CN108623559A - A kind of dibenzothiophenes formic acid ester lightlike initiating agent and the preparation method and application thereof - Google Patents
A kind of dibenzothiophenes formic acid ester lightlike initiating agent and the preparation method and application thereof Download PDFInfo
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- CN108623559A CN108623559A CN201810262792.8A CN201810262792A CN108623559A CN 108623559 A CN108623559 A CN 108623559A CN 201810262792 A CN201810262792 A CN 201810262792A CN 108623559 A CN108623559 A CN 108623559A
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- formic acid
- dibenzothiophenes
- acid ester
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 42
- -1 dibenzothiophenes formic acid ester Chemical class 0.000 title claims abstract description 23
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 title claims description 12
- 238000002360 preparation method Methods 0.000 title claims description 4
- 230000000977 initiatory effect Effects 0.000 title description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 238000003847 radiation curing Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical class C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- 238000009472 formulation Methods 0.000 claims abstract description 5
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 8
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 claims description 8
- 150000003384 small molecules Chemical group 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical group COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 3
- 238000007641 inkjet printing Methods 0.000 claims description 3
- 238000007639 printing Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical class ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 claims description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical class CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- 125000006519 CCH3 Chemical group 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- RMRFFCXPLWYOOY-UHFFFAOYSA-N allyl radical Chemical compound [CH2]C=C RMRFFCXPLWYOOY-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-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
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 239000004035 construction material Substances 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- PFPYHYZFFJJQFD-UHFFFAOYSA-N oxalic anhydride Chemical compound O=C1OC1=O PFPYHYZFFJJQFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000005022 packaging material Substances 0.000 claims description 2
- 238000010422 painting Methods 0.000 claims description 2
- 239000006223 plastic coating Substances 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 125000006850 spacer group Chemical group 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 2
- 125000002252 acyl group Chemical group 0.000 claims 1
- 239000013538 functional additive Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 5
- 230000005855 radiation Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- ZXUQEPZWVQIOJE-UHFFFAOYSA-N methyl 2-chloro-2-oxoacetate Chemical compound COC(=O)C(Cl)=O ZXUQEPZWVQIOJE-UHFFFAOYSA-N 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- MSFXCTCHNFTKMQ-UHFFFAOYSA-N 2-bromo-3,4-diphenylthiophene Chemical class BrC=1SC=C(C=2C=CC=CC=2)C=1C1=CC=CC=C1 MSFXCTCHNFTKMQ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- DASXZNZQIQRRHV-UHFFFAOYSA-N BrC=1C=CC2=C(C3=C(S2)C(=CC=C3)C(C(=O)OC)=O)C=1 Chemical compound BrC=1C=CC2=C(C3=C(S2)C(=CC=C3)C(C(=O)OC)=O)C=1 DASXZNZQIQRRHV-UHFFFAOYSA-N 0.000 description 1
- KXYFMYQPFZGASY-UHFFFAOYSA-N BrC=1C=CC2=C(C3=C(S2)C=CC(=C3)C(C(=O)OC)=O)C=1 Chemical compound BrC=1C=CC2=C(C3=C(S2)C=CC(=C3)C(C(=O)OC)=O)C=1 KXYFMYQPFZGASY-UHFFFAOYSA-N 0.000 description 1
- XCIJRXQHCKAKHQ-UHFFFAOYSA-N C1=C(C=CC=2SC3=C(C=21)C=CC=C3)C(C(=O)OC)=O Chemical compound C1=C(C=CC=2SC3=C(C=21)C=CC=C3)C(C(=O)OC)=O XCIJRXQHCKAKHQ-UHFFFAOYSA-N 0.000 description 1
- JNRGJAVZOZHNML-UHFFFAOYSA-N C1=CC=C(C=2SC3=C(C=21)C=CC=C3)C(C(=O)OC)=O Chemical compound C1=CC=C(C=2SC3=C(C=21)C=CC=C3)C(C(=O)OC)=O JNRGJAVZOZHNML-UHFFFAOYSA-N 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
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical group CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/76—Dibenzothiophenes
-
- 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)
- Polymerisation Methods In General (AREA)
Abstract
The present invention relates to new material organic chemicals technical fields, more particularly to a photoinitiator, more particularly to using one kind using dibenzothiophenes formic acid ester as the noval chemical compound of nuclear structure, the photoinitiator is based on dibenzothiophenes parent nucleus and realizes that long wavelength absorbs, and has stronger absorption to the UV LED light sources of 365 425nm.All kinds of target products, chemical preparating process technique to high-efficiency, environmental protection, low cost, easy to operate, suitable industrialized production are obtained by friedel-crafts acylation and appropriate modification.In the purposes of radiation curing photoinitiator, radiation curable formulation product, many occasions such as photocureable coating or ink that especially UV Vis LED can be excited have broad application prospects.
Description
【Technical field】
It is the present invention relates to new material organic chemicals technical field, more particularly to a new class of to contain dibenzothiophenes formyl
The compound of formic acid ester structure, chemical preparating process technology, as radiation curing photoinitiator purposes and its
Radiation curable formulation product waits the application purpose of many occasions especially in UV-Vis-LED photocureable coating or ink.
【Background technology】
Photoinitiator compound is a kind of important Fine Organic Chemical product material.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 generated under light radiation parameter freely
The photoinitiator compound of base active specy is the key species for inducing the system of unsaturation containing alkene and carrying out efficient photopolymerization reaction, because
This is important one of radiation curable formulation component.In the numerous photoinitiator products for having obtained business application, formyl first
Acid esters compound occupies an important position, and mainstream product is such as " methyl benzoylformate " (trade name MBF), main unsaturated
Prepolymer is (such as：Acrylate) UV solidification.For this kind of compound due to having both high initiation activity, yellowing resistance and UV-LED are wide
It composes applicability and obtains increasingly extensive application.In addition, the also above-mentioned formyl first of existing a considerable amount of reports in technical literature
The example of acid esters photoinitiator and other types photoinitiator composite usage.
MBF
On the other hand, for photocuring light source usually using mercury lamp, mercuryvapour does not meet world's energy conservation and environmental protection industry development
Strategic new trend, thus LED light source obtains increasingly extensive attention and quickly development in recent years, and LED light cures skill
The application of art considerably reduces energy consumption and ozone generates, industry sustainable growth powerful.LED systems are cured,
It is also required to both have the light-initiated of sensitive absorption for LED longwave transmissions wavelength (365-420 nanometers, especially 395-405 nanometer)
Agent.Therefore, it designs, research and development and the novel photoinitiator compound of industrialization, are that the key technique that current this field faces is chosen
War problem.The maximum absorption wavelength of known MBF classes compound is located at 325nm, and the range of further its absorption spectrum of red shift is
One feasible approach.
【Invention content】
It challenges in view of the above technology, the present invention passes through the study found that some contain two via what simple method for synthesizing obtained
The formic acid ester type compound of benzothiophene, have with the very matched absorbing wavelengths of LED, we further demonstrate that, in this way
Novel photoinitiator can be effectively compatible with light-cured resin and compound to form storage stable light-curable ink or coating, this
The technology of sample possesses far-reaching influence to woodenware green application, environmental printing, inkjet printing, the fields such as energy-saving material.
This item application, which discloses, leads to dibenzothiophenes formic acid ester type compound shown in formula (I)：
In above-mentioned logical formula (I) compound structure：
R1, R2, R3, R4, R5, R6, R7, R8In there are one or it is multiple be formic acid ester group, remaining be hydrogen independent of each other,
Halogen atom, R, OR, SR, NRR ', CH2OH, CH2OR or CH2NRR ', wherein R or R ' independent of each other are containing 1-24 carbon
Atom (is labeled as-C1-C24, similarly hereinafter) linear chain or branched chain alkyl or-C6-C12It can contain 1-6 in aryl, R or R ' structures
A discrete oxygen, nitrogen or element sulphur can also form the ring system structure of a 3-6 member therebetween when R and R ' are existed simultaneously.It is excellent
Choosing, R1For formic acid ester group, R6=halogen atom or CH3Or OCH3Or phenyl etc., R2=R3=R4=R5=R7=R8=H,
R0=CH3, CH2CH3Or phenyl etc.；Or R3For formic acid ester group, R6=halogen atom or CH3Or OCH3Or phenyl etc. and R1=
R2=R4=R5=R7=R8=H, R0=CH3Or CH2CH3Or phenyl etc.；Or R1=it is formic acid ester group, R3=R6=halogen is former
Son or CH3Or OCH3Or phenyl etc. and R2=R4=R5=R7=R8=H, R0=CH3Or CH2CH3Or phenyl etc..
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.
As n=1, R0- Q is hydrogen, the C containing 0-4 substituent group6-C24Aryl (preferably phenyl, xenyl, naphthalene
Base), methyl, propyl, butyl, amyl, hexyl and straight chain and branched alkyl containing 7-24 carbon, CH2CH=CH2, CH2Ph, C
(O)CEt3, C (O) CMe3, xenyl, 2,4,6- trimethylbenzoyls, 2,6- Dimethoxybenzoyls or 2,6- dichloro-benzenes
Formoxyl, 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) OY, CH2OC (O)-NHY or CH2CH2OC (O) NHY, Y is one containing 2-6 here
- the C of C=C double bonds2-C36Group, preferably Y are one containing 2-6 acrylic ester unit-C2-C36Group, preferred Y
It is one of following shown group：
When n values 2 or the integer more than 2 ,-R0- Q structures are a n member spacer groups；-R0Preferably-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 Q is a small molecule or polymeric groups with 2 or more-NHC (O) O- units, and Q
Preferably following groups：
Alternatively, Q is a small molecule or polymeric groups with 2 or more-C (O) O- units, and Q is preferably
Following groups (wherein R11It is hydrogen or R)：
Alternatively, when n values 2 or the integer more than 2 ,-R0- 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 Q is following groups：
Alternatively, when n values 2 or the integer more than 2 ,-R0- Q structures are one and contain n members-CH2CH (OH)-, or-
CH2The small molecule or polymeric groups of CH (OR)-unit, it is preferred that Q is row group：
One of the universality preparation method of logical formula (I) compound：
By dibenzothiophenes (one or more substituent groups can be contained) and contain R0The oxalyl chloride or oxalic acid or oxalic anhydride of base exist
Suitable solvent and under catalyst action, target product (I) is made by friedel-crafts acylation.Reaction temperature is -10-80
DEG C, it reacts 0.5-10 hours.Reaction solution is poured into ice water, is divided and is taken organic phase, after anhydrous sodium sulfate drying, boils off organic solvent,
Up to crude product, fine work is obtained after column chromatography for separation.The solvent includes but dichloromethane, chloroform, toluene, dimethylbenzene, tetrahydrochysene furan
It mutters, is in 2- methyltetrahydrofurans, methyl tertiary butyl ether(MTBE), ethyl acetate or butyl acetate etc. one or more；The catalyst
Including but not limited to anhydrous AlCl3Or anhydrous FeCl3, H2SO4, H3PO4, BF3, one or more in HF etc..
The exemplary compounds for meeting logical formula (I) structure are listed below：
The present invention further discloses a kind of light radiation curing formula system containing above-mentioned logical formula (I) compound, such light
Radiation curable formulation system can be photocureable coating or ink, the photocureable coating or ink of announcement, in inkjet printing, paper
Printing, adhesive, woodwork coating, plastic coating, painting dressing automobiles, packaging material, display technology, construction material, flexible electronic, light
Lie prostrate the application in the fields such as material.
This kind of light radiation curing formula system is characterized in：
(1) contain compound described at least one logical formula (I) as one of photoinitiator or photoinitiator component；
(2) contain at least one containing ethylene linkage (C=C) unsaturated compound.
Calculated with the every 100 parts of weight of the component of unsaturation containing ethylene linkage total amount in system, the logical formula (I) compound contained it is suitable
Amount be 0.01-30 parts by weight, preferred 0.5-10 parts by weight.What the appropriate radiation curing system that this item application discloses included gathers
The component of unsaturation containing ethylene linkage closed is can be by compound or mixture that the Raolical polymerizable of the double bond is crosslinked, this
Kind of the component of unsaturation containing ethylene linkage can be monomer, oligomer or prepolymer or their mixture or copolymer or above-mentioned
The water-borne dispersions of component.
Appropriate radiation curing system described above can contain inorganic or organic filling out of being added according to actual needs
Fill agent and/or colorant (such as pigments or dyes etc.) and other additives (such as ultra-violet absorber, light stabilizer, resistance
Fire agent, levelling agent or antifoaming agent etc.) and any ingredients such as solvent.
The monomer of suitable free radical polymerization is such as polymerisable monomer containing ethylene linkage, including but 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 are sub-
Vinyl halide etc..
Suitable prepolymer containing ethylene linkage and oligomer include but 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)
Acrylate, siloxanes (methyl) acrylate, epoxy resin (methyl) acrylate etc..
It is above-mentioned either to contain alkene monomer or oligomer, prepolymer or copolymer, to this profession working technical staff
Speech, is all well known, is not particularly limited.
Compared with prior art, the beneficial effects of the present invention are：It is light-initiated that photoinitiator of the present invention belongs to I types
Agent can generate free radicals etc. in the case where that need not add other aided initiatings and cause the poly- of monomer or resin system
It closes；Photoinitiator synthetic route is simple and environmentally-friendly, efficient；It can be excited, be met at present using the LED light source become increasingly popular
UV cures the trend of industry.
【Description of the drawings】
Fig. 1：The ultraviolet-visible light of molecule PI-p, PI-o, Br-PI-p, Br-PI-o in acetonitrile in example 1,2,3,4
Spectrum.
【Specific implementation mode】
For the gist of the invention, we will further illustrate in conjunction with following series embodiments.
Embodiment 1：According to following route synthesis PI-p (methyl 2- (dibenzo [b, d] thiophen-2-yl) -2-
oxoacetate)
(a)：Normal-temperature reaction, 2.5h is added dropwise in aluminum trichloride (anhydrous), anhydrous methylene chloride, ice bath；
It is put into magnetic stick in the 100mL three-necked flasks equipped with constant pressure funnel, condenser pipe, is added successively in ice bath
Enter 2.00g (1eq) dibenzothiophenes, 200ml anhydrous methylene chlorides (solvent), 3.62g (2.5eq) alchlor (catalyst),
After stirring evenly, be slowly added to 3.33g (2.5eq) methyl oxalyl chloride (acylting agent), keep system temperature at 10 DEG C hereinafter,
After being added dropwise, restores to room temperature reaction about 2.5h, tracked by thin layer silica gel plate in reaction.After the reaction was complete, by mixture
It is placed in ice water, hydrochloric acidolysis is added dropwise, is extracted with dichloromethane, organic layer is washed till neutrality with saturated nacl aqueous solution, and use is anhydrous
Sodium sulphate is dried, and decompression boils off organic solvent, and gained crude product uses column chromatography, and is collected the smaller product of polarity, is obtained pure
Product 1.24g, pale yellow powder.
1H-NMR(CDCl3):8.82 (s, 1H), 8.24 (dd, J=6.2,2.6Hz, 1H), 8.09 (dd, J=8.4,
1.7Hz, 1H), 7.95 (d, J=8.4Hz, 1H), 7.91-7.84 (m, 1H), 7.56-7.48 (td/td, 2H), 4.04 (s, J=
5.0Hz,3H).
13C NMR(CDCl3):185.52 (C=O), 164.19 (C=O), 146.87 (Cq), 139.69 (Cq), 135.90
(Cq),134.90(Cq),128.97(Cq),127.86(CH),127.48(CH),125.25(CH),123.79(CH),123.22
(CH),123.03(CH),122.14(CH),53.03(CH3).
Embodiment 2：According to following route synthesis PI-o (methyl 2- (dibenzo [b, d] thiophen-4-yl) -2-
oxoacetate)
(a)：Normal-temperature reaction, 2.5h is added dropwise in aluminum trichloride (anhydrous), anhydrous methylene chloride, ice bath；
It is put into magnetic stick in the 100mL three-necked flasks equipped with constant pressure funnel, condenser pipe, is added successively in ice bath
Enter 2.00g (1eq) dibenzothiophenes, 200ml anhydrous methylene chlorides (solvent), 3.62g (2.5eq) alchlor (catalyst),
After stirring evenly, be slowly added to 3.33g (2.5eq) methyl oxalyl chloride (acylting agent), keep system temperature at 10 DEG C hereinafter,
After being added dropwise, restores to room temperature reaction about 2.5h, tracked by thin layer silica gel plate in reaction.After the reaction was complete, by mixture
It is placed in ice water, hydrochloric acidolysis is added dropwise, is extracted with dichloromethane, organic layer is washed till neutrality with saturated nacl aqueous solution, and use is anhydrous
Sodium sulphate is dried, and decompression boils off organic solvent, and gained crude product uses column chromatography, and is collected the larger product of polarity, is obtained pure
Product 1.13g, pale yellow powder.
1H-NMR(CDCl3):8.44 (dd, J=7.8,1.0Hz, 1H), 8.29-8.12 (dd/dd, 2H), 8.04-7.90
(dd, 1H), 7.60 (t, J=7.7Hz, 1H), 7.56-7.48 (t/t, 2H), 4.05 (s, 3H)
13C NMR(CDCl3):185.13 (C=O), 163.82 (C=O), 141.77 (Cq), 140.80 (Cq), 137.68
(Cq),133.60(Cq),131.80(CH),127.81(CH),127.66(CH),126.51(Cq),125.00(CH),124.32
(CH),123.02(CH),121.59(CH),53.13(CH3).
Embodiment 3：According to following route synthesis Br-PI-p (methyl 2- (8-bromodibenzo [b, d]
thiophen-2-yl)-2-oxoacetate)
Normal-temperature reaction, 25h is added dropwise in aluminum trichloride (anhydrous), anhydrous methylene chloride, ice bath；
It is put into magnetic stick in the 100mL three-necked flasks equipped with constant pressure funnel, condenser pipe, is added successively in ice bath
Enter 1.0g (1eq) 2- bromodiphenylthiophenes, 200ml anhydrous methylene chlorides (solvent), 2.03g (4eq) alchlor (catalyst),
After stirring evenly, it is slowly added to 0.93g (2eq) methyl oxalyl chloride (acylting agent), keeps system temperature at 10 DEG C hereinafter, drop
After adding, restores to room temperature reaction about 2.5h, tracked by thin layer silica gel plate in reaction.After the reaction was complete, mixture is set
Enter in ice water, hydrochloric acidolysis is added dropwise, is extracted with dichloromethane, organic layer is washed till neutrality with saturated nacl aqueous solution, with anhydrous sulphur
Sour sodium drying, decompression boil off organic solvent, and gained crude product uses column chromatography, and collects the smaller product of polarity, obtains sterling
0.54g, pale yellow powder
1H-NMR(CDCl3):8.74 (s, 1H), 8.32 (s, 1H), 8.08 (dd, J=8.5,1.6Hz, 1H), 7.90 (d, J
=8.5Hz, 1H), 7.68 (d, J=8.5Hz, 1H), 7.57 (dd, J=8.6,1.9Hz, 1H), 3.98 (d, 3H)
13C NMR(CDCl3):184.86 (C=O), 163.55 (C=O), 141.18 (Cq), 140.46 (Cq), 136.45
(Cq),135.37(Cq),132.36(CH),130.53(CH),127.91(CH),126.57(Cq),124.63(CH),124.49
(CH),124.32(CH),118.98(Cq),53.22(CH3).
Embodiment 4：According to following route synthesis Br-PI-o (methyl 2- (8-bromodibenzo [b, d]
thiophen-4-yl)-2-oxoacetate)
(a)：Normal-temperature reaction, 2.5h is added dropwise in aluminum trichloride (anhydrous), anhydrous methylene chloride, ice bath；
It is put into magnetic stick in the 100mL three-necked flasks equipped with constant pressure funnel, condenser pipe, is added successively in ice bath
Enter 1.0g (1eq) 2- bromodiphenylthiophenes, 200ml anhydrous methylene chlorides (solvent), 2.03g (4eq) alchlor (catalyst),
After stirring evenly, it is slowly added to 0.93 (2eq) methyl oxalyl chloride (acylting agent), keeps system temperature at 10 DEG C hereinafter, drop
After adding, restores to room temperature reaction about 2.5h, tracked by thin layer silica gel plate in reaction.After the reaction was complete, mixture is set
Enter in ice water, hydrochloric acidolysis is added dropwise, is extracted with dichloromethane, organic layer is washed till neutrality with saturated nacl aqueous solution, with anhydrous sulphur
Sour sodium drying, decompression boil off organic solvent, and gained crude product uses column chromatography, and collect the larger product of polarity, obtain sterling
0.49g, pale yellow powder.
1H-NMR(CDCl3):8.34 (dd, J=10.9,5.4Hz, 1H), 8.25 (s, 1H), 8.21 (dd, J=7.7,
1.0Hz, 1H), 7.76 (d, J=8.5Hz, 1H), 7.64-7.50 (t/d, 2H), 3.99 (d, J=4.6Hz, 3H)
13C NMR(CDCl3):185.12 (C=O), 163.95 (C=O), 147.13 (Cq), 138.31 (Cq), 136.63
(Cq),134.68(Cq),130.78(CH),129.27(Cq),128.01(CH),125.01(CH),124.31(CH),124.06
(CH),123.35(CH),119.31(Cq),53.16(CH3).
Embodiment 5：The photochemistry physical property of molecule
UV-Vis spectra point has been carried out to molecule PI-p, PI-o, Br-PI-p, Br-PI-o in embodiment 1,2,3,4
It analyses (solvent is acetonitrile), if Fig. 1 is the ultraviolet spectrogram of each photoinitiator molecules, according to Lambert-Beer laws and by figure
The relationship of middle absorbance and concentration, which carries out linear fit, can be calculated the molar extinction coefficient of target product under different wave length,
As shown in the table：
The molar extinction coefficient of table 1 molecule PI-p, PI-o, Br-PI-p, Br-PI-o under different wave length ultraviolet-visible light
(solvent is acetonitrile)
Embodiment 6：The Light lnduced Free Radicals polymerization test of target molecule
Photoinitiator molecules PI-p, PI-o, Br-PI-p, Br-PI-o molecule in embodiment 1,2,3,4 is made into and accounts for list
The photocuring system of body 3wt%, monomer are using TPGDA, specific test method：It is tested with the double-deck PP films, the scanning back of the body
After scape, last layer photocuring system is scratched on film, is respectively then 365nm (light intensity 64mW/cm in LED light source2),
385nm (light intensity 65mW/cm2), 405nm (light intensity 50mW/cm2), 425nm (light intensity 60mW/cm2) ultraviolet LED lamp under
Polymerization detects in Light Curing the variation at monomer double bond peak and right at interval of 1.43s scanned infrared spectrum in illumination 220s
Its area is integrated, and obtains final monomer conversion, as shown in the table.See mesh with being apparent from according to list data
Marking when molecule causes free radical type monomer polymerization as photoinitiator has higher monomer conversion.
Table 2 causes TPGDA using molecule PI-p, PI-o, Br-PI-p, Br-PI-o of 3wt% as photoinitiator and is aggregated in
Conversion ratio under different wave length ultraviolet-visible light
Foregoing description is only the description to present pre-ferred embodiments, is not any restriction to the scope of the invention.Appoint
Any change or modification what those skilled in the art makes according to the technology contents of the disclosure above should all regard
For equivalent effective embodiment, the range of technical solution of the present invention protection is belonged to.
Claims (10)
1. dibenzothiophenes formic acid ester type compound shown in logical formula (I)：
In above-mentioned logical formula (I) compound structure：
R1, R2, R3, R4, R5, R6, R7, R8In there are one or it is multiple be formic acid ester group, remaining be hydrogen independent of each other, halogen
Atom, R, OR, SR, NRR ', CH2OH, CH2OR or CH2NRR ', wherein R or R ' independent of each other are containing 1-24 carbon atom
(it is labeled as-C1-C24, similarly hereinafter) linear chain or branched chain alkyl or-C6-C12It is discontinuous containing 1-6 in aryl, R or R ' structures
Oxygen, nitrogen or element sulphur can form the ring system structure of a 3-6 member therebetween when R and R ' are existed simultaneously；
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；
As n=1, R0- Q is hydrogen, the C containing 0-4 substituent group6-C24Aryl (preferably phenyl, xenyl, naphthalene), first
Base, propyl, butyl, amyl, hexyl and straight chain and branched alkyl containing 7-24 carbon, CH2CH=CH2, CH2Ph, C (O)
CEt3, C (O) CMe3, xenyl, 2,4,6- trimethylbenzoyls, 2,6- Dimethoxybenzoyls or 2,6- dichloro-benzenes first
Acyl group, 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) OY, CH2OC (O)-NHY or CH2CH2OC (O) NHY, Y is one containing 2-6 here
- the C of C=C double bonds2-C36Group；
When n values 2 or the integer more than 2 ,-R0- Q structures are a n member spacer group ,-R0Preferably-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 Q is a small molecule or polymeric groups with 2 or more-NHC (O) O- units, Q is excellent
Choosing is following groups：
Alternatively, Q is a small molecule or polymeric groups with 2 or more-C (O) O- units, Q is preferably following base
Group (wherein R11It is hydrogen or R)：
Alternatively, when n values 2 or the integer more than 2 ,-R0- 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 polymeric groups of CH (Me) S (O) R- units, it is preferred that Q
It is following groups：
Alternatively, when n values 2 or the integer more than 2 ,-R0- Q structures are one and contain n members-CH2CH (OH)-, or-CH2CH
(OR) small molecule or polymeric groups of-unit, it is preferred that Q is row group：
2. dibenzothiophenes formic acid ester type compound according to claim 1, it is characterised in that：
R1For formic acid ester group, R6=halogen atom or CH3Or OCH3Or phenyl, R2=R3=R4=R5=R7=R8=H, R0=
CH3, CH2CH3Or phenyl；
Or R3For formic acid ester group, R6=halogen atom or CH3Or OCH3Or phenyl and R1=R2=R4=R5=R7=R8=H,
R0=CH3Or CH2CH3Or phenyl；
Or R1=it is formic acid ester group, R3=R6=halogen atom or CH3Or OCH3Or phenyl and R2=R4=R5=R7=R8=
H, R0=CH3Or CH2CH3Or phenyl.
3. dibenzothiophenes formic acid ester type compound according to claim 1, it is characterised in that：Work as n=1, R0- Q is
CH2CH2C (O) OY, CH2OC (O)-NHY or CH2CH2When OC (O) NHY, the Y is one and contains 2-6 acrylic ester unit
- C2-C36Group.
4. dibenzothiophenes formic acid ester type compound according to claim 3, it is characterised in that：The Y is following
One of shown group：
5. a kind of claim 1 leads to the preparation method of the ester compounds of dibenzothiophenes formic acid shown in formula (I), feature exists
In：：
By dibenzothiophenes (one or more substituent groups can be contained) and contain R0The oxalyl chloride or oxalic acid or oxalic anhydride of-Q bases are suitable
Solvent and under catalyst action, target product (I) is made by friedel-crafts acylation；Reaction temperature is -10-80 DEG C,
Reaction 0.5-10 hours；Reaction solution is poured into ice water, point takes organic phase, after anhydrous sodium sulfate drying, boil off organic solvent to get
Crude product, after column chromatography for separation compound shown in logical formula (I)；
The solvent includes dichloromethane, chloroform, toluene, dimethylbenzene, tetrahydrofuran, 2- methyltetrahydrofurans, methyl- tert fourth
It is one or more in base ether, ethyl acetate or butyl acetate etc.；
The catalyst includes anhydrous AlCl3Or anhydrous FeCl3, H2SO4, H3PO4, BF3, one or more in HF etc..
6. a kind of claim 1 leads to the ester type compound of dibenzothiophenes formic acid shown in formula (I) in photocurable formulation system
As the purposes of photoinitiator or other functional additive ingredients, and its as intermediate or raw material or examination in chemical synthesis
The purposes of agent.
7. a kind of leading to the ester type compound of dibenzothiophenes formic acid shown in formula (I) containing claim 1, (ultraviolet via light
Or visible light or LED light or equal lamp-house) radiation curing light radiation curing formula system, it is characterised in that：
Contain compound shown at least one logical formula (I) as one of photoinitiator or photoinitiator component；And contain at least one
Kind contains ethylene linkage (C=C) unsaturated compound, and described ethylene linkage (C=C) unsaturated compound that contains is the radical polymerization by the double bond
The compound or mixture that reaction is crosslinked are closed, described ethylene linkage (C=C) unsaturated compound that contains is monomer, oligomer or pre-polymerization
Object or their mixture or copolymer；
It is calculated with the every 100 parts of weight of the component of unsaturation containing ethylene linkage total amount in system, which contains logical
The suitable amount of formula (I) compound is 0.01-30 parts by weight.
8. light radiation curing formula system according to claim 7, it is characterised in that：The light radiation curing formula system contains
Logical formula (I) compound it is suitable amount be 0.5-10 parts by weight.
9. light radiation curing formula system according to claim 7, it is characterised in that：The light radiation curing formula system is
Photocureable coating or ink.
10. light radiation curing formula system described in a kind of claim 9 is applied in inkjet printing, paper printing, adhesive, woodenware
Dress, plastic coating, painting dressing automobiles, packaging material, display technology, construction material, flexible electronic, the fields such as photovoltaic material are answered
With.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112321823A (en) * | 2020-11-22 | 2021-02-05 | 同济大学 | Dendritic macromolecular photoinitiator with low biotoxicity and preparation and application thereof |
| WO2022238591A1 (en) * | 2021-10-08 | 2022-11-17 | Igm Resins Italia S.R.L. | Novel photoinitiators |
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| US3897453A (en) * | 1972-05-13 | 1975-07-29 | Merck Patent Gmbh | Dibenzofuran and dibenzothiophene acetic acid derivatives |
| WO2006120212A1 (en) * | 2005-05-13 | 2006-11-16 | Lamberti Spa | Phenylglyoxalic esters generating by photolysis low migratable fragments |
| WO2016034963A1 (en) * | 2014-09-04 | 2016-03-10 | Basf Se | Polycyclic photoinitiators |
| WO2018041935A1 (en) * | 2016-09-02 | 2018-03-08 | Igm Group B.V. | Polycyclic glyoxylates as photoinitiators |
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| US3897453A (en) * | 1972-05-13 | 1975-07-29 | Merck Patent Gmbh | Dibenzofuran and dibenzothiophene acetic acid derivatives |
| WO2006120212A1 (en) * | 2005-05-13 | 2006-11-16 | Lamberti Spa | Phenylglyoxalic esters generating by photolysis low migratable fragments |
| WO2016034963A1 (en) * | 2014-09-04 | 2016-03-10 | Basf Se | Polycyclic photoinitiators |
| WO2018041935A1 (en) * | 2016-09-02 | 2018-03-08 | Igm Group B.V. | Polycyclic glyoxylates as photoinitiators |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112321823A (en) * | 2020-11-22 | 2021-02-05 | 同济大学 | Dendritic macromolecular photoinitiator with low biotoxicity and preparation and application thereof |
| WO2022238591A1 (en) * | 2021-10-08 | 2022-11-17 | Igm Resins Italia S.R.L. | Novel photoinitiators |
| WO2022207945A3 (en) * | 2021-10-08 | 2022-12-01 | Igm Resins Italia S.R.L. | "novel photoinitiators" |
| IT202100025868A1 (en) * | 2021-10-08 | 2023-04-08 | Igm Resins Italia Srl | NEW PHOTO STARTERS |
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Application publication date: 20181009 |