CN113683714B - Thioether type naphthalimide derivative photoinitiator containing hydrogen donor and suitable for UV-LED aerobic light curing - Google Patents
Thioether type naphthalimide derivative photoinitiator containing hydrogen donor and suitable for UV-LED aerobic light curing Download PDFInfo
- Publication number
- CN113683714B CN113683714B CN202010418614.7A CN202010418614A CN113683714B CN 113683714 B CN113683714 B CN 113683714B CN 202010418614 A CN202010418614 A CN 202010418614A CN 113683714 B CN113683714 B CN 113683714B
- Authority
- CN
- China
- Prior art keywords
- photoinitiator
- chloride
- anhydrous
- hydrogen donor
- intermediate product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical class C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000000852 hydrogen donor Substances 0.000 title claims abstract description 37
- 150000003568 thioethers Chemical class 0.000 title claims abstract description 21
- 238000000016 photochemical curing Methods 0.000 claims abstract description 16
- 238000001723 curing Methods 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 44
- 239000013067 intermediate product Substances 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 33
- 239000003960 organic solvent Substances 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 31
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 239000012043 crude product Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 22
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 18
- 239000012044 organic layer Substances 0.000 claims description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000004925 Acrylic resin Substances 0.000 claims description 10
- 229920000178 Acrylic resin Polymers 0.000 claims description 10
- -1 N, N-dimethylamino Chemical group 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 9
- 150000001263 acyl chlorides Chemical class 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 150000004698 iron complex Chemical class 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 150000007529 inorganic bases Chemical class 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- DTUOTSLAFJCQHN-UHFFFAOYSA-N 4-bromo-1,8-naphthalic anhydride Chemical compound O=C1OC(=O)C2=CC=CC3=C2C1=CC=C3Br DTUOTSLAFJCQHN-UHFFFAOYSA-N 0.000 claims description 7
- 239000002274 desiccant Substances 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- UKSZBOKPHAQOMP-SVLSSHOZSA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 UKSZBOKPHAQOMP-SVLSSHOZSA-N 0.000 claims description 5
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 150000007530 organic bases Chemical class 0.000 claims description 5
- 150000003254 radicals Chemical class 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 5
- 235000019798 tripotassium phosphate Nutrition 0.000 claims description 5
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 4
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical class [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical group CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 4
- 239000012346 acetyl chloride Substances 0.000 claims description 4
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- RTGAJOPJZJDWAX-XVGSOSPHSA-N (1e,4e)-1,5-bis(3,5-dimethoxyphenyl)penta-1,4-dien-3-one;palladium Chemical compound [Pd].COC1=CC(OC)=CC(\C=C\C(=O)\C=C\C=2C=C(OC)C=C(OC)C=2)=C1.COC1=CC(OC)=CC(\C=C\C(=O)\C=C\C=2C=C(OC)C=C(OC)C=2)=C1 RTGAJOPJZJDWAX-XVGSOSPHSA-N 0.000 claims description 2
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical class [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical class N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- XOJNEFQLMRCOMS-UHFFFAOYSA-N ditert-butyl(phenyl)phosphane Chemical compound CC(C)(C)P(C(C)(C)C)C1=CC=CC=C1 XOJNEFQLMRCOMS-UHFFFAOYSA-N 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 229940032296 ferric chloride Drugs 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- QJPQVXSHYBGQGM-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 QJPQVXSHYBGQGM-UHFFFAOYSA-N 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 2
- 229940007718 zinc hydroxide Drugs 0.000 claims description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 14
- 239000001301 oxygen Substances 0.000 abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 13
- 238000006116 polymerization reaction Methods 0.000 abstract description 10
- 229920000642 polymer Polymers 0.000 abstract description 7
- 230000000977 initiatory effect Effects 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000005764 inhibitory process Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 239000003963 antioxidant agent Substances 0.000 abstract description 2
- 230000003078 antioxidant effect Effects 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical compound SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229920006254 polymer film Polymers 0.000 description 6
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 5
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 150000003141 primary amines Chemical class 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 108010055682 3-hydroxybutyryl-CoA dehydrogenase Proteins 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- PTDVPWWJRCOIIO-UHFFFAOYSA-N (4-methoxyphenyl)methanethiol Chemical compound COC1=CC=C(CS)C=C1 PTDVPWWJRCOIIO-UHFFFAOYSA-N 0.000 description 1
- CXSDOJZNGWCOBC-UHFFFAOYSA-N 1-methoxy-4-[(4-methoxyphenyl)methylsulfanylmethyl]benzene Chemical compound C1=CC(OC)=CC=C1CSCC1=CC=C(OC)C=C1 CXSDOJZNGWCOBC-UHFFFAOYSA-N 0.000 description 1
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical compound [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/04—Ortho- or peri-condensed ring systems
- C07D221/06—Ring systems of three rings
- C07D221/14—Aza-phenalenes, e.g. 1,8-naphthalimide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polymerisation Methods In General (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a thioether type naphthalimide derivative photoinitiator containing a hydrogen donor, which is suitable for UV-LED aerobic light curing, relates to the field of photosensitive polymers, and is provided based on the problem that the initiation performance of the existing photoinitiator is poor under the irradiation of a UV-LED light source and in the presence of oxygen; the invention prepares a photoinitiator containing hydrogen donor thioether type naphthalimide derivative, and provides a preparation method and application thereof in a photocuring system; the invention has the beneficial effects that: (1) the ultraviolet absorption wavelength of the photoinitiator prepared by the invention is obviously prolonged, and the photoinitiator has better ultraviolet absorption capacity within the wavelength range of an LED light source. (2) The photoinitiator prepared by the invention has obvious antioxidant polymerization inhibition effect. (3) The migration stability of the photoinitiator prepared by the invention is obviously improved.
Description
Technical Field
The invention relates to the field of photosensitive polymers, in particular to a preparation method and application of a hydrogen donor-containing thioether type naphthalimide derivative photoinitiator suitable for UV-LED (ultraviolet-light emitting diode) aerobic light curing.
Background
The UV light curing technology is a novel technology appeared in the middle of the 20 th century, and is a process for initiating a liquid substance with chemical reaction activity to be quickly converted into a solid substance by using ultraviolet light (the wavelength is 200-400 nm) as an energy source. Compared with the traditional heat curing technology, the method has the advantages of high speed, high efficiency, low pollution and low cost, and is a new 'green' technology which is developed rapidly. UV light curable products are composed of three parts of materials, namely photoinitiators, light curable resins and monomers (also known as reactive diluents).
Ultraviolet light emitting diodes (UV-LEDs) are semiconductor electronic devices that convert electrical energy into optical radiation, and UV-LEDs have been widely used as radiation devices in the fields of radiation curing reactions and the like. Compared with the traditional UV light source, the UV-LED light source has the following characteristics: (1) Almost can emit monochromatic light, and has very narrow spectral line width (5-20 nm); (2) luminous output is almost 100%; (3) the energy consumption is low; (4) no ozone is generated; (5) no ultraviolet radiation; (6) the amount of heat generated is low; (7) the operation cost is low; (8) the service life is long; (9) the operation is safe and simple; (10) the design is compact, and the carrying is convenient. The UV-LED light source with low energy consumption and high safety performance is used in industry, so that the safety of personnel can be ensured, and the expenditure can be reduced. In view of the characteristics of advancement, economy, environmental friendliness and the like, the UV-LED has a good development prospect and is applied to some potential new fields.
UV-LED photocuring technology is currently limited by the absorption wavelength of the photoinitiator and the problem of oxygen inhibition during curing. Most of the reported or commercialized photoinitiators have poor absorption of light energy at wavelengths above 365nm, and have poor initiation properties under irradiation with a UV-LED light source. In addition, these commercial photoinitiators are sensitive to oxygen, and must be strictly removed of oxygen during use, which severely limits the development and popularization of UV-LED photocuring technology.
Disclosure of Invention
The invention provides a thioether type naphthalimide derivative photoinitiator containing a hydrogen donor and suitable for UV-LED aerobic photocuring and a preparation method thereof. The photoinitiator can well initiate the photopolymerization of monomers to generate a polymer film in the presence of oxygen and has low mobility. Through extensive and intensive research, a series of hydrogen donor-containing thioether type naphthalimide derivative photoinitiators suitable for UV-LED aerobic light curing are prepared through molecular design.
In order to realize the purpose, the invention adopts the following technical scheme:
1. a thioether-type naphthalimide derivative photoinitiator containing a hydrogen donor and suitable for UV-LED aerobic light curing is characterized in that: the chemical structural general formula of the photoinitiator is shown as follows:
wherein the value range of n is 1-10; r 1 Is selected from C 3 -C 20 Aliphatic alkyl groups, hydroxyl groups, vinyl groups, propenyl groups, methyl groups, ethyl groups, alkoxy groups, halogen atoms, aralkyl groups, or phenyl groups; r 2 Selected from carboxyl, benzoyl, acetyl, acryloyl, methoxy, ethoxy, nitro.
2. The method of item 1, wherein: the value range of n is 1-5; r 1 Selected from vinyl, methyl; r 2 Selected from methoxy.
3. The method of item 2, wherein: the value of n is 1.
4. A method for preparing the photoinitiator containing hydrogen donor thioether type naphthalimide derivative and suitable for UV-LED aerobic light curing in the item 1, which is characterized in that: the general synthesis process is as follows:
5. the method of item 4, wherein: the preparation method of the hydrogen donor-containing thioether type naphthalimide derivative photoinitiator suitable for UV-LED aerobic light curing comprises the following steps:
(1) In the step a, primary amine and 4-bromo-1,8-naphthalic anhydride are added into a reaction vessel and react for 24 hours at the temperature of 60-100 ℃; after the reaction is finished, cooling, and then washing the crude product with absolute ethyl alcohol for multiple times to obtain a brownish red solid intermediate product A;
(2) In the step a, adding the intermediate product A and acyl chloride into a reaction vessel, adding an anhydrous organic solvent, and reacting for 6 hours at the temperature of 0-5 ℃; after the reaction is finished, carrying out reduced pressure distillation to remove the anhydrous solvent to obtain a crude product, and then purifying the crude product by using a chromatographic column to obtain a light yellow solid intermediate product B;
(3) In the step c, adding benzylmercaptan, acetic anhydride and a catalyst into a reactor, heating and refluxing for 12 hours, and stirring; after the reaction is finished, cooling, extracting by dichloromethane, combining organic layers, washing the organic layers by using a carbonate aqueous solution with a certain concentration respectively, then washing by using deionized water, drying the organic layers by using a drying agent, filtering, distilling under reduced pressure to remove a solvent to obtain a crude product, and then purifying the crude product by using a chromatographic column to obtain a colorless liquid intermediate product C;
(4) In the step d, mixing the intermediate product B prepared in the step B, the intermediate product C prepared in the step C, a palladium catalyst, an iron complex and alkali, adding a proper amount of an organic solvent 1 and an organic solvent 2, and reacting for 24 hours at 80-120 ℃ in a nitrogen atmosphere; and after the reaction is finished, cooling, pouring the reaction liquid into a proper amount of saturated salt solution for washing, then extracting with dichloromethane, combining organic phases, washing an organic layer with saturated saline water, drying the organic layer with a drying agent, filtering, distilling under reduced pressure to remove the solvent to obtain a crude product, and then purifying the crude product by using a chromatographic column to obtain a final product.
6. The method of item 5, wherein: in the step a, the mole number of the primary amine is 1-10 times of that of 4-bromo-1,8-naphthalic anhydride; the reaction temperature is 70-90 ℃.
7. The method of item 6, wherein: in the step a, the mole number of the primary amine is 3 to 6 times of that of 4-bromo-1,8-naphthalic anhydride.
8. The method of item 7, wherein: in the step a, the mole number of the primary amine is 5 times that of 4-bromo-1,8-naphthalic anhydride; the reaction temperature was 85 ℃.
9. The method of item 5, wherein: in the step b, the acyl chloride is one or more selected from acetyl chloride, acryloyl chloride, methacryloyl chloride, benzoyl chloride, terephthaloyl chloride, oxalyl chloride and p-toluenesulfonyl chloride; the mole number of the acyl chloride is 1 to 6 times of that of the intermediate product A; the organic base is selected from one or more of triethylamine, diethylamine, 4-dimethylamino pyridine, 3-methylpyridine and 2-methylpyridine; the mole number of the organic alkali is 1 to 7 times of that of the intermediate product A; the anhydrous organic solvent is selected from one or more of anhydrous dichloromethane, anhydrous ethanol, anhydrous petroleum ether, anhydrous acetone, anhydrous toluene and anhydrous tetrahydrofuran; the reaction temperature is 0-2 ℃.
10. The method of item 9, wherein: in the step b, the acyl chloride is selected from acetyl chloride and acryloyl chloride; the mole number of the acyl chloride is 2-4 times of that of the intermediate product A; the organic base is selected from triethylamine; the mole number of the organic alkali is 2-5 times of that of the intermediate product A; the anhydrous organic solvent is selected from anhydrous dichloromethane.
11. The method of item 10, wherein: in the step b, the mole number of the acyl chloride is 3 times that of the intermediate product A; the mole number of the organic base is 4 times that of the intermediate product A; the reaction temperature was 0 ℃.
12. The method of item 5, wherein: in the step c, the mole number of the acetic anhydride is 0.5 to 4.5 times that of the benzylmercaptan; the catalyst is one or more of ferric chloride, ferrous chloride, cupric chloride, cuprous chloride, nickel chloride, aluminum chloride, sodium nitrate, potassium nitrate and magnesium nitrate; the mole number of the catalyst is 0.001-0.020 times of that of benzyl mercaptan; the carbonate aqueous solution is one or more of a sodium carbonate aqueous solution, a potassium carbonate aqueous solution, an ammonium carbonate aqueous solution, a sodium bicarbonate aqueous solution, a potassium bicarbonate aqueous solution and an ammonium bicarbonate aqueous solution; the concentration of the carbonate aqueous solution is 1-25%.
13. The method of item 12, wherein: in the step c, the mole number of the acetic anhydride is 1.5 to 2.5 times that of the benzylmercaptan; the catalyst is nickel chloride; the mole number of the catalyst is 0.008 to 0.012 times of that of benzyl mercaptan; the carbonate aqueous solution is sodium bicarbonate aqueous solution; the concentration of the carbonate aqueous solution is 9-12%.
14. The method of item 13, wherein: in the step c, the mole number of the acetic anhydride is 2.0 times that of the benzylmercaptan; the mole number of the catalyst is 0.010 times of that of the benzylmercaptan; the concentration of the aqueous carbonate solution was 10%.
15. The method of item 5, wherein: in the step d, the palladium catalyst is selected from one or more of bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, bis (triphenylphosphine) palladium acetate, bis (di-tert-butylphenyl phosphine) palladium dichloride and bis (3,5,3 ',5' -dimethoxydibenzylideneacetone) palladium; the iron complex is selected from one or more of 1,1' -bis (diphenylphosphino) ferrocene, 1,1-bis diphenylphosphino ferrocene nickelous chloride, (S, S) - (-) -2,2' -bis [ - (N, N-dimethylamino) (phenyl) methyl ] -1,1' -bis (diphenylphosphino) ferrocene; the inorganic base is selected from one or more of sodium hydroxide, calcium hydroxide, aluminum hydroxide, lithium hydroxide, magnesium hydroxide, zinc hydroxide and anhydrous tripotassium phosphate; the mole number of the palladium catalyst is 0.1-0.8 times of that of the intermediate product B; the mole number of the iron complex is 0.10-0.20 times of that of the intermediate product B; the mole number of the inorganic base is 1.0-5.0 times of that of the intermediate product B; the mole number of the intermediate product C is 1-5 times that of the intermediate product B; the reaction temperature is 90-115 ℃; the organic solvent 1 and the organic solvent 2 are the same or different and are respectively and independently selected from one or more of toluene, dichloromethane, methanol, acetone, petroleum ether, ethyl acetate and ethanol; the volume of the organic solvent 1 is 1-6 times of that of the organic solvent 2; the total volume of the organic solvent 1 and the organic solvent 2 is 1-24 mL; the saturated salt solution is selected from one or more of a saturated ammonium chloride solution, a saturated ammonium sulfate solution, a saturated magnesium chloride solution, a saturated sodium sulfate solution, a saturated potassium chloride solution and a saturated potassium nitrate solution.
16. The method of item 15, wherein: in step d, the palladium catalyst is selected from bis (dibenzylideneacetone) palladium; the iron complex is selected from 1,1' -bis (diphenylphosphino) ferrocene; the inorganic base is selected from anhydrous tripotassium phosphate; the mole number of the palladium catalyst is 0.3-0.7 times of that of the intermediate product B; the mole number of the iron complex is 0.12-0.18 times of that of the intermediate product B; the mole number of the inorganic base is 2.0-3.0 times of that of the intermediate product B; the mole number of the intermediate product C is 2-3 times that of the intermediate product B; the reaction temperature is 110 ℃; the organic solvent 1 is toluene; the organic solvent 2 is acetone; the volume of the organic solvent 1 is 2-4 times of that of the organic solvent 2; the total volume of the organic solvent 1 and the organic solvent 2 is 5-17 mL; the saturated salt solution is a saturated ammonium chloride solution.
17. The method of item 16, wherein: in the step d, the mole number of the palladium catalyst is 0.6 times that of the intermediate product B; the mole number of the iron complex is 0.14 times that of the intermediate product B; the mole number of the inorganic base is 2.4 times that of the intermediate product B; the mole number of the intermediate product C is 3 times that of the intermediate product B; the volume of the organic solvent 1 is 2 times of that of the organic solvent 2; the total volume of the organic solvent 1 and the organic solvent 2 is 12mL.
18. The method of item 5, wherein: in the step c and the step d, the drying agent is one or more selected from anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous magnesium chloride and anhydrous calcium chloride.
19. The method of claim 18, wherein: in the step b and the step c, the drying agent is anhydrous sodium sulfate.
20. A free radical photocurable composition comprising the hydrogen donor thioether-containing naphthalimide derivative photoinitiator suitable for UV-LED aerobic photocuring according to item 1; the composition comprises 0.1 to 5 percent of the photoinitiator containing the hydrogen donor thioether type naphthalimide derivative and 95 to 99.9 percent of light-cured resin or monomer based on the total weight of the composition.
21. The composition of item 20, wherein: the light-cured resin is selected from one or more of epoxy (methyl) acrylic resin, polyurethane (methyl) acrylic resin, polyester (methyl) acrylic resin, polyether (methyl) acrylic resin and acrylated poly (methyl) acrylic resin; the monomer is one or more of monofunctional or polyfunctional (methyl) acrylate.
In the following description of the present invention, numerical values in this application are to be considered modified by the word "about", unless expressly stated otherwise. However, the inventors have reported numerical values in the examples as precisely as possible, although such numerical values inevitably include certain errors.
In the present application, specific or preferred embodiments of the present invention may be combined, unless explicitly excluded. Each element of the embodiments of the present application is a specific preferred choice of the generic technical features corresponding thereto. If a feature of the above description can be combined with another feature of the above description, the elements of the embodiments, that is, the specific preferred options, can also be combined with the other feature of the above description. These combinations should be considered part of the original disclosure of the present application.
The invention also provides the application of the photoinitiator in a photocuring system.
The invention has the beneficial effects that: compared with the traditional photoinitiator, the photoinitiator prepared by the invention has obviously prolonged ultraviolet absorption wavelength, obviously improved anti-oxygen polymerization resistance, higher photocuring efficiency under the action of a UV-LED light source and in the presence of oxygen, and is beneficial to the development of the UV-LED photocuring industry; has lower mobility, and is beneficial to the development of food packaging industry.
Drawings
FIG. 1 is a diagram of the photoinitiation mechanism of the hydrogen donor-containing thioether-type naphthalimide derivative photoinitiator provided by the invention;
FIG. 2 is a diagram of the mechanism of the antioxidant inhibition of the photoinitiator containing hydrogen donor thioether type naphthalimide derivative provided by the invention;
FIG. 3 is a diagram showing an ultraviolet absorption spectrum of a hydrogen donor-containing thioether-type naphthalimide derivative photoinitiator prepared in example 1-2 of the present invention;
FIG. 4 is a real-time IR spectrum of a hydrogen donor-containing thioether-type naphthalimide derivative photoinitiator prepared in example 1-2 of the present invention and photoinitiators 2959, 184 and 1173 initiating polymerization of monomers in the presence of oxygen;
FIG. 5 is a graph showing migration stability of a hydrogen donor-containing thioether-type naphthalimide derivative photoinitiator prepared in example 1-2 of the present invention in a polymer film;
Detailed Description
The invention will be described in further detail below with reference to the drawings and examples of the specification.
The hydrogen donor-containing thioether type naphthalimide derivative photoinitiator can be subjected to two-way cleavage under the irradiation of an LED light source with the wavelength of 405nm to generate free radicals with initiating activity. As shown in the attached figure 1, under illumination, the photoinitiator firstly reaches an excited singlet state, and then a few excited-state molecules generate a p-methoxybenzyl radical and an aryl sulfur radical through a cracking mode 1; most excited molecules generate p-methoxybenzyl sulfide free radicals and aryl free radicals through a cracking mode 2, so that the monomer 1,6-hexanediol diacrylate (HDDA) is initiated to polymerize to generate the polymer film. The photoinitiator molecules containing the hydrogen donor thioether type naphthalimide derivative can still effectively initiate the monomer polymerization process in the presence of oxygen, as shown in figure 2, the photoinitiator molecules can generate a hydrogen abstraction reaction in an excited singlet state to generate alkyl radicals, and then the alkyl radicals are combined with the oxygen to generate peroxy radicals with a six-membered ring stable structure, but the peroxy radicals can not initiate the monomer polymerization; then, the peroxy radical generates new alkyl radicals to initiate the polymerization of the monomer through two ways of intramolecular hydrogen extraction (mode 1) and intermolecular hydrogen extraction (mode 2), thereby endowing the photoinitiator containing the hydrogen donor thioether-type naphthalimide derivative with the performance of reducing oxygen inhibition.
The experimental materials and reagents used in the following examples are commercially available unless otherwise specified.
[ example 1 ]
The photoinitiator NABS-HD-1 has the following structural formula:
the preparation method comprises the following steps:
(a) Adding 4-bromo-1,8-naphthalic anhydride (7.20g, 0.026mol), diglycolamine (13.67g, 0.13mol) and 100mL of absolute ethanol into a 250mL single-neck flask, heating to 85 ℃ under the protection of nitrogen, refluxing and stirring for 4 hours; after the reaction is finished, cooling the reaction liquid to room temperature, filtering to obtain a crude product, washing filter residues for multiple times by using absolute ethyl alcohol, and drying in vacuum to obtain an intermediate product, namely BHBD.
(b) BHBD (5.83g, 116mmol) synthesized in example 1, triethylamine (6.48g, 64 mmol) and 150mL of anhydrous dichloromethane were charged in a 250mL single-neck flask, acetyl chloride (3.77 g, 48mmol) was dissolved in 20mL of anhydrous dichloromethane, and the solution was added dropwise to the single-neck flask in an ice-water bath at 0 ℃ and stirred for 6 hours; after the reaction is finished, the solvent is removed by reduced pressure distillation to obtain a crude product, and then the crude product is purified by a chromatographic column to obtain an intermediate product which is named as BDBIEA.
(c) P-methoxybenzyl mercaptan (3.09g, 0.02mol), acetic anhydride (4.08g, 0.04mol) and anhydrous nickel chloride (259mg, 2mmol) were charged into a 50mL one-neck flask, heated to 75 deg.C, and stirred for 4h. After the reaction is finished, adding a proper amount of deionized water into the reactorExtracting with water and dichloromethane for 3 times, mixing organic layers, washing the organic layer with 10% sodium bicarbonate water solution and deionized water for 3 times, and passing the organic layer over anhydrous Na 2 SO 4 Drying, filtering, distilling under reduced pressure to remove the solvent to obtain a crude product, and purifying the crude product by using a chromatographic column to obtain an intermediate product MOBET;
(d) BDBIEA (812.46mg, 2mmol), MOBET (1.18g, 6mmol), bis (dibenzylideneacetone) palladium (690.60mg, 1.2mmol), 1,1' -bis (diphenylphosphino) ferrocene (98.70mg, 0.024mmol), anhydrous tripotassium phosphate (1.02g, 4.8mmol), 8mL toluene, and 4mL acetone synthesized in example 1 were charged into a 50mL three-necked flask, and the temperature was raised to 110 ℃ under nitrogen and stirred for 12 hours. After the reaction is finished, cooling the reaction liquid to room temperature, pouring the reaction liquid into 10mL of saturated ammonium chloride aqueous solution, extracting for 3 times by dichloromethane, combining organic phases, washing an organic layer for 3 times by saturated saline solution, and passing the organic layer through anhydrous Na 2 SO 4 Drying, filtering, distilling under reduced pressure to remove solvent to obtain crude product, purifying with chromatographic column to obtain final product NABS-HD-1, and performing structure identification by nuclear magnetic resonance spectroscopy.
The nuclear magnetic hydrogen spectrum data of the photoinitiator NABS-HD-1 are as follows: 1 H NMR(400MHz,Chloroform- d)δ8.63(dd,J＝7.6,1.2Hz,1H),8.58(dd,J＝8.4,1.2Hz,1H),8.46(d,J＝7.6Hz, 1H),7.76(dd,J＝8.8,7.6Hz,1H),7.60(d,J＝7.6Hz,1H),7.33(d,J＝8.8Hz,2H), 6.88(d,J＝8.8Hz,2H),4.45(t,J＝6.4Hz,2H),4.33(s,2H),4.19(dd,J＝4.8，4.4 Hz,2H),3.85(t,J＝6.0Hz,2H),3.80(s,2H),3.76(dd,J＝4.8，4.8Hz,2H),1.98(s, 3H)。
the nuclear magnetic carbon spectrum data of the photoinitiator NABS-HD-1 are as follows: 13 C NMR(100MHz,Chloroform- d)δ171.1,164.1,159.3,144.9,131.6,130.9,130.3,130.1,129.7,127.1,126.7,124.1, 123.1,119.5,114.3,68.5,67.9,63.7,55.3,38.9,37.1,29.7,20.9。
[ example 2 ] A method for producing a polycarbonate
The photoinitiator NABS-HD-2 has the following structural formula:
the preparation method comprises the following steps:
(a) BHBD (5.83g, 116mmol) synthesized in example 1, triethylamine (6.48g, 64 mmol) and 150mL of anhydrous dichloromethane were charged in a 250mL single-neck flask, acryloyl chloride (4.35g, 48mmol) was dissolved in 20mL of anhydrous dichloromethane, and the solution was added dropwise to the single-neck flask in an ice-water bath at 0 ℃ and stirred for 6 hours; after the reaction is finished, the solvent is removed by reduced pressure distillation to obtain a crude product, and then the crude product is purified by a chromatographic column to obtain an intermediate product which is named as BDBIEB.
(b) BDBIEB (836.90mg, 2mmol), MOBET (1.18g, 6mmol), bis (dibenzylideneacetone) palladium (690.60mg, 1.2mmol), 1,1' -bis (diphenylphosphino) ferrocene (98.70mg, 0.024mmol), anhydrous tripotassium phosphate (1.02g, 4.8mmol), 8mL toluene, and 4mL acetone synthesized in example 1 were charged into a 50mL three-necked flask, and the temperature was raised to 110 ℃ under nitrogen protection and stirred for 12 hours. After the reaction is finished, cooling the reaction liquid to room temperature, pouring the reaction liquid into 10mL of saturated ammonium chloride aqueous solution, extracting for 3 times by dichloromethane, combining organic phases, washing an organic layer for 3 times by saturated saline solution, and passing the organic layer through anhydrous Na 2 SO 4 Drying, filtering, distilling under reduced pressure to remove solvent to obtain crude product, purifying with chromatographic column to obtain final product NABS-HD-2, and performing structure identification by nuclear magnetic resonance spectroscopy.
The nuclear magnetic hydrogen spectrum data of the photoinitiator NABS-HD-2 is as follows: 1 H NMR(400MHz,Chloroform- d)δ8.63(dd,J＝7.2，1.2Hz,1H),8.59(dd,J＝7.2，1.2Hz,1H),8.46(d,J＝8.0Hz, 1H),7.76(dd,J＝8.4,7.2Hz,1H),7.61(d,J＝8.0Hz,1H),7.34(d,J＝8.4Hz,2H), 6.89(d,J＝8.4Hz,2H),6.33(dd,J＝17.2，1.6Hz,1H),6.05(d,J＝17.6，10.4Hz, 1H),5.73(d,J＝10.4，1.6Hz,1H),4.46(t,J＝6.0Hz,2H),4.43(s,2H),4.29(dd,J＝ 4.8，4.8Hz,2H),3.87(t,J＝6.0Hz,2H),3.81(s,2H),3.80(dd,J＝4.8，4.4Hz,2H)。
the nuclear magnetic carbon spectrum data of the photoinitiator NABS-HD-2 are as follows: 13 C NMR(100MHz,Chloroform- d)δ166.1,164.0,163.9,159.3,144.9,131.5,130.8,130.7,130.2,130.1,129.5,128.2, 128.1,126.9,126.6,123.8,122.9,119.3,114.2,68.5,67.9,63.7,55.3,38.9,36.9。
[ examples 3 to 8 ]
Examples 3 to 8 are intended to demonstrate that the photoinitiator containing a hydrogen donor thioether-type naphthalimide derivative prepared in examples 1 to 2 can effectively initiate the polymerization of the monomer 1,6-hexanediol diacrylate (HDDA) in an oxygen-existing environment under the irradiation of a UV-LED light source; the initiation activity is higher than that of the prior photoinitiators 2959, 184 and 1173.
(1) Preparing a photosensitive resin composition: the mixture ratio is as follows:
a:1,6 hexanediol diacrylate (99.5 or 98 parts by mass)
B: photoinitiator (0.5 parts by mass)
C: photoinitiator (2.0 parts by mass)
Table 1 shows the composition ratios in the examples:
(2) Test for polymerization Properties
The test method comprises the following steps: stirring the above composition uniformly in dark, coating on potassium bromide salt sheet with capillary tube to form a film of about 30 μm, and placing in real-time infrared instrument (American Saimer Feishell science and technology Co., model UVEC-411, light intensity 100 mW/cm) 2 ) The coating film was exposed to light at a wavelength of 405nm for a period of 900s.
And (3) testing results: FIG. 3 shows that the hydrogen donor-containing thioether-type naphthalimide derivative photoinitiators prepared in examples 1-2 have good ultraviolet absorption capacity at the emission wavelength of the LED light source; FIG. 4 shows that the photosensitive resin composition containing three commercial photoinitiators can not initiate the polymerization of monomers under the irradiation of a 405nm UV-LED light source and in the presence of oxygen (examples 3-5), while the photosensitive resin composition containing the photoinitiator of thioether type naphthalimide derivative containing a hydrogen donor prepared by the invention can successfully initiate the photopolymerization under the irradiation of a 405nm UV-LED light source and in the presence of oxygen (examples 6-8), which indicates that the photoinitiator of thioether type naphthalimide derivative containing a hydrogen donor prepared by the invention has better applicability in a UV-LED oxygen photocuring system.
[ example 9 ]
This example is intended to illustrate that NABS-HD-2, a photoinitiator of thioether type naphthalimide derivative containing hydrogen donor prepared in example 2, can have a lower mobility in a polymer film.
The test method comprises the following steps: weighing 0.01g of the thioether-type naphthalimide derivative photoinitiator containing the hydrogen donor prepared in the embodiment 1-2 and 2.00g of 1,6-hexanediol diacrylate (HDDA) respectively, and mixing to prepare a photosensitive solution; preparing a template by using a silica gel film with the thickness of 1-2mm, and padding a glass sheet with the thickness of 2mm on the bottom of the template; introducing the photosensitive solution into the template, uniformly coating without bubbles, and covering a cover glass; irradiating the photosensitive solution by using an LED light source with the wavelength of 405nm until the photosensitive solution is solidified; grinding the cured resin into powder, taking 1g of the ground resin powder, and soaking the powder in 20mL of anhydrous acetone for 3 days; the sample was filtered to remove solids to obtain a liquid, and a liquid chromatogram was obtained using a liquid chromatograph-mass spectrometer (Waters, USA), as shown in FIG. 5.
And (3) testing results: FIG. 5 shows that, in the liquid chromatogram after extraction of the polymer film containing NABS-HD-1, the peak a appearing at 5.71min is assigned to HDDA molecules, and the peak b appearing at 6.40min is assigned to NABS-HD-1 molecules contained in the polymer, and the peaks are very distinct, which indicates that the NABS-HD-1 molecules are free in the polymer and easily migrate out of the polymer. In contrast, in the liquid chromatogram after the extraction of the polymer film of NABS-HD-2, only the peak of HDDA appears in the figure, and the chromatographic peak of NABS-HD-2 is not found. This indicates that the probability of NABS-HD-2 migrating out of the polymer matrix is much lower than that of NABS-HD-1, because the carbon-carbon double bond existing in the molecule of NABS-HD-2 can also participate in polymerization reaction and be anchored on the polymer skeleton, making it difficult to migrate. The photoinitiator NABS-HD-2 has excellent migration stability.
The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above examples, and various process schemes having no substantial difference from the concept of the present invention are within the protection scope of the present invention.
Claims (10)
1. The hydrogen donor-containing thioether type naphthalimide derivative photoinitiator suitable for UV-LED aerobic light curing is characterized in that the structural formula of the hydrogen donor-containing thioether type naphthalimide derivative photoinitiator is as follows:
wherein n is 1; r 1 Is vinyl or methyl; r is 2 Is methoxy.
2. The preparation method of the hydrogen donor-containing thioether type naphthalimide derivative photoinitiator applicable to UV-LED aerobic light curing in claim 1 is characterized in that the synthesis process is as follows:
(a)
(b)
(c)
(d)
3. the method for preparing the hydrogen donor-containing thioether-type naphthalimide derivative photoinitiator suitable for UV-LED aerobic photo-curing according to claim 2, wherein the method comprises the following steps: the preparation method of the photoinitiator comprises the following steps:
(1) In the step a, primary amine and 4-bromo-1,8-naphthalic anhydride are added into a reaction vessel and react for 24 hours at the temperature of 60-100 ℃; after the reaction is finished, cooling, and then washing the crude product with absolute ethyl alcohol for multiple times to obtain a brownish red solid intermediate product A;
(2) In the step b, adding the intermediate product A, acyl chloride and organic base into a reaction vessel, adding an anhydrous organic solvent, and reacting for 6 hours at the temperature of 0-5 ℃; after the reaction is finished, carrying out reduced pressure distillation to remove the anhydrous organic solvent to obtain a crude product, and then purifying the crude product by using a chromatographic column to obtain a light yellow solid intermediate product B;
(3) In step c, mixing
Adding acetic anhydride and a catalyst into a reactor, heating and refluxing for 12 hours, and stirring; after the reaction is finished, cooling, extracting by dichloromethane, combining organic layers, washing the organic layers by using a carbonate aqueous solution with a certain concentration respectively, then washing by using deionized water, drying the organic layers by using a drying agent, filtering, distilling under reduced pressure to remove a solvent to obtain a crude product, and then purifying the crude product by using a chromatographic column to obtain a colorless liquid intermediate product C;
(4) In the step d, mixing the intermediate product B prepared in the step B, the intermediate product C prepared in the step C, a palladium catalyst, an iron complex and an inorganic base, adding a proper amount of an organic solvent 1 and an organic solvent 2, and reacting for 24 hours at 80-120 ℃ in a nitrogen atmosphere; after the reaction is finished, cooling, pouring the reaction solution into a proper amount of saturated salt solution for washing, then extracting with dichloromethane, combining organic phases, washing an organic layer with saturated saline water, drying the organic layer with a drying agent, filtering, distilling under reduced pressure to remove the solvent to obtain a crude product, and then purifying the crude product with a chromatographic column to obtain a final product; the organic solvent 1 is the same as or different from the organic solvent 2, and is respectively and independently selected from one or more of toluene, dichloromethane, methanol, acetone, petroleum ether, ethyl acetate and ethanol.
4. The method for preparing the photoinitiator containing hydrogen donor thioether-type naphthalimide derivative suitable for UV-LED aerobic photo-curing according to claim 3, wherein in the step a, the mole number of the primary amine is 1-10 times that of 4-bromo-1,8-naphthalic anhydride; the reaction temperature is 70-90 ℃.
5. The method for preparing the thioether-type naphthalimide derivative photoinitiator containing hydrogen donors for aerobic photocuring of UV-LED according to claim 3, wherein the thioether-type naphthalimide derivative photoinitiator comprises the following steps: in the step b, the acyl chloride is selected from acetyl chloride or acryloyl chloride; the mole number of the acyl chloride is 1 to 6 times of that of the intermediate product A; the organic base is selected from one or more of triethylamine, diethylamine, 4-dimethylamino pyridine, 3-methylpyridine and 2-methylpyridine; the mole number of the organic alkali is 1 to 7 times of that of the intermediate product A; the anhydrous organic solvent is selected from one or more of anhydrous dichloromethane, anhydrous ethanol, anhydrous petroleum ether, anhydrous acetone, anhydrous toluene and anhydrous tetrahydrofuran; the reaction temperature is 0-2 ℃.
6. The method for preparing the hydrogen donor-containing thioether-type naphthalimide derivative photoinitiator suitable for UV-LED aerobic photo-curing according to claim 3, wherein the method comprises the following steps: in the step c, the mole number of the acetic anhydride is
0.5-4.5 times of the total weight of the composition; the catalyst is one or more of ferric chloride, ferrous chloride, cupric chloride, cuprous chloride, nickel chloride, aluminum chloride, sodium nitrate, potassium nitrate and magnesium nitrate; the mole number of the catalyst is
0.001 to 0.020 times of; the carbonate aqueous solution is one or more of a sodium carbonate aqueous solution, a potassium carbonate aqueous solution, an ammonium carbonate aqueous solution, a sodium bicarbonate aqueous solution, a potassium bicarbonate aqueous solution and an ammonium bicarbonate aqueous solution; the concentration of the carbonate aqueous solution is 1-25%.
7. The method for preparing the hydrogen donor-containing thioether-type naphthalimide derivative photoinitiator suitable for UV-LED aerobic photo-curing according to claim 3, wherein the method comprises the following steps: in the step d, the palladium catalyst is selected from one or more of bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, bis (triphenylphosphine) palladium acetate, bis (di-tert-butylphenyl phosphine) palladium dichloride and bis (3,5,3 ',5' -dimethoxydibenzylideneacetone) palladium; the iron complex is selected from one or more of 1,1' -bis (diphenylphosphino) ferrocene, 1,1-bis diphenylphosphino ferrocene nickelous chloride, (S, S) - (-) -2,2' -bis [ - (N, N-dimethylamino) (phenyl) methyl ] -1,1' -bis (diphenylphosphino) ferrocene; the inorganic base is selected from one or more of sodium hydroxide, calcium hydroxide, aluminum hydroxide, lithium hydroxide, magnesium hydroxide, zinc hydroxide and anhydrous tripotassium phosphate; the mole number of the palladium catalyst is 0.1-0.8 times of that of the intermediate product B; the mole number of the iron complex is 0.10-0.20 times of that of the intermediate product B; the mole number of the inorganic base is 1.0-5.0 times of that of the intermediate product B; the mole number of the intermediate product C is 1-5 times that of the intermediate product B; the reaction temperature is 90-115 ℃; the volume of the organic solvent 1 is 1-6 times of that of the organic solvent 2; the total volume of the organic solvent 1 and the organic solvent 2 is 1-24 mL; the saturated salt solution is selected from one or more of a saturated ammonium chloride solution, a saturated ammonium sulfate solution, a saturated magnesium chloride solution, a saturated sodium sulfate solution, a saturated potassium chloride solution and a saturated potassium nitrate solution.
8. The method for preparing the hydrogen donor-containing thioether-type naphthalimide derivative photoinitiator suitable for UV-LED aerobic photo-curing according to claim 3, wherein the method comprises the following steps: in the step c, the drying agent is one or more selected from anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous magnesium chloride and anhydrous calcium chloride.
9. A free radical photo-curable composition comprising the hydrogen donor-containing thioether-type naphthalimide derivative photoinitiator according to claim 1, wherein the photoinitiator is suitable for UV-LED aerobic photo-curing; the composition comprises 0.1 to 5 percent of the photoinitiator containing the hydrogen donor thioether type naphthalimide derivative and 95 to 99.9 percent of light-cured resin or monomer based on the total weight of the composition.
10. The composition of claim 9, wherein the photo-curable resin is selected from one or more of epoxy (meth) acrylic resins, polyurethane (meth) acrylic resins, polyester (meth) acrylic resins, polyether (meth) acrylic resins, acrylated poly (meth) acrylic resins; the monomer is one or more of monofunctional or polyfunctional (methyl) acrylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010418614.7A CN113683714B (en) | 2020-05-18 | 2020-05-18 | Thioether type naphthalimide derivative photoinitiator containing hydrogen donor and suitable for UV-LED aerobic light curing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010418614.7A CN113683714B (en) | 2020-05-18 | 2020-05-18 | Thioether type naphthalimide derivative photoinitiator containing hydrogen donor and suitable for UV-LED aerobic light curing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113683714A CN113683714A (en) | 2021-11-23 |
| CN113683714B true CN113683714B (en) | 2022-10-28 |
Family
ID=78575448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010418614.7A Active CN113683714B (en) | 2020-05-18 | 2020-05-18 | Thioether type naphthalimide derivative photoinitiator containing hydrogen donor and suitable for UV-LED aerobic light curing |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113683714B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114409830B (en) * | 2022-01-21 | 2023-07-28 | 深圳市普利凯新材料股份有限公司 | Naphthalimide photoinitiator, synthesis method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400529A (en) * | 2018-12-05 | 2019-03-01 | 安庆北化大科技园有限公司 | Suitable for the naphthalimide aryl benzyl thioether-type photoinitiator and preparation method of UV-LED photocuring and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7410746B2 (en) * | 2002-03-29 | 2008-08-12 | Dai Nippon Printing Co., Ltd. | Photoradical polymerization initiator, radical generator, photosensitive compound and photosensitive resin composition containing these materials and product or its accessory portions using the composition |
-
2020
- 2020-05-18 CN CN202010418614.7A patent/CN113683714B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400529A (en) * | 2018-12-05 | 2019-03-01 | 安庆北化大科技园有限公司 | Suitable for the naphthalimide aryl benzyl thioether-type photoinitiator and preparation method of UV-LED photocuring and application |
Non-Patent Citations (1)
| Title |
|---|
| UV-LED 光固化体系光引发剂研究新进展;邓琳等;《精细化工》;20200229;第37卷(第2期);第222-230页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113683714A (en) | 2021-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109970696B (en) | Coumarin oxime ester photoinitiator | |
| Xu et al. | High-efficient carbazole-based photo-bleachable dyes as free radical initiators for visible light polymerization | |
| WO2016192610A1 (en) | Acyloxime ester compound used for uv curing material, synthesis method of same, and application of same | |
| Ren et al. | A UV-LED excited photoinitiator with low toxicity and low migration for photocurable inks | |
| CN113683714B (en) | Thioether type naphthalimide derivative photoinitiator containing hydrogen donor and suitable for UV-LED aerobic light curing | |
| Guo et al. | Substituted Stilbene-based D-π-A and A-π-A type oxime esters as photoinitiators for LED photopolymerization | |
| CN112028893A (en) | Photoinitiator with pyrrolopyrrole structure and preparation method and application thereof | |
| CN113248636B (en) | Thioxanthone visible light initiator, preparation method and application | |
| CN105153330B (en) | The double-branched light-sensitive compound of one class biphenyl type, preparation method and applications | |
| CN114716315A (en) | Application of aromatic vinyl alpha-carbonyl acid ester compound as photoinitiator in LED photopolymerization and preparation method thereof | |
| WO2016192611A1 (en) | Oxime ester compound, synthesis method of same, and application of same | |
| Balta et al. | Chemical incorporation of thioxanthone into β-cyclodextrin and its use in aqueous photopolymerization of methyl methacrylate | |
| CN109400529B (en) | Naphthalimide aryl benzyl thioether type photoinitiator suitable for UV-LED photocuring, and preparation method and application thereof | |
| Shen et al. | Synthesis and photolytic properties of 1, 5-di-N, N′-dialkylaminoanthraquinones containing acryloyl groups | |
| CN107129458B (en) | Carbazole oxime ester compound and synthesis method and application thereof | |
| CN113072440A (en) | Amphiphilic fluorine-containing benzoyl formate photoinitiator suitable for LED photopolymerization and preparation method thereof | |
| CN112939779B (en) | Terephthaloyl formate type photoinitiator suitable for UV-LED deep photopolymerization and preparation method thereof | |
| CN109400530B (en) | Naphthalimide aryl thioether type photoinitiator suitable for UV-LED photocuring, and preparation method and application thereof | |
| CN114262395A (en) | Photocuring system containing sulfonium salt hybrid photoinitiator and application | |
| CN108503556B (en) | Carbonyl compound with biphenyl diphenylamine as conjugated main structure and preparation method and application thereof | |
| Zheng et al. | The photoinitiator of bifunctional α-hydroxy ketone with long-wavelength in photopolymerization under UV-LEDs | |
| CN110078693B (en) | Alpha-hydroxy ketone compound containing coumarin and preparation method and application thereof | |
| CN112194742B (en) | Sulfonium salt photoinitiator and preparation method and application thereof | |
| CN112961165A (en) | Preparation and application of novel carbazole benzopyran compound | |
| CN114409830B (en) | Naphthalimide photoinitiator, synthesis method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |