc..
Suitable prepolymer containing ethylene linkage and oligomer include but is not limited to (methyl) propylene of (methyl) acryloyl functional group
Acid copolymer, polyurethane formic acid esters (methyl) acrylate, polyester (methyl) acrylate, unsaturated polyester (UP), polyethers (methyl)
The water solubility of acrylate, siloxanes (methyl) acrylate, epoxy resin (methyl) acrylate etc., and above-mentioned substance or
The analog of water dispersible.The monomer of suitable cationic polymerization is that polymerizable prepolymer and oligomer for example containing epoxy include
But it is not limited to poly- (methyl) glycidyl acrylate, poly allyl glycidylether etc..
Above-mentioned monomer or oligomer, prepolymer, or copolymer either containing alkene or epoxy, to this professional working technology
For personnel, all it is well known, is not particularly limited.
For idea of the invention, we will further illustrate with reference to following series embodiments.
【Embodiment】
Embodiment zero：7-methoxy-3-(3-(methylthio)phenyl)-2H-chromen-2-one
Under nitrogen protection, into acetonitrile (50mL) solution containing ayapanin (5.00g, 28.40mmol)
Add after N-bromosuccinimide (7.61g, 42.61mmol) and ammonium acetate (0.22g, 2.84mmol), be stirred at room temperature 10 small
When.After reaction terminates, mixture is extracted with ethyl acetate (3 × 100mL), saturated aqueous common salt and water washing, and organic layer is with anhydrous
Sodium sulphate is dried, and (eluent is separated with silica gel column chromatography after solvent evaporated：Dichloromethane/petroleum ether, 2：1,500 milliliter) obtain
White product (5.79g, yield 80.0%).1H NMR(400MHz,CDCl3) δ 8.02 (s, 1H), 7.36 (d, J=8.7Hz,
1H), 6.87 (d, J=8.7Hz, 1H), 6.82 (d, J=2.4Hz, 1H), 3.88 (s, 3H).
Under nitrogen protection, the bromo- 7- methoxyl groups of 3- are sequentially added in the 150mL flasks equipped with reflux condensing tube and agitator
Cumarin (2.05g, 7.84mmol), 3- first mercaptophenyl boronic acid (1.32g, 7.84mmol), potassium carbonate (3.30g,
23.52mmol), Pd (PPh3)4(0.50g, 0.39mmol) and toluene/ethanol/water (v/v/v, 5:3:1,40mL:24mL:8mL)
As reaction dissolvent, it is heated to reflux under stirring 48 hours.It is cooled to after room temperature and (3 × 100mL) is extracted with dichloromethane, saturation food
After salt solution and deionized water washing, solvent evaporated (eluent is separated with silica gel column chromatography：Dichloromethane/petroleum ether, 1：1,500
Milliliter) obtain light product (2.05g, yield 87.5%).1H NMR(400MHz,CDCl3)δ7.75(s,1H),7.56(s,
1H), 7.44 (m, 2H), 7.34 (m, 1H), 7.26 (d, J=7.8Hz, 1H), 6.86 (m, 2H), 3.88 (s, 3H), 2.52 (s,
3H)。13C NMR(101MHz,CDCl3)δ162.76,160.71,155.38,140.26,138.78,135.68,128.96,
128.80,126.60,126.47,125.24,124.27,113.23,112.85,100.42,55.83,15.94.HRMS(M+H)
for C17H15O3S:299.0742(calculated),299.0756(experimental)；(M+Na)for C17H14NaO3S:
321.0561(calculated),321.0568(experimental)。
Embodiment one：7-methoxy-3-(4-methoxyphenyl)-2H-chromen-2-one
It is raw material with 4- methoxyphenylboronic acids with the same synthetic method of above-described embodiment zero.Yield：90.2%.
HRMS(M+H)for C17H15O4:283.0970(calculated),283.0982(experimental)；(M+Na)for
C17H14NaO4:305.0790(calculated),305.0810(experimental)。
Embodiment two：3-mesityl-7-methoxy-2H-chromen-2-one
It is raw material with 2,4,6- trimethylbenzene boric acid with the same synthetic method of above-described embodiment zero.Yield：
75.2%.HRMS(M+H)for C19H19O3:295.1334(calculated),295.1352(experimental)；(M+Na)
for C19H18NaO3:317.1154(calculated),317.1146(experimental)。
Embodiment three：(E)-7-methoxy-3-(3-(methylthio)styryl)-2H-chromen-2-one
Under nitrogen protection, sequentially add at room temperature into 30mL DMF the bromo- ayapanins of 3- (0.85g,
3.33mmol), 3- first sulfydryl styrene (0.50g, 3.33mmol), Anhydrous potassium carbonate (1.39g, 9.99mmol) and catalyst Pd
(PPh3)2Cl2(30.00mg, 0.04mmol), 130 degree of stirring reactions are after 48 hours, and reactant mixture is poured into cold water, uses dichloro
Methane extracts (3 × 50mL), distills water washing, and anhydrous magnesium sulfate is dried, is concentrated under reduced pressure, the purification of crude product purified by silica gel column chromatography,
Leacheate is dichloromethane/petroleum ether (1/1), obtains yellow solid product (0.86g, yield 80.0%).1H NMR
(400MHz,CDCl3) δ 7.61 (s, 1H), 7.38 (d, J=17.5Hz, 1H), 7.29 (m, 2H), 7.17 (d, J=6.7Hz,
2H), 7.06 (d, J=6.4Hz, 1H), 6.95 (d, J=16.3Hz, 1H), 6.72 (m, 2H), 3.76 (s, 3H), 2.42 (s,
3H)。HRMS(M+H)for C19H17O3S:325.0898(calculated),325.0910(experimental)；(M+Na)
for C19H16NaO3S:347.0718(calculated),347.0721(experimental)。
Example IV：3-(3-(hydroxymethyl)-2,4,6-trimethylphenyl)-7-methoxy-2H-
chromen-2-one
Protected in nitrogen and at room temperature, 1.5 grams of paraformaldehyde solids and 5.65 grams of alchlor powder are dispersed in 120 millis
Rise in dry dichloroethanes, 3.48 grams of products of embodiment two are slowly added dropwise when system is warming up to 45 degree thereto at 80 milliliter two
Solution in chloroethanes, maintenance reaction is less than reflux temperature, and reaction solution is poured on frozen water by drop after finishing half an hour, and point liquid is dried,
Concentration, solid re-crystallizing in ethyl acetate obtains 3.43 grams of flaxen target products, is used directly for the next step.
Protected in nitrogen and at room temperature, previous step product is placed in 10 milliliters of DMF and 10 milliliter of Acetic acid-sodium acetate bufferings molten
In liquid (pH~8), reaction is poured on frozen water after being stirred at room temperature overnight, point liquid, is dried, concentration, solid with ethyl acetate-oneself
Alkane gradient elution on silica gel column chromatography obtains 0.68 gram of faint yellow solid target product.HRMS(M+H)for C20H21O4:
325.1440(calculated),325.1452(experimental)；(M+Na)for C20H20NaO4:347.1259
(calculated),347.1262(experimental)。
Embodiment five：3-(4-hydroxyphenyl)-7-methoxy-2H-chromen-2-one
Under nitrogen protection, the product of 3.6 grams of embodiments one is scattered in 20 milliliters of HI solution, is heated to reflux 1 hour,
TLC monitoring reactions terminate, and system is cooled to after room temperature and is poured into water, and dichloromethane extracts three times (50 milliliters), and saturation is used successively
Saline solution and water washing, point liquid, sodium sulphate are dried, filtering, and obtained clear liquid concentration, which is removed, obtains crude product with anhydrous after solution
Ethyl alcohol recrystallization obtains 3.1 grams of light yellow product.HRMS(M+H)for C16H13O4:269.0814(calculated),
269.0802(experimental)；(M+Na)for C16H12NaO4:291.0633(calculated),291.0628
(experimental)。
Embodiment six：3,3'-((ethane-1,2-diylbis(oxy))bis(4,1-phenylene))bis(7-
methoxy-2H-chromen-2-one)
Under nitrogen protection, carbon is added into acetone (30 milliliters) solution containing embodiment five (3.46 grams) at room temperature
Sour potassium (2.76 grams) afterwards with 1,2- Bromofumes (0.94 gram), finish reaction system and continue to be stirred at reflux after 24 hours, be poured into 100
In milliliter water, extracted with dichloromethane, organic phase is successively with 1% sodium bicarbonate aqueous solution and saturated common salt water washing, point liquid, sulphur
Sour sodium is dried, filtering, and obtained clear liquid concentration, which is removed, uses ethyl alcohol recrystallization after dichloromethane, obtain 3.26 grams of powdered targeteds
Compound.HRMS(M+H)for C34H27O8:563.1706(calculated),563.1726(experimental)；(M+Na)
for C34H26NaO8:585.1525(calculated),585.1536(experimental)。
Embodiment seven：LED light solidity test
Made (by weight percentage) by following formula containing ethylene linkage (acrylate) sample system：
Bisphenol A epoxy acrylate (Ebecryl 605)：25%；Amino acrylates (Ebecryl7100)：8%；Third
Epoxide glycerol tri-acrylate：25%；Hexanediyl ester：22%；Silicone acrylates：0.5%；Ethyoxyl
Tetramethylol methane tetraacrylate：3.5%；Sensitising agent：2% the present embodiment sensitising agent；Initiator：Benzoin dimethylether.
Above-mentioned preparation embodiment mixture is coated on about 30-35 microns of coating is formed on cardboard, 1 Shenzhen and day
The unit power of scientific ＆ technical corporation's production is 16W/cm2Launch wavelength be 395 nanometers of LED/light source (3 centimetres wide and 80 centimeter lengths
LED area light source), Variable-speed conveyor belt experiment.Press to scrape at quarter repeatedly using nail and do not produce criterion of the trace as photopolymerization curing completion.
Remaining smell test separately evaluates smell rank with 5 people, and the standard of assessment is as follows with numeral sign：0
Level：There is no smell；1 grade：Very slight smell；2 grades：Slight smell；3 grades：Obvious smell；4 grades：Strong smell；5
Level：Smell strongly.
As a result show the formula system containing embodiment compound one to six and consolidated with the Speed Efficient higher than 45 ms/min
Change, and oder levels are 0 or 0-1 grades.
It is above-mentioned test result indicates that these light triggers of the invention prepared are while have good LED light curing efficiency
Can be with (net) or low odor characteristics.
It is emphasized that the above-mentioned embodiment enumerated only is some exemplary tests, limited examination is not considered as
Test or condition.The innovation scope that the present patent application is covered should be recorded by claims and is defined.
Claims (4)
1. coumarin kind compound shown in logical formula (I)：
In above-mentioned logical formula (I) compound structure：
X-R0And R2- Q is containing R independently of one another3, R4, R5, R6, R7Substituted aryl (as shown in the figure), or R8, R9, R10Substitution
Tertiary alkyl, wherein R3, R4, R5, R6, R7Independent of each other is hydrogen, halogen atom, R, OR, SR, NRR ', CH2OH, CH2OR, or
CH2NRR ', wherein R or R ' independent of each other are (to be labeled as-C containing 1-24 carbon atom1-C24, similarly hereinafter) straight or branched
Alkyl or-C6-C12Can be containing 1-6 discrete oxygen, nitrogen, or element sulphur in aryl, R or R ' structures, R and R ' are deposited simultaneously
When can also form the ring system structure of 3-6 member therebetween.R8, R9, R10Independent of each other is any two among R, three
Person can also form the carbocyclic ring structure of a 3-6 member.It is preferred that, R3=R5=R7=CH3And R4=R6=H, or R3=R4=R6=
R7=H and R5=CH3, or R4=R5=OCH3And R3=R6=R7=H, or R3=R5=R7=CH3And R4=R6=CH2OH, or R3
=R5=R6=R7=H and R4=SCH3, or R3=R4=R6=R7=H and R5=SCH3, or R3=R5=R7=CH3And R4=R6=
CH2OC (O) R, or R3=R5=R7=CH3And R4=CH2OH and R6=H, or R3=R5=R7=CH3And R4=R6=CH2OR, or
R3=R5=R7=CH3And R4=R6=CH2NRR ', or R3=R5=R7=CH3And R4=CH2OH and R6=CH2NRR’.It is preferred that,
R8=R9=R10=H, or R8=R9=CH3, R10=H, or R8=R9=R10=CH2CH3, or R8=CH3And R9-R10It is hexamethylene
Structure；
Y is CH=CH, and oxygen element, or Y are not present；
Integer between n values 1-1000, it is preferred that the integer between n values 1-100, it is furthermore preferred that between n values 1-10
Integer；
R1It is H or R or-C (O)-R0, R preferably1It is H, CH3, CH2CH3, CH (CH3)2, C6H5, p-CH3OC6H4, CH2CH=CH2,
CH2Ph, C (O) CEt3, C (O) CMe3, xenyl；
As n=1, X-R0And R2- Q structures are hydrogen, the C containing 0-4 substituent6-C24Aryl (is preferably phenyl, biphenyl
Base, naphthyl), CH3, CH2CH3, CH (CH3)2, OR, CH2OH, CH2OR, CH2OC (O) R, CH2NRR ', CHR (OH), CRR ' (OH),
CCH3(CH2OH) OH, C (CH2OH)2OH, CH2CH2OH, CH2CHMeOH, CHMeCH2OH, CH2CHPhOH, CH2C (O) R, CH2CO2H
Or its metal salt or amine salt, CH2CH2CO2H or its metal salt or amine salt, CH2CH2C(O)OCH2CH2OH, CH2CHMeC(O)
OCH2CH2OH, CH2CH2C(O)OCH2CH2OCH2CH2OH, CH2CH2C (O) OZ, CH2OC (O)-NHZ, or CH2CH2OC (O) NHZ,
Here Z is one containing 2-6 C=C double bonds-C2-C36Group, preferably Z are one containing 2-6 acrylic ester unit
- C2-C36Group, preferred Z is one of following shown group：
When n values 2 or the integer more than 2, X and Q structures are a n member spacer groups；X or Q are preferably-CH2- ,-
CH2CH2- ,-CH2CH(OH)CH2- ,-CH2CH(OR)CH2- ,-CH2CH(OC(O)R)CH2- ,-CH2CH2C(O)OCH2CH2- ,-
CH2CH(Me)C(O)OCH2CH2- ,-CH2CH2C(O)OCH2CH2OCH2CH2- ,-CH2CH2C(O)OCH2CH2CH2- ,-CH2CH2C
(O)OCH2CH2CH2CH2-, and the small molecule or polymeric groups of X or Q to be one have 2 or more-NHC (O) O- units,
And X or Q are preferably following groups：
Or, X or Q are one has the small molecule or polymeric groups of 2 or more-C (O) O- units, and X or Q is preferred
It is following groups (wherein R11It is hydrogen or R)：
Or, when n values 2 or the integer more than 2 and work as R1When being R, X or Q structures are one and contain n members-CH2CH2C(O)
O- ,-CH2CH (Me) C (O) O- ,-CH2CH2C (O) C (O) O- ,-CH2CH (Me) C (O) C (O) O- ,-CH2CH2C (O) C (O)-,-
CH2CH (Me) C (O) C (O)-,-CH2CH2C (O) C (O) NH- ,-CH2CH (Me) C (O) C (O) NH- ,-CH2CH2C (O)-,-CH2CH
(Me) C (O)-,-CH2CH2C (O) NH- ,-CH2CH (Me) C (O) NH- ,-CH2CH2C (O) NR- ,-CH2CH (Me) C (O) NR- ,-
CH2CH2SO2- ,-CH2CH(Me)SO2- ,-CH2CH2S (O) R-, or-CH2The small molecule or polymer matrix of CH (Me) S (O) R- units
Group, it is preferred that X or Q are following groups：
Or, when n values 2 or the integer more than 2, X or Q structures are one and contain n members-CH2CH (OH)-, or-CH2CH
(OR) small molecule or polymeric groups of-unit, it is preferred that X or Q are following groups：
2. prepare the method for coumarin compound shown in partial Formula (I)：
Set out from monosubstituted or disubstituted organic halogenation cumarin (Hal is halogen), via known references method, for example
Suzuki-Miyaura and Heck reactions, with substitution phenyl boric acid or substituted phenylethylene in Pd catalyst (such as Pd (Ph4)3,Pd
(CH3COO)2) under, by alkali (such as triethanolamine, potassium carbonate) as acid-binding agent, prepare biphenyl group or styrene group
Substituted cumarin, that is, obtain partial Formula (I) product；
Or, demethylation prepares the intermediate with hydroxyl on the basis of with methoxy based products, then carries out into ether, epoxy
Ring-opening reaction, isocyanates addition reaction (esterification), Michael's conjugate addition reaction, esterification etc., obtain another portion
Divide logical formula (I) product.
Or, via class coumarin compound (I)-A for the formula of a starting, occur institute under acid and formaldehyde collective effect
The Blanc reactions of meaning, obtain corresponding halide (I)-B (wherein r values 1 or 2), acid is Louis or Bronsted acid here, excellent
The acid of choosing is alchlor, alchlor, hydrochloric acid, hydrobromic acid, acetic acid, or above-mentioned sour appropriate mixture；It is former that Hal represents halogen
Son, Hal preferably is chlorine.Under suitable nucleopilic reagent HNu effects nucleophilic substitution occurs for key intermediate (I)-B, i.e.,
Prepare target compound (I).It is preferred that nucleopilic reagent HNu be contain aerobic, nitrogen, sulphur, or phosphorus atoms species, particularly preferably
HNu be water, NR3, HNRR ', H2NR, HSR, RSSR ', HP (O) RR ', or the heterocycle containing aerobic, nitrogen, sulphur, or phosphorus atoms.
3. coumarin kind compound shown in logical formula (I) is used as sensitising agent or other functional additives in photocurable formulation system
The purposes of composition, and the purposes in chemical synthesis as intermediate or raw material or reagent.
4. it is a kind of containing above-mentioned logical formula (I) compound, it can be radiated via light (ultraviolet or visible ray or LED light or equal lamp-house)
The mixture of solidification.
Such light radiation curing formula system, it is characterized in that：
(1) compound described by least one logical formula (I) is contained as sensitising agent, simultaneously containing at least one light trigger；
And (2) are containing at least one is containing ethylene linkage (C=C) unsaturated compound or contains at least one compound containing epoxy or two
Person's mixture.
Calculated with the every 100 parts of weight of insatiable hunger containing ethylene linkage in system and/or epoxy component total amount, the conjunction of the logical formula (I) compound contained
Suitable amount is 0.01-30 parts by weight, preferably 0.5-10 parts by weight.
Polymerizable unsaturated component or epoxy component or both the mixture containing ethylene linkage that suitable Radiation-curing system is included is
The compound or mixture that can be crosslinked by the Raolical polymerizable of double bond or the cationic polymerization of epoxy bond, this
Kind of the unsaturated component containing ethylene linkage can be monomer, oligomer or prepolymer, or their mixture or copolymer, or above-mentioned
The water-borne dispersions of component, this can be monomer, oligomer or prepolymer containing epoxy component, or their mixture or altogether
Polymers.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110256424A (en) * | 2019-07-03 | 2019-09-20 | 武汉工程大学 | A kind of synthetic method of Pa Boxini key intermediate V |
| CN111324009A (en) * | 2018-12-13 | 2020-06-23 | 常州强力先端电子材料有限公司 | Photocurable composition and use thereof |
| CN111601795A (en) * | 2017-12-14 | 2020-08-28 | 意大利艾坚蒙树脂有限公司 | Water-soluble 3-coumarin ketones |
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| US20060147840A1 (en) * | 2005-01-06 | 2006-07-06 | Konica Minolata Medical & Graphic, Inc. | Photopolymerizable composition, light sensitive planographic printing plate material and manufacturing method of planographic printing plate |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111601795A (en) * | 2017-12-14 | 2020-08-28 | 意大利艾坚蒙树脂有限公司 | Water-soluble 3-coumarin ketones |
| CN111601795B (en) * | 2017-12-14 | 2024-03-19 | 意大利艾坚蒙树脂有限公司 | Water-soluble 3-coumarin ketone |
| CN111324009A (en) * | 2018-12-13 | 2020-06-23 | 常州强力先端电子材料有限公司 | Photocurable composition and use thereof |
| CN110256424A (en) * | 2019-07-03 | 2019-09-20 | 武汉工程大学 | A kind of synthetic method of Pa Boxini key intermediate V |
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