CN112961165A - 新型咔唑并吡喃类化合物制备及其应用 - Google Patents
新型咔唑并吡喃类化合物制备及其应用 Download PDFInfo
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- CN112961165A CN112961165A CN202110188388.2A CN202110188388A CN112961165A CN 112961165 A CN112961165 A CN 112961165A CN 202110188388 A CN202110188388 A CN 202110188388A CN 112961165 A CN112961165 A CN 112961165A
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- carbazole
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- -1 carbazole benzopyran compound Chemical class 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 238000003847 radiation curing Methods 0.000 claims abstract description 7
- 238000000016 photochemical curing Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 238000009472 formulation Methods 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- SEPQTYODOKLVSB-UHFFFAOYSA-N 3-methylbut-2-enal Chemical compound CC(C)=CC=O SEPQTYODOKLVSB-UHFFFAOYSA-N 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- UEOHATPGKDSULR-UHFFFAOYSA-N 9h-carbazol-4-ol Chemical compound N1C2=CC=CC=C2C2=C1C=CC=C2O UEOHATPGKDSULR-UHFFFAOYSA-N 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 claims description 3
- LZMMZBXPCWKECN-UHFFFAOYSA-N pyrano[3,2-a]carbazole Chemical class O1C=CC=C2C3=NC4=CC=CC=C4C3=CC=C21 LZMMZBXPCWKECN-UHFFFAOYSA-N 0.000 claims description 3
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- ACWQBUSCFPJUPN-UHFFFAOYSA-N Tiglaldehyde Natural products CC=C(C)C=O ACWQBUSCFPJUPN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001263 acyl chlorides Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000008064 anhydrides Chemical class 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
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 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
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000006146 oximation reaction Methods 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims 4
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 239000013538 functional additive Substances 0.000 claims 1
- 239000000543 intermediate Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
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- 239000003973 paint Substances 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 33
- 239000000047 product Substances 0.000 description 16
- 238000001035 drying Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000002904 solvent Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 238000001723 curing Methods 0.000 description 5
- 238000012544 monitoring process Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HFWVMVDBCKOHRA-UHFFFAOYSA-N O1CC=CC=C1.C1=CC=CC=2C3=CC=CC=C3NC12 Chemical group O1CC=CC=C1.C1=CC=CC=2C3=CC=CC=C3NC12 HFWVMVDBCKOHRA-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Substances ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- 238000006748 scratching Methods 0.000 description 2
- 230000002393 scratching effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- YTLYLLTVENPWFT-UPHRSURJSA-N (Z)-3-aminoacrylic acid Chemical compound N\C=C/C(O)=O YTLYLLTVENPWFT-UPHRSURJSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 description 1
- SHUQFBKCOHURJQ-UHFFFAOYSA-N 9-hexylcarbazole Chemical compound C1=CC=C2N(CCCCCC)C3=CC=CC=C3C2=C1 SHUQFBKCOHURJQ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- HPGWAEIBNAULOL-UHFFFAOYSA-N C(C=C)(=O)OC(C(COC(C=C)=O)(COC(C=C)=O)COC(C=C)=O)OCC Chemical compound C(C=C)(=O)OC(C(COC(C=C)=O)(COC(C=C)=O)COC(C=C)=O)OCC HPGWAEIBNAULOL-UHFFFAOYSA-N 0.000 description 1
- TXSJAMJYKKJMKI-UHFFFAOYSA-N CCCCCCN(C(C=C1)=C2C=C1C(C(OC)=O)=O)C(C=C1)=C2C2=C1C=CC(C)(C)O2 Chemical compound CCCCCCN(C(C=C1)=C2C=C1C(C(OC)=O)=O)C(C=C1)=C2C2=C1C=CC(C)(C)O2 TXSJAMJYKKJMKI-UHFFFAOYSA-N 0.000 description 1
- LAVNKXPPNSNYCT-UHFFFAOYSA-N CCCCCCN(C(C=C1)=C2C=C1C(C(OCC)=O)=O)C(C=C1)=C2C2=C1C=CC(C)(C)O2 Chemical compound CCCCCCN(C(C=C1)=C2C=C1C(C(OCC)=O)=O)C(C=C1)=C2C2=C1C=CC(C)(C)O2 LAVNKXPPNSNYCT-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-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
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- ZXUQEPZWVQIOJE-UHFFFAOYSA-N methyl 2-chloro-2-oxoacetate Chemical compound COC(=O)C(Cl)=O ZXUQEPZWVQIOJE-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000006223 plastic coating Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/04—Ortho-condensed systems
- C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
- C07D491/052—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being six-membered
-
- 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
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- 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
- 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)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Indole Compounds (AREA)
Abstract
本发明涉及新材料有机化学品技术领域,新型咔唑并吡喃化合物及其应用。特别涉及式(I)所示以咔唑并吡喃为核心结构的新化合物,其化学制备工艺技术,其作为辐射固化光敏引发剂的用途,以及其在辐射固化配方产品,特别是UV‑Vis‑LED可激发的光固化涂料或油墨,等诸多场合的应用用途。
Description
【技术领域】
本发明涉及新材料有机化学品技术领域,特别涉及一类新的含有咔唑并吡喃结构的化合物,其化学制备工艺技术,其作为辐射固化光敏引发剂的用途,以及其在辐射固化配方产品,特别是在UV-Vis-LED光固化涂料或油墨,等诸多场合的应用用途。
【背景技术】
光引发剂化合物是一类重要的精细有机化学品材料。在发射紫外光或可见光的光源的辐射下生成自由基活性物种的光引发剂化合物,是诱发含烯不饱和体系进行高效光聚合反应的关键物种,因此是重要的辐射固化配方组分之一。在另一方面,光固化光源通常使用汞灯,汞蒸汽不符合世界节能环保产业发展的战略新趋势,因而在近年来LED光源获得了日益广泛的重视和快速的发展,且LED光固化技术的应用大幅度降低了能源消耗和臭氧生成,产业持续增长动力强劲。对于LED体系固化,也需要既针对LED长波发射波长(365-420纳米,特别是 395-405纳米)有灵敏吸收的光引发剂。因此,设计、研发和产业化新型的光引发剂化合物,是当前本领域面对的关键性技术挑战问题。设计新的共轭结构,使其吸收光谱进一步红移是一个可行的途径。
【发明内容】
针对上述技术挑战,本发明发现咔唑并吡喃化合物化合物,具备与LED非常匹配的吸收波长,在LED激发的各类光聚合体系中具有良好的应用前景。并且在如引入极性基团后,具有合适的水溶性或水分散性。这样的技术对木器绿色涂装,环保印刷,喷墨打印,节能材料等领域拥有深远的影响。
本项申请披露如下通式(I)所示的新型咔唑并吡喃类化合物:
在上述通式(I)化合物结构中:
R1是R,(CH2)nOR,(CH2)nSR,或(CH2)nNRR’,R3,R4和R5,独立地是R, OR,NRR’,CH2OH,CH2OR,C(O)R,COOR,C(NOCOR)R’或CH2NRR’中的一种结构,其中R或R’彼此独立的是含有1-24个碳原子(标记为-C1-C24,下同) 的直链或支链的烷基或-C6-C12芳基,R或R’结构中可以含有1-6个非连续的氧,氮,或硫元素,R和R’同时存在时其间也可以形成一个3-6元的环系结构。R1优选的甲基,乙基,丙基,异丙基,丁基,异丁基,己基等;R2优选的是甲基,乙基,丙基,异丙基,丁基,异丁基,COOCH3,COOC2H5,C(NOCOCH3)C2H5, C(NOCOC6H5)C2H5等;
通式(I)化合物的具体合成路线为:
自4-羟基咔唑出发,经由已知文献方法,与3-甲基-2-丁烯醛扣环即可得到通式(I)的咔唑并吡喃共轭主体产物,再在此基础上和R1取代的卤代烷反应引入烷基链增加产物的溶解性,最后经由傅氏酰基化反应制得通式(I)产物,或在经过与亚硝酸异戊酯的肟化、与酸酐或酰氯的酯化反应得到另外一部分通式(I) 产物。
上述通式(I)化合物的制备方法我们将结合实施例子做进一步的示例性说明。
符合通式(I)结构的示例性化合物列举如下:
本发明进一步披露一种含有上述通式(I)化合物的、可经由光(紫外或可见光或LED光或等价光源)辐射固化的混合物,以及这类配方材料体系在喷墨打印,纸张印刷,粘合剂,木器涂装,塑胶涂装,汽车涂装,包装材料,柔性电子,光伏材料等领域的应用。
这类光辐射固化配方体系的特征是:
(1)含有至少一种通式(I)所描述的化合物作为光引发剂或光引发剂组分之一;
(2)含有至少一种含烯键(C=C)不饱和化合物。
以体系中含烯键不饱和组分总量每100份重量计算,含有的通式(I)化合物的合适的量是0.01-30重量份,优选0.5-10重量份。本项申请披露的合适辐射固化体系包含的可聚合的含烯键不饱和组分是可以通过该双键的自由基聚合反应被交联的化合物或混合物,这种含烯键不饱和组分可以是单体,低聚物或预聚物,或是它们的混合物或共聚物,或是上述组分的水性分散体。
上述所述的合适辐射固化体系均可以含有根据实际需要所添加的无机或有机填充剂和/或着色剂(例如颜料或染料等),以及其它添加剂(例如紫外线吸收剂,光稳定剂,阻燃剂,流平剂,或消泡剂等)和溶剂等任意成分。
合适的自由基聚合的单体是例如含烯键可聚合单体,包括但不限于(甲基) 丙烯酸酯,丙烯醛,烯烃,共轭双烯烃,苯乙烯,马来酸酐,富马酸酐,乙酸乙烯酯,乙烯基吡咯烷酮,乙烯基咪唑,(甲基)丙烯酸,(甲基)丙烯酸衍生物例如(甲基)丙烯酰胺,乙烯基卤化物,亚乙烯基卤化物等。
合适的含烯键预聚物和低聚物包括但不限于(甲基)丙烯酰官能基的(甲基) 丙烯酸共聚物,聚氨酯甲酸酯(甲基)丙烯酸酯,聚酯(甲基)丙烯酸酯,不饱和聚酯,聚醚(甲基)丙烯酸酯,硅氧烷(甲基)丙烯酸酯,环氧树脂(甲基) 丙烯酸酯等,以及上述物质的水溶性或水分散性的类似物。
上述无论是含烯单体还是低聚物,预聚物,或共聚物,对本专业从业技术人员而言,都是熟知的,并无特别限定。
对于本发明的要旨,我们将结合下述系列实施例进一步说明。
【具体实施方式】
实施例一:Methyl 2 -(7-hexyl-2,2-dimethyl-2,7-dihydropyrano[3,2-c]carbazol-10-yl)-2-oxoacetate
(a)乙酰乙酸乙酯,90℃,24h;(b)溴己烷,K2CO3,THF,75℃;(c)甲基草酰氯,4 h.
1.合成化合物2,2-二甲基-2,7-二氢吡喃并咔唑(A)
按照文献方法,将4-羟基咔唑与3-甲基丁-2-烯醛在回流的对二甲苯中反应 12小时。反应完成后,减压除去溶剂。残余物通过柱色谱纯化,得到产物A。1H NMR(400MHz,CDCl3)δ=8.23(d,J=7.7,1H),7.84(s,1H),7.32–7.22(m,2H), 7.15(d,J=7.9,1H),6.94(d,J=8.1,1H),6.76(d,J=8.1,1H),6.37(d,J=9.8,1H),5.44 (dd,J=11.8,6.0,1H),1.49(s,6H).
2.合成2,2-二甲基-2,7-二氢吡喃并(N-己基)咔唑(B)
在圆底烧瓶中加入化合物A(1mol eq),碳酸钾(2mol eq),溴己烷(10 mol eq),及少量的碘化钾和18-C-6,并加入适量DMF,摇匀后搅拌100℃反应 24h,直至TLC(薄层层析法)检测无原料点反应结束后,过滤出去不溶物,将滤液减压蒸馏除去大部分溶剂,而后用二氯甲烷或乙酸乙酯萃取,收集有机层,无水硫酸钠干燥,柱层析法提纯,得到产物B。1HNMR(400MHz,CDCl3)δ(ppm) =8.26(d,J=7.7,1H,PhH),7.32(t,J=8.1Hz,1H,PhH),7.23(d,J=8.1,1H,PhH),7.12 (t,J=7.8,1H,PhH),6.97(d,J=8.1,1H,PhH),6.74(d,J=8.1,1H,PhH),6.37(d, J=9.8,1H,PhH),5.41(d,J=9.8,1H,PhH),4.10(t,J=7.3,2H,CH2),1.77–1.69(m, 2H,CH2),1.48(s,6H,CH3),1.23–1.13(m,6H,CH2),0.76(t,J=7.0,3H,CH3).
3.合成目标光引发剂(C)
在100℃烘干的三口烧瓶中,快速加入三氯化铝(2mol eq)和化合物B(1 mol eq),而后抽真空充氮气反复三次,再注入适量无水二氯甲烷,冷浴下缓慢滴草酰氯单甲酯(1.5mol eq)。升至室温后TCL监测反应至反应完全,缓慢倒入水中,用二氯甲烷萃取多次,经无水硫酸钠干燥,减压蒸馏除去溶剂,柱层析或重结晶提纯后真空烘箱干燥制的产物,产率65%。
该合成目标光引发剂(C)应用于实施例四。
实施例二:Ethyl 2 -(7-hexyl-2,2-dimethyl-2,7-dihydropyrano[3,2-c]carbazol-10-yl)-2-oxoacetate
1.合成目标光引发剂(D)
在100℃烘干的三口烧瓶中,快速加入三氯化铝(2mol eq)和化合物B(1 mol eq),而后抽真空充氮气反复三次,再注入适量无水二氯甲烷,冷浴下缓慢滴加草酰氯单乙酯(1.5mol eq)。升至室温后TCL监测反应至反应完全,缓慢倒入水中,用二氯甲烷萃取多次,经无水硫酸钠干燥,减压蒸馏除去溶剂,柱层析提纯后真空烘箱干燥制得产物,产率66%。
该合成目标光引发剂(D)应用于实施例四。
实施例三:制备肟酯
1.合成中间体(E)
在100℃烘干的三口烧瓶中,快速加入三氯化铝(2mol eq)和化合物B(1 mol eq),而后抽真空充氮气反复三次,再注入适量无水二氯甲烷,冷浴下缓慢滴加丁酰氯(1.5moleq)。升至室温后TCL监测反应至反应完全,缓慢倒入水中,用二氯甲烷萃取三次,经无水硫酸钠干燥,减压蒸馏除去溶剂,柱层析提纯后真空烘箱干燥制得产物,产率76%。
2.合成中间体(F)
在烧瓶中加入中间体E(1mol eq),溶于适量的四氢呋喃中,常温搅拌下,加入1.1当量浓盐酸,再加入1.1当量亚硝酸异戊酯,TCL监测反应至反应完全,缓慢倒入水中,用二氯甲烷萃取三次,经无水硫酸钠干燥,减压蒸馏除去溶剂,用石油醚沉淀得到纯品,真空烘箱干燥制得产物,产率83%。
3.合成光引发剂(G)
在100度烘箱中干燥的烧瓶中,氮气保护下加入中间体F(1当量),溶于适量的无水二氯甲烷中,用注射器注入干燥的三乙胺(1.1当量),冰浴冷却下滴加乙酸酐的二氯甲烷溶液(1当量),TCL监测反应至反应完全,缓慢倒入水中,用二氯甲烷萃取三次,水洗,饱和食盐水洗涤,经无水硫酸钠干燥,减压蒸馏除去溶剂,经柱层析得到纯品,真空烘箱干燥制得产物,产率90%。
上述合成目标光引发剂(G)应用于实施例四。
实施例四:LED光固化试验
含烯键(丙烯酸酯)样品体系按下列配方制作(以重量百分比计):
双酚A环氧丙烯酸酯(Ebecryl 605):25%;氨基丙烯酸酯(Ebecryl 7100): 8%;丙氧基化甘油三丙烯酸酯:25%;己二醇二丙烯酸酯:22%;聚硅氧烷丙烯酸酯:0.5%;乙氧基季戊四醇四丙烯酸酯:3.5%;光引发剂:2%本实施例光引发剂;助引发剂:甲基二乙醇胺(MDEA)。
将上述配制实施例混合物涂覆于卡纸板上形成约30-35微米的涂层,1单位功率为16W/cm2的发射波长为395纳米的LED光源(3厘米宽和40厘米长LED 面光源),变速传送带试验。以指甲反复压刻刮擦不产生印迹为光聚合固化完成的判据。
残余气味测试以5个人分别独立地评价气味级别,评估的标准以数字标示如下: 0级:没有气味;1级:非常轻微的气味;2级:轻微的气味;3级:明显的气味; 4级:强烈的气味;5级:非常强烈的气味。
结果表明含有上述各实施例化合物(C,D,G)的配方体系以高于30米/分钟的速度高效固化(用于表征光固化效率性能),且气味等级为0或0-1级。
上述实验结果表明本发明制备的这些光引发剂同时具有良好的LED光固化效率性能和(净)或低气味特征。
需要强调的是,上述列举的实施例仅是一些示例性试验,不应被视为是限定性试验或条件。本发明申请所涵盖的创新范围应以权利要求书记载为准。
Claims (5)
1.一种通式(I)所示咔唑并吡喃类化合物,特征是:
在上述通式(I)化合物结构中:
R1是R,(CH2)nOR,(CH2)nSR,或(CH2)nNRR’,R3,R4和R5,独立地是R,OR,NRR’,CH2OH,CH2OR,C(O)R,COOR,C(NOCOR)R’或CH2NRR’中的一种结构,其中R或R’彼此独立的是含有1-24个碳原子(标记为-C1-C24,下同)的直链或支链的烷基或-C6-C12芳基,R或R’结构中可以含有1-6个非连续的氧,氮,或硫元素,R和R’同时存在时其间也可以形成一个3-6元的环系结构。R1优选的甲基,乙基,丙基,异丙基,丁基,异丁基,己基等;R2优选的是甲基,乙基,丙基,异丙基,丁基,异丁基,COOCH3,COOC2H5,C(NOCOCH3)C2H5,C(NOCOC6H5)C2H5。
2.一种制备权利要求1部分通式(I)所示咔唑并吡喃化合物的方法,特征是:
自4-羟基咔唑出发,与3-甲基-2-丁烯醛扣环即可得到通式(I)的咔唑并吡喃共轭主体产物,再在此基础上和R1取代的卤代烷反应引入烷基链增加产物的溶解性,最后经由傅氏酰基化反应制得通式(I)产物,或在经过与亚硝酸异戊酯的肟化、与酸酐或酰氯的酯化反应得到另外一部分通式(I)产物。
3.一种权利要求1通式(I)所示咔唑并吡喃类化合物在光固化配方体系中作为光引发剂或其它功能性添加剂成分的用途,及在化学合成中作为中间体或原料或试剂的用途。
4.一种含有权利要求1通式(I)化合物的,可经由光(紫外或可见光或LED光或等价光源)辐射固化的混合物构成的光辐射固化配方体系;其特征在于,
该类光辐射固化配方体系:(1)含有至少一种通式(I)所描述的化合物作为光引发剂或光引发剂组分之一;且(2)含有至少一种含烯键(C=C)不饱和化合物。
5.如权利要求4所述光辐射固化配方体系,其特征在于,以体系中含烯键不饱和组分总量每100份重量计算,含有的通式(I)化合物的合适的量是0.01-30重量份,优选0.5-10重量份;合适的辐射固化体系包含的可聚合的含烯键不饱和组分是可以通过该双键的自由基聚合反应被交联的化合物或混合物,这种含烯键不饱和组分可以是单体,低聚物或预聚物,或是它们的混合物或共聚物,或是上述组分的水性分散体。
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CN114133402A (zh) * | 2021-10-28 | 2022-03-04 | 同济大学 | 可自由基引发聚合的香豆素并咔唑类光引发剂和制备方法及其应用 |
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