CN107129487B - One kind can excite the preparation method and applications of sulfosalt using thioxanthone as the LED of conjugated structure - Google Patents
One kind can excite the preparation method and applications of sulfosalt using thioxanthone as the LED of conjugated structure Download PDFInfo
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- CN107129487B CN107129487B CN201710228125.3A CN201710228125A CN107129487B CN 107129487 B CN107129487 B CN 107129487B CN 201710228125 A CN201710228125 A CN 201710228125A CN 107129487 B CN107129487 B CN 107129487B
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- thioxanthone
- acid
- photo
- acid agent
- light
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- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 47
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- -1 tetrafluoroborate Chemical compound 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- WHSFSWJDZYZLNF-UHFFFAOYSA-N 1-bromothioxanthen-9-one Chemical compound BrC1=CC=CC=2SC3=CC=CC=C3C(C1=2)=O WHSFSWJDZYZLNF-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- RADLTTWFPYPHIV-UHFFFAOYSA-N (2-sulfanylphenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1S RADLTTWFPYPHIV-UHFFFAOYSA-N 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims description 4
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 229960004889 salicylic acid Drugs 0.000 claims description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 238000004587 chromatography analysis Methods 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000006505 p-cyanobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C#N)C([H])([H])* 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- WCGIGOVLOFXAMG-UHFFFAOYSA-N silver;trifluoromethanesulfonic acid Chemical compound [Ag].OS(=O)(=O)C(F)(F)F WCGIGOVLOFXAMG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001868 water Inorganic materials 0.000 claims description 3
- UMLFTCYAQPPZER-UHFFFAOYSA-N 4-(bromomethyl)benzonitrile Chemical compound BrCC1=CC=C(C#N)C=C1 UMLFTCYAQPPZER-UHFFFAOYSA-N 0.000 claims description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 2
- 238000003847 radiation curing Methods 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 238000010898 silica gel chromatography Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 7
- 239000005977 Ethylene Substances 0.000 claims 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- 235000011089 carbon dioxide Nutrition 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 claims 1
- 239000006185 dispersion Substances 0.000 claims 1
- 238000010828 elution Methods 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 239000013538 functional additive Substances 0.000 claims 1
- 239000004615 ingredient Substances 0.000 claims 1
- 238000010526 radical polymerization reaction Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000005284 excitation Effects 0.000 abstract description 3
- 230000000977 initiatory effect Effects 0.000 abstract 2
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000003321 amplification Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- OEWATJNLOFPPAP-UHFFFAOYSA-N 1-bromo-9H-thioxanthene Chemical compound BrC1=CC=CC=2SC3=CC=CC=C3CC12 OEWATJNLOFPPAP-UHFFFAOYSA-N 0.000 description 1
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- RYKLZUPYJFFNRR-UHFFFAOYSA-N 3-hydroxypiperidin-2-one Chemical compound OC1CCCNC1=O RYKLZUPYJFFNRR-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 102100025403 Epoxide hydrolase 1 Human genes 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 101100451963 Homo sapiens EPHX1 gene Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000009500 colour coating Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001393 microlithography Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000005409 triarylsulfonium group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
- C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
- C07D335/12—Thioxanthenes
- C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
- C07D335/16—Oxygen atoms, e.g. thioxanthones
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The present invention relates to one kind can excite the preparation method and applications of sulfosalt using thioxanthone as the LED of conjugated structure.By introducing biphenyl class formation in thioxanthone structure, the absorbing wavelength of molecule extends near ultraviolet-visible region, to realize a kind of sulfosalt photogenerated acid agent molecule that commercialization LED can be excited.This kind of photo-acid agent synthesis step is simple, is easy to purify, and cost is relatively low, and yield is higher.And such photo-acid agent be LED can excitated type photo-acid agent, adapt to wavelength it is wide, embody preferable absorbing properties in ultraviolet-visible light area, the light initiation polymerization suitable for ultra-violet (UV) band to visible region.In addition, such photo-acid agent can save for a long time under the conditions of being protected from light, chemical stability is high.There is huge application value in the ultraviolet-visible light initiation system of LED excitation.
Description
Technical field
The present invention relates to new material organic chemicals technical field, in particular to it is a new class of containing thioxanthone be conjugation
The sulphur salt compounds of structure, chemical preparating process technology, as the purposes of radiation curing photoinitiator, Yi Jiqi
In radiation curable formulation product, especially in UV-Vis-LED photocureable coating or ink, the application purpose of many occasions is waited.
Background technique
Photo-acid agent is a kind of compound that strong acid can be generated under extraneous light stimulus.It is well known that photo-acid agent by
In itself having the characteristics that good chemical amplification, and it is widely used in chemical amplification imaging system such as microlithography, scale collection
At fields such as circuit manufacture, microelectronics, Microfluidics, data storages.Such as in microelectronics domain, one kind is very important
Technology is exactly to manufacture microcircuit card, by the way that one layer of thin polymer film (photoresist Photoresist) containing photo-acid agent is heavy
Then product uses up through exposure mask on the surface of silicon wafer and irradiates this thin polymer film, strong acid is generated in the part of exposure, thus right
Specific macromolecule resin plays catalytic action (crosslinking or decomposition), the reaction of quantum yield >=1 is brought it about, so as to cause exposure
Relevant chemical change occurs for region, and the difference of dissolution or affine performance, the shape after development treatment are formed with unexposed area
At image.This kind of catalytic action is just called " chemical amplification effect ".And in photo-acid agent system, ionic photo-acid agent, example
As salt compounded of iodine and sulfosalt occupy always consequence.Especially triaryl sulfonium salts etc..But the molecule of these commercializations
For structure since its conjugated structure is substantially phenyl ring, maximum absorption wavelength is usually located at ultra-violet (UV) band.This is for new light sources
Application produce certain limitation, such as light emitting diode.
LED is the abbreviation of light emitting diode, is the special light sources to grow up at present.With energy conservation, environmental protection, monochromaticjty
Well, the advantages that long service life.Very more advantages is embodied compared with traditional high-pressure sodium lamp, low pressure mercury lamp etc., especially
Environmentally friendly aspect.It is the novel light being all widely used by various countries worldwide at present because not needing the mercury using severe toxicity
Source.But LED also has the limitation of its own, essentially consists in its launch wavelength and is near ultraviolet-near infrared region (365nm
~), it is difficult to realize sufficiently high light intensity in ultraviolet and far-ultraviolet region, to cause a series of application.It is obvious that LED and sulphur
The excitation of salt is conflict.
Summary of the invention
For the challenge of the above-mentioned prior art, the present invention is it has been unexpectedly discovered that some obtain via novel synthesis
The sulphur salt compounds containing thioxanthone group arrived, have with the very matched absorbing wavelength of LED, and such as introduce
After biphenyl group, good photogenerated acid property is embodied.Inventor further confirms, the sulphur that such New LED can excite
Salt photo-acid agent molecule can be used as free radical or cation light initiator causes esters of acrylic acid or epoxy monomer
Photopolymerization.In particular, such photoinitiator is suitable for energy-saving environment-friendly LED photocuring technology, such technology is green to woodenware
Color coating, environmental printing, inkjet printing, the fields such as energy-saving material possess far-reaching influence.
The present invention prepares biphenyl structural using thioxanthone as conjugated structure, by Suzuki-Miyaura reaction,
Position replaces upper sulfosalt group, to synthesize a kind of novel photo-acid agent, can have outstanding light in ultraviolet-visible light area
The performance of absorption.
The technical solution that the present invention provides is as follows:
Using thioxanthone as the sulfosalt type photo-acid agent of conjugated structure, which has one kind proposed by the present invention
Following below formula:
Wherein, R1It can be any in methyl, benzyl or 4- cyanobenzyls；R2For trifluoromethayl sulfonic acid root, hexafluorophosphoric acid
It is any in root or tetrafluoroborate.
One kind proposed by the present invention is using thioxanthone as the preparation method of the sulfosalt type photo-acid agent of conjugated structure, specifically
Steps are as follows:
(1) bromo thioxanthone is prepared
At room temperature, the concentrated sulfuric acid is added into single-necked flask, bromobenzene liquid is then added, it is small to stir 0.5~1.0 at room temperature
When, white opacity liquid is obtained, sulfydryl salicylic acid is then added portionwise, stirs at room temperature 20-24 hours, then heats 2 at 100 DEG C
~3h after being cooled to room temperature, is carefully poured into ice water, is filtered, is obtained solid, and 20% NaOH aqueous solution, stirring 2 is then added
~3h is filtered, is washed to neutrality, obtains yellow solid, i.e. bromo thioxanthone.
(2) target photoproduction acid precursor is prepared
Under nitrogen protection, bromo thioxanthone, 3- first are sequentially added in the flask equipped with reflux condensing tube and blender
Mercaptophenyl boronic acid, potassium carbonate, Pd (PPh3)4And toluene/ethanol/H2O is heated to reflux 24 under stirring as reaction dissolvent
~48 hours.It is extracted with dichloromethane after being cooled to room temperature, saturated salt solution and deionized water washing, uses silica gel after solvent evaporated
Pillar layer separation (eluent: methylene chloride/petroleum ether, 1:2) obtains light yellow product, i.e. photoproduction acid precursor.
(3) target photo-acid agent is prepared
Photoproduction acid precursor is dissolved in anhydrous methylene chloride, system is placed and is cooled to -78 DEG C in dry ice acetone bath,
Equimolar trifluoro-methane sulfonic acid silver and halogenated alkane or halogenated aryl hydrocarbon is added under the conditions of being protected from light later, low temperature stirs 1 hour.
Dry ice acetone bath is removed later, and room temperature stirs 22~24 hours under the conditions of being protected from light.Thin plate chromatography detection reaction terminates, by dichloromethane
Alkane is evaporated, and is dissolved with acetonitrile, and solid impurity is filtered off, and concentrate solution is precipitated with the ether of 10 times of volumes, obtains product, filtered, done
It is dry, obtain yellow powder, as photo-acid agent target product trifluoro-methanyl sulfonate.When salt being needed to exchange, trifluoromethayl sulfonic acid
Salt carries out in acetone and aqueous solution with corresponding tetrafluoroborate, hexafluorophosphate, hexafluoro antimonate.It is after filtering drying
Specific objective product.
In the present invention, inert gas described in step 2) is nitrogen or argon gas.
In the present invention, halogenated alkane described in step (3) can use iodomethane, any one in benzyl bromine or 4- cyano benzyl bromine
Kind.
In the present invention, the 3- first mercaptophenyl boronic acid, potassium carbonate, Pd (PPh3)4, halogenated alkane, halogenated aryl hydrocarbon, trifluoro
Utilized as silver methane sulfonate and Potassium Hexafluorophosphate and sodium tetrafluoroborate are commercial product.
The invention has the characteristics that
1. selecting thioxanthone as photo-acid agent parent.Thioxanthone itself is a kind of with UV-Visible absorption
Chromophore, can have preferable absorbing properties in ultraviolet-visible light area；In addition, it be the very big electronics of electron density to
Body can increase the length and coplanar structure of conjugation segment, simultaneously so as to improve performance of the photo-acid agent in LED excitation；
2. selecting the position of substitution of meta position as sulfosalt structure, the fracture of C-S key in photo-acid agent structure can be utilized,
To promote the generation of light acid；
3. synthesis process is simple, step is less, improves yield；
4. red shift has occurred in maximum absorption wavelength, there are good UV-Vis absorption properties, be suitable for cost more
The LED of low, more efficient such as 385nm, 405nm, 425nm, ultra-violet (UV) band to the near visible area of 450nm excite photopolymerization；
5. having very high chemical stability to be able to maintain prolonged preservation under conditions of dark room temperature.
Detailed description of the invention
Fig. 1 is uv-visible absorption spectra data of the target product in acetonitrile in the embodiment of the present invention 1,2,3, can be seen
The a length of 385nm of maximum absorption wave out is suitable for LED and excites.
Specific embodiment
Below using specific example as to further instruction of the present invention, but it is not to be taken as limitation of the invention.
Embodiment 1
In invention, parent material 1 is sulfydryl salicylic acid, obtains intermediate bromo thioxanthone by reaction；Again by anti-
Intermediate bromo thioxanthone and 3- first mercaptophenyl boronic acid should be coupled, and then obtained using thioxanthone as conjugated structure
Photo-acid agent；The R1For methyl, R2For trifluoromethayl sulfonic acid root, synthetic route used in the preparation method is expressed as follows:
1. preparing bromo thioxanthone
At room temperature, the 20ml concentrated sulfuric acid is added into 50ml single-necked flask, 6ml bromobenzene liquid is then added, stirs at room temperature
Half an hour is mixed, white opacity liquid is obtained, 1.0g sulfydryl salicylic acid then is added portionwise in half an hour, it is small to stir 20-24 at room temperature
When, it then in 100 DEG C of heating 2-3h, after being cooled to room temperature, carefully pours into ice water, filters, obtain solid, be then added 20%
NaOH aqueous solution, stir 2h, filter, be washed to neutrality, obtain yellow solid, yield 80.3%.
2. preparing precursor I TX-P
Under nitrogen protection, bromo thioxanthene is sequentially added in 250 milliliters of flasks equipped with reflux condensing tube and blender
Ketone (5.00g, 15.00mmol), 3- first mercaptophenyl boronic acid (2.52g, 15.00mmol), potassium carbonate (6.21g, 44.93mmol),
Pd(PPh3)4(0.88g, 0.75mmol) and toluene/ethanol/H2O (v/v/v, 5:3:1,40mL:24mL:8mL) as
Reaction dissolvent is heated to reflux 48 hours under stirring.(3 × 100mL), saturated salt solution is extracted with dichloromethane after being cooled to room temperature
It is washed with deionized water, separates (eluent: methylene chloride/petroleum ether, 1:2,500 milliliters) with silica gel column chromatography after solvent evaporated
Obtain light yellow product, yield 75.5%.
3. preparing target photo-acid agent
241mg photoproduction acid precursor is dissolved in 15mL anhydrous methylene chloride, system is placed and is dropped in dry ice acetone bath
Equimolar trifluoro-methane sulfonic acid silver and iodomethane is added to -78 DEG C in temperature under the conditions of being protected from light later, and low temperature stirs 1 hour.It
It moves back except dry ice acetone bath, room temperature stirs 24 hours under the conditions of being protected from light.Thin plate chromatography detection reaction terminates, and methylene chloride is steamed
It is dry, it is dissolved with acetonitrile, filters off solid impurity, concentrate solution is precipitated with the ether of 10 times of volumes, obtains product, filtered, and it is dry, it obtains
Yellow powder 329mg, as trifluoro-methanyl sulfonate are the photo-acid agent target product of anion, gross production rate are as follows: 69.8%.
Embodiment 2
It is identical as 1 preparation method of embodiment, only when preparing target product, iodomethane is substituted for the 4- cyano of equivalent
Benzyl bromine or cylite, remaining step is constant, and the target light that 4- cyanobenzyls or benzyl replace then is synthesized after being handled
Raw acid agent.
Embodiment 3
The product of Examples 1 and 2 is dissolved in proper amount of acetone, the aqueous solution containing different corresponding anion salts is added dropwise to
In, it is protected from light stirring 2 hours, filters the precipitating of precipitation.It is repeated twice, that is, prepares the target product with different anions.
Embodiment 4
The various photo-acid agents that embodiment 1,2,3 is prepared are dissolved in dry acetonitrile, are that light source is each to excite with LED
Kind photo-acid agent solution uses rhodamine B as acid indicator, measures variousization with the measurement of light intensity meter by the light intensity of optical filter
Close the product acid activity of object.As a result prove that the sample prepared in each embodiment shows the photoproduction acid quantum yield of 0.05-0.4.
The test of embodiment 5:LED photocuring
The system of sample containing epoxy group is by following formula production (by weight percentage):
Double-functional group resin (EPOX): 98%；
2% photoinitiator (preparation of embodiment 3 provides).
By above-mentioned preparation embodiment mixture coated on the coating for forming about 30-35 microns on cardboard, 1 Shenzhen and day
The unit power of scientific & technical corporation's production is 16W/cm2Launch wavelength be 395 nanometers of LED light source (3 centimetres wide and 80 centimeter lengths
LED area light source), Variable-speed conveyor belt test.Press the criterion for carving and scraping and not generating that trace is photopolymerization curing completion repeatedly with nail.
The result shows that being solidified containing embodiment compound with the Speed Efficient higher than 30 ms/min.
It is above-mentioned the experimental results showed that these photoinitiators prepared by the present invention have a good LED light curing efficiency simultaneously
Energy.
Claims (8)
1. one kind is the sulfosalt class photo-acid agent molecule of conjugated structure containing thioxanthone, which is characterized in that sulfosalt substituent group
Positioned at the meta position of biphenyl class group, general structure are as follows:
Wherein: R1For methyl, benzyl or 4- cyanobenzyls；R2For trifluoromethayl sulfonic acid root, tetrafluoroborate, hexafluoro-phosphate radical, six
The correspondence anion of fluorine metaantimmonic acid root.
2. a kind of a kind of system containing the sulfosalt class photo-acid agent molecule that thioxanthone is conjugated structure as described in claim 1
Preparation Method, which is characterized in that specific step is as follows:
(1) bromo thioxanthone is prepared
At room temperature, the concentrated sulfuric acid is added into single-necked flask, bromobenzene is then added, stirs 0.5~1.0 hour, obtains white at room temperature
Then sulfydryl salicylic acid is added portionwise in color troubled liquor, stir at room temperature 20-24 hours, cold then in 100 DEG C of heating 2~3h
But it to after room temperature, carefully pours into ice water, filters, obtain solid, 20% NaOH aqueous solution is then added, stirs 2~3h, takes out
Filter, is washed to neutrality, obtains yellow solid, i.e. bromo thioxanthone；
(2) target photoproduction acid precursor is prepared
Under inert gas shielding, bromo thioxanthone, 3- first are sequentially added in the flask equipped with reflux condensing tube and blender
Mercaptophenyl boronic acid, potassium carbonate, Pd (PPh3)4And toluene/ethanol/H2O is heated to reflux 24 under stirring as reaction dissolvent
It~48 hours, is extracted with dichloromethane after being cooled to room temperature, saturated salt solution and deionized water washing, uses silica gel after solvent evaporated
Pillar layer separation obtains light yellow product, i.e. photoproduction acid precursor；
(3) target photo-acid agent is prepared
Photoproduction acid precursor is dissolved in anhydrous methylene chloride, system is placed in dry ice acetone bath and is cooled to -78 DEG C, later
Equimolar trifluoro-methane sulfonic acid silver and halogenated alkane are added under the conditions of being protected from light, low temperature stirs 1 hour, removes dry ice third later
Ketone bath, room temperature stir 22~24 hours under the conditions of being protected from light；Thin plate chromatography detection reaction terminates, and methylene chloride is evaporated, acetonitrile is used
Dissolution filters off solid impurity, and concentrate solution is precipitated with the ether of 10 times of volumes, obtains product, filtered, dry, obtains yellow powder,
As photo-acid agent target product trifluoro-methanyl sulfonate；When salt being needed to exchange, trifluoro-methanyl sulfonate and corresponding tetrafluoro
Borate, hexafluorophosphate, hexafluoro antimonate carry out in acetone and aqueous solution；It is total for as containing thioxanthone after suction filtration is dry
The sulfosalt class photo-acid agent molecule of yoke structure；
Halogenated alkane described in step (3) in iodomethane, benzyl bromine or 4- cyano benzyl bromine any one.
3. preparation method according to claim 2, which is characterized in that the elution in step (2) in silica gel column chromatography separation
Agent are as follows: methylene chloride/petroleum ether, volume ratio 1:2.
4. a kind of one kind according to claim 1 exists containing the sulfosalt class photo-acid agent molecule that thioxanthone is conjugated structure
Purposes in photocurable formulation system as photoinitiator or other functional additive ingredients, and be used as in chemical synthesis
The purposes of mesosome or raw material or reagent.
5. a kind of containing described in claim 1 a kind of containing the sulfosalt class photo-acid agent molecule that thioxanthone is conjugated structure
Mixture solidifies via light radiation,
It is characterized in that,
(1) contain compound described at least one logical formula (I) as one of photoinitiator or photoinitiator component；
And (2) contain at least one unsaturated compound containing ethylene linkage or epoxy group；
It is calculated with the every 100 parts of weight of the component of unsaturation containing ethylene linkage total amount in system, the suitable amount of the logical formula (I) compound contained
It is 0.01-30 parts by weight；Surplus is the unsaturated compound containing ethylene linkage or epoxy group；
The polymerizable component of unsaturation containing ethylene linkage that suitable Radiation-curing system includes is the radical polymerization by this containing ethylene linkage
Compound or mixture that reaction is crosslinked are closed, this group of unsaturation containing ethylene linkage is selected from monomer, oligomer or prepolymer, or
The water-borne dispersions of their mixture or copolymer or said components.
6. mixture according to claim 5, which is characterized in that light in the light radiation be selected from ultraviolet, visible light or
LED light.
7. mixture according to claim 5, which is characterized in that the ethylene linkage that contains is C=C.
8. mixture according to claim 5, which is characterized in that the amount of the logical formula (I) compound contained is 0.5-10 weight
Measure part.
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| CN109776419B (en) * | 2019-03-07 | 2021-06-08 | 同济大学 | Pyrazoline group-containing sulfonium salt and preparation method and application thereof |
| CN112300042B (en) * | 2020-09-27 | 2022-06-07 | 同济大学 | 4-benzo five-membered ring-phenyl sulfonium salt compound and preparation method and application thereof |
| CN113698563A (en) * | 2021-08-05 | 2021-11-26 | 明光科迪新材料有限公司 | Thioxanthone polyurethane modified epoxy acrylate LED (light-emitting diode) photocuring resin |
| CN113831428B (en) * | 2021-09-22 | 2023-02-28 | 贵州师范学院 | Thioxanthone-chalcone photoinitiator as well as preparation method and application thereof |
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