CN111559963A - 一种长波长苯甲酰甲酸甲酯类光引发剂及其制备方法 - Google Patents
一种长波长苯甲酰甲酸甲酯类光引发剂及其制备方法 Download PDFInfo
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- CN111559963A CN111559963A CN202010428093.3A CN202010428093A CN111559963A CN 111559963 A CN111559963 A CN 111559963A CN 202010428093 A CN202010428093 A CN 202010428093A CN 111559963 A CN111559963 A CN 111559963A
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- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- -1 ketone compound Chemical class 0.000 claims abstract description 22
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 13
- 238000006482 condensation reaction Methods 0.000 claims abstract description 12
- 125000003172 aldehyde group Chemical group 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 125000003545 alkoxy group Chemical group 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 17
- 125000003342 alkenyl group Chemical group 0.000 claims description 16
- 125000000304 alkynyl group Chemical group 0.000 claims description 16
- 229910052736 halogen Inorganic materials 0.000 claims description 14
- 150000002367 halogens Chemical class 0.000 claims description 14
- 125000005842 heteroatom Chemical group 0.000 claims description 14
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 14
- FAQJJMHZNSSFSM-UHFFFAOYSA-N phenylglyoxylic acid Chemical compound OC(=O)C(=O)C1=CC=CC=C1 FAQJJMHZNSSFSM-UHFFFAOYSA-N 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 12
- 239000012265 solid product Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 6
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 6
- NZFLWVDXYUGFAV-UHFFFAOYSA-N 1-methyl-2-acetylpyrrole Chemical compound CC(=O)C1=CC=CN1C NZFLWVDXYUGFAV-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 229940043279 diisopropylamine Drugs 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 17
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Natural products ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 238000002390 rotary evaporation Methods 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000001914 filtration Methods 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 11
- 238000000862 absorption spectrum Methods 0.000 description 11
- 239000003999 initiator Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- SZTDMXSGQVDHMG-UHFFFAOYSA-N COC(C(C1=CC=C(C=O)C=C1)=O)=O Chemical compound COC(C(C1=CC=C(C=O)C=C1)=O)=O SZTDMXSGQVDHMG-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- GGAUKKFBDRHCPI-UHFFFAOYSA-N COC(C(C1=CC(OC)=C(C=O)C=C1)=O)=O Chemical compound COC(C(C1=CC(OC)=C(C=O)C=C1)=O)=O GGAUKKFBDRHCPI-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 150000004702 methyl esters Chemical class 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- UIIIPQVTXBPHTI-UHFFFAOYSA-N 2-(4-methylphenyl)-2-oxoacetic acid Chemical compound CC1=CC=C(C(=O)C(O)=O)C=C1 UIIIPQVTXBPHTI-UHFFFAOYSA-N 0.000 description 2
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- IGFZBRICJIHTBI-UHFFFAOYSA-N methyl 2-(4-methylphenyl)-2-oxoacetate Chemical compound COC(=O)C(=O)C1=CC=C(C)C=C1 IGFZBRICJIHTBI-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- CVEDVJRENZAPPJ-UHFFFAOYSA-N potassium;ethanol;2-methylpropan-2-olate Chemical compound [K+].CCO.CC(C)(C)[O-] CVEDVJRENZAPPJ-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- ZABQZTCLFVFVQO-UHFFFAOYSA-N C(C)O.CC(C)(C)[O-].[Na+] Chemical compound C(C)O.CC(C)(C)[O-].[Na+] ZABQZTCLFVFVQO-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RYDMHGMXZHJUHB-UHFFFAOYSA-N lithium;cyclohexane;di(propan-2-yl)azanide Chemical compound [Li+].C1CCCCC1.CC(C)[N-]C(C)C RYDMHGMXZHJUHB-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
- C07C69/738—Esters of keto-carboxylic acids or aldehydo-carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member 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 to ring carbon atoms
- C07D207/24—Oxygen or sulfur atoms
- C07D207/26—2-Pyrrolidones
- C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
- C07D207/267—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/333—Radicals substituted by oxygen or sulfur atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/337—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members 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 to ring carbon atoms
- C07D207/36—Oxygen or sulfur atoms
- C07D207/38—2-Pyrrolones
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- 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
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- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及有机合成技术领域,尤其涉及一种长波长苯甲酰甲酸甲酯类光引发剂及其制备方法。目前市面上所使用的LED光源的发射波长范围均在365nm以上,而传统的光引发剂MBF的最大吸收波长为255nm,与LED光源的发射波长不相匹配,为了使得MBF光引发剂的最大吸收波长与LED光源的主要发射波长范围相匹配,本发明提供一种长波长苯甲酰甲酸甲酯类光引发剂,其由醛基和/或R1官能化的苯甲酰甲酸甲酯衍生物与含有αH原子的酮类化合物发生缩合反应得到,其最大吸收波长可以达到365nm以上,与市面上使用的LED光源相匹配,具有良好的商业应用前景。
Description
技术领域
本发明涉及有机合成技术领域,尤其涉及一种长波长苯甲酰甲酸甲酯类光引发剂及其制备方法。
背景技术
光引发剂MBF,又称是苯甲酰甲酸甲酯。苯甲酰甲酸甲酯为无色或浅黄色液体,能溶于甲苯、乙醇、***等有机溶剂,是近几年发展起来的一种光引发剂,其往往与汞灯一起使用,有引发效率高、热稳定性好、气味低等诸多优点,在光聚合体系中有着重要地位。
随着中国签署水俣公约,汞灯将被禁止使用。LED光源在是一种新型的低功率光源,相对于汞灯来说有着诸多优势,例如效率高、无臭氧的产生、无汞污染、寿命长等,近年来在光聚合领域中得到了普及使用。但是由于封装技术等原因,LED光源无法持续稳定地发射短波长的紫外光,其主要的发射波长集中在365nm-400nm,而传统光引发剂MBF的主要吸收波长为255nm和325nm。若使用LED光源提供光聚合反应的能量,MBF作为光聚合反应的光引发剂,则光聚合反应中聚合单体的双键转化率会比较小。因此,开发与LED光源的发射波长相匹配的长波长光引发剂具有很大的商业价值。
发明内容
针对现有技术中存在的问题,本发明要解决的技术问题是:如何提高传统光引发剂MBF的最大吸收波长,使其与LED光源的主要发射波长相适应,提高光聚合反应中的双键转化率。
本发明解决其技术问题所采用的技术方案是:
本发明提供一种长波长苯甲酰甲酸甲酯类光引发剂,具有通式Ⅰ、Ⅱ、Ⅲ、Ⅳ所示的分子结构:
上述通式中:
4R1表示苯环上4个任意空位上的取代基;
R1是氢原子、烷基、烯基、烷氧基、炔基、羟基、硝基、卤素、磺酸基以及被杂原子,卤素、烯基、炔基、硝基、氰基、磺酸基取代的烷基、烯基、烷氧基或炔基中的任意一种;
R2是烷基、含杂原子的烷基以及被杂原子,卤素、烯基、炔基、硝基、氰基、磺酸基取代的烷基中的任意一种;
R3和R4是氢原子、烷基、烷氧基以及被杂原子、卤素、烯基、炔基、硝基、氰基、磺酸基、芳香基、杂环芳香基取代的烷基或烷氧基中的任意一种;
R5是烷基、烷氧基以及被杂原子、卤素、烯基、炔基、硝基、氰基、磺酸基取代的烷基中的任意一种;
R6是烷基、烷氧基以及被杂原子、卤素、烯基、炔基、硝基、氰基、磺酸基、芳香基、杂环芳香基取代的烷基或烷氧基中的任意一种;
R7可以为氢原子、烷基、烷氧基以及被杂原子、卤素、烯基、炔基、硝基、氰基、磺酸基、芳香基、杂环芳香基取代的烷基或烷氧基中的任意一种。
具体地,所述的一种长波长苯甲酰甲酸甲酯类光引发剂,其特征在于,具有以下化学式:
具体地,一种长波长苯甲酰甲酸甲酯类光引发剂的制备方法,按照以下步骤制备:
(1)首先制备醛基和/或R1官能化的苯甲酰甲酸甲酯衍生物;
(2)醛基和/或R1官能化的苯甲酰甲酸甲酯衍生物与含有αH原子的酮类化合物进行缩合反应,将反应得到的固体产物纯化后,即得到长波长苯甲酰甲酸甲酯类光引发剂。
具体地,所述苯甲酰甲酸甲酯衍生物的化学式如下:
具体地,所述含有αH原子的酮类化合物为:丙酮、3-戊酮、环己酮、4,4-二甲基环己酮、苯乙酮、N-甲基吡咯烷酮、N-乙烯基吡咯烷酮、2-乙酰基-1-甲基吡咯或2-戊酮。
具体地,所述缩合反应中醛基和/或R1官能化的苯甲酰甲酸甲酯衍生物与含有αH原子的酮类化合物的摩尔比为1-2:1。
具体地,所述缩合反应的温度为0-80℃,反应时间为0.05-5h,pH=8-13。
具体地,所述缩合反应的溶剂为甲醇、乙醇、异丙醇、叔丁醇、四氢呋喃、二甲基甲酰胺或二甲基亚砜。
具体地,所述缩合反应的催化剂为氢氧化钠、氢氧化钾、叔丁醇钠、叔丁醇钾、碳酸氢钠、二异丙胺、吡啶、二异丙基氨基锂、三乙醇胺、甲基二乙醇胺或六甲基二硅基氨基锂。
本发明的有益效果是:
(1)本发明所制备的长波长苯甲酰甲酸甲酯类光引发剂的最大吸收波长可达356nm以上,与光聚合领域常用的LED光源的发射波长相匹配,性能更加优异、市场化潜力更强。
(2)本发明制备长波长苯甲酰甲酸甲酯类光引发剂的方法简单,仅通过一步缩合反应即可得到产物,制备成本低,容易进行工业化生产。
附图说明
图1:传统商业MBF光引发剂的紫外吸收光谱。
图2:实施例1所制备长波长光引发剂的紫外吸收光谱。
图3:实施例2所制备长波长光引发剂的紫外吸收光谱。
图4:实施例3所制备长波长光引发剂的紫外吸收光谱。
图5:实施例4所制备长波长光引发剂的紫外吸收光谱。
图6:实施例5所制备长波长光引发剂的紫外吸收光谱。
图7:实施例6所制备长波长光引发剂的紫外吸收光谱。
图8:实施例7所制备长波长光引发剂的紫外吸收光谱。
图9:实施例8所制备长波长光引发剂的紫外吸收光谱。
图10:实施例9所制备长波长光引发剂的紫外吸收光谱。
图11:实施例10所制备长波长光引发剂的紫外吸收光谱。
具体实施方式
现在结合附图对本发明作进一步详细的说明。
实施例1
(1)2-(4-甲酰基苯基)-2-氧乙酸甲酯的制备实施例:
将2mol 4-甲基苯乙酮和4mol二氧化硒溶解与1000mL吡啶中,在120℃氮气氛围下反应18h,反应结束后,将反应液过滤、蒸发去除有机溶剂得到剩余反应液,随后,在剩余反应液中加入200ml 2mol/L的氢氧化钠溶液,再加入200ml乙酸乙酯,再滴加100ml质量浓度为65%的浓盐酸,直接分液旋蒸有机相得到淡黄色油状的2-氧-2-(对甲苯基)乙酸;
(2)将0.5mol的2-氧-2-(对甲苯基)乙酸与1.7mol碳酸钾在200mL的DMSO中溶解,逐滴加入57ml硫酸二甲酯,在室温搅拌0.5h后,将反应混合物与200ml***混合,分液,收集***相,用50ml 1mol/L碳酸钾溶液洗涤3次,并用100ml的饱和食盐水洗涤1次,无水硫酸镁干燥后,过滤、旋蒸滤液,得到2-氧-2-(对甲苯基)乙酸甲酯;
(3)将0.2mol 2-氧-2-(对甲苯基)乙酸甲酯溶于100ml乙醇中,加入3.4g的二氧化锰,再缓慢滴加20ml的质量浓度为74%H2SO4水溶液,反应0.5h后,在反应产物中加入25ml饱和食盐水和25ml乙酸乙酯萃取后,即可得到2-(4-甲酰基苯基)-2-氧乙酸甲酯;
(4)将0.10mol的2-(4-甲酰基苯基)-2-氧乙酸甲酯与0.05mol丙酮加入50mL乙醇中溶解,以质量分数为1wt%NaOH水溶液为催化剂,调节pH=8,80℃下反应5h后,反应体系在降温中不断析出固体,将固体过滤、洗涤、真空干燥,最终得到长波长苯甲酰甲酸甲酯类光引发剂,反应方程式如下:
所制备的新型苯甲酰甲酸甲酯光引发剂的结构通过1H-NMR和MS得到确认,1H-NMR(d-DMSO,400MHz):δ(ppm)3.61(s,6H),7.03(s,2H),7.53(m,4H),7.80(m,4H),7.82(s,2H);MS(m/z):406(M+1)+。
所制备的长波长苯甲酰甲酸甲酯类光引发剂的最大吸收波长为369nm(见说明书附图2),在波长为365nm的LED点光源照射下,引发剂浓度为质量分数1w%,聚合单体1,6-己二醇二丙烯酸酯在250s内的双键转化率为79%。
实施例2
将0.19mol的2-(4-甲酰基苯基)-2-氧乙酸甲酯与0.1mol 3-戊酮加入60mL乙醇中溶解,以质量分数为1.5wt%NaOH水溶液为催化剂,调节pH=9,70℃下反应4h后,停止加热,室温冷却,发现有固体析出,将固体过滤、用少量甲醇洗涤、重结晶、真空干燥,最终得到长波长苯甲酰甲酸甲酯类光引发剂,反应方程式如下:
所制备的新型苯甲酰甲酸甲酯光引发剂的结构通过1H-NMR和MS得到确认,1H-NMR(d-DMSO,400MHz):δ(ppm)2.34(s,6H),3.61(s,6H),7.37(s,2H),7.53(m,4H),7.80(m,4H);MS(m/z):434(M+1)+;
所制备的长波长苯甲酰甲酸甲酯类光引发剂的最大吸收波长为365nm(见说明书附图3),在波长为365nm的LED点光源照射下,引发剂浓度为质量分数1w%,聚合单体1,6-己二醇二丙烯酸酯在250s内的双键转化率为82%。
实施例3
将0.135mol的2-(4-甲酰基苯基)-2-氧乙酸甲酯与0.075mol 4,4-环己酮加入45mL乙醇中溶解,以质量分数为1wt%KOH水溶液为催化剂,调节pH=10,60℃下反应3h后,降温缓慢析出固体,过滤、用少量乙醇洗涤、真空干燥,最终得到长波长苯甲酰甲酸甲酯类光引发剂,反应方程式如下:
所制备的新型苯甲酰甲酸甲酯光引发剂的结构通过1H-NMR和MS得到确认,1H-NMR(d-DMSO,400MHz):δ(ppm)1.00(s,6H),1.82(s,4H),3.61(s,6H),7.37(s,2H),7.53(m,4H),7.80(m,4H);MS(m/z):474(M+1)+;
所制备的长波长苯甲酰甲酸甲酯类光引发剂的最大吸收波长为360nm(见说明书附图4),在波长为365nm的LED点光源照射下,引发剂浓度为质量分数1w%,聚合单体1,6-己二醇二丙烯酸酯在250s内的双键转化率为78%。
实施例4
将0.15mol的2-(4-甲酰基苯基)-2-氧乙酸甲酯与0.15mol 1-(1-甲基-1H-吡咯-2-基)乙-1-酮加入60mL甲醇中溶解,以质量分数为2wt%KOH水溶液为催化剂,调节pH=11,25℃下反应2h后,以二氯甲烷饱和食盐水多次萃取反应产物,将有机萃取液用旋转蒸发仪旋蒸得到固体产物,将固体产物用乙醇洗涤、真空干燥,最终得到长波长苯甲酰甲酸甲酯类光引发剂,反应方程式如下:
所制备的新型苯甲酰甲酸甲酯光引发剂的结构通过1H-NMR和MS得到确认,1H-NMR(d-DMSO,400MHz):δ(ppm)3.61(s,3H),3.91(s,3H),6.49(m,1H),6.70(d,1H),7.54(m,3H),7.70(d,1H),7.78(m,3H);MS(m/z):297(M+1)+。
所制备的长波长苯甲酰甲酸甲酯类光引发剂的最大吸收波长为370nm(见说明书附图5),在波长为365nm的LED点光源照射下,引发剂浓度为质量分数1w%,聚合单体1,6-己二醇二丙烯酸酯在250s内的双键转化率为79%。
实施例5
将0.18mol的2-(4-甲酰基苯基)-2-氧乙酸甲酯与0.1mol 2-戊酮加入50mL乙醇中溶解,以2wt%叔丁醇钾乙醇溶液为催化剂,调节pH=11左右,15℃下反应1h后,用少量1:1的二氯甲烷饱和食盐水多次萃取反应液体,旋蒸得到固体产物,将固体产物用甲醇洗涤、真空干燥,最终得到长波长苯甲酰甲酸甲酯类光引发剂,反应方程式如下:
所制备的新型苯甲酰甲酸甲酯光引发剂的结构通过1H-NMR和MS得到确认,1H-NMR(d-DMSO,400MHz)δ(ppm):1.07(t,3H),2.44(m,2H),3.61(s,6H),7.03(d,1H),7.37(s,1H),7.53(m,4H),7.81(m,5H);MS(m/z):434(M+1)+。
所制备的长波长苯甲酰甲酸甲酯类光引发剂的最大吸收波长为365nm(见说明书附图6),在波长为365nm的LED点光源照射下,引发剂浓度为质量分数1w%,聚合单体1,6-己二醇二丙烯酸酯在250s内的双键转化率为83%。
实施例6
(1)2-(4-甲酰基-3-甲氧基苯基)-2-氧乙酸甲酯
将0.2mol的2-(4-甲酰基苯基)-2-氧乙酸甲酯溶于200ml乙醇中,冰浴下滴加45ml质量浓度为65%H2SO4水溶液,反应1.5h,再加入0.2mol氢氧化钠,滴加50ml质量浓度为10%HCl水溶液,最后加入0.2mol的CH3I,0.3gAlBr3,反应0.3h,加入20ml水,旋蒸除去有机溶剂,过滤得到2-(4-甲酰基-3-甲氧基苯基)-2-氧乙酸甲酯;
(2)将0.12mol的2-(4-甲酰基-3-甲氧基苯基)-2-氧乙酸甲酯与0.1mol苯乙酮加入30mLDMF中溶解,加入质量浓度为2wt%叔丁醇钠乙醇溶液为催化剂,调节pH=13左右,0℃下反应0.5h后,直接将反应液旋蒸得到粘稠状固体,用乙醇洗涤,加入二氯甲烷,将二氯甲烷收集再次旋蒸,得到固体产物,将固体产物过滤、洗涤、重结晶、真空干燥,最终得到长波长苯甲酰甲酸甲酯类光引发剂,反应方程式如下:
所制备的新型苯甲酰甲酸甲酯光引发剂的结构通过1H-NMR和MS得到确认,1H-NMR(d-DMSO,400MHz)δ(ppm):3.61(s,6H),3.90(s,3H),7.30(s,1H),7.43(d,1H),7.48-7.57(m,5H),7.81(m,2H),8.33(d,2H);MS(m/z):324(M+1)+。
所制备的长波长苯甲酰甲酸甲酯类光引发剂的最大吸收波长为366nm(见说明书附图7),在波长为365nm的LED点光源照射下,引发剂浓度为质量分数1w%,聚合单体1,6-己二醇二丙烯酸酯在250s内的双键转化率为81%。
实施例7
(1)2-(3-氯-4-甲酰基苯基)-2-氧乙酸甲酯
将0.2mol的2-(4-甲酰基-3-甲氧基苯基)-2-氧乙酸甲酯溶于300mL质量浓度为50%的乙醇水溶液中,不断通入氯气,加入1g FeCl3,反应0.25h,旋蒸除去乙醇,过滤得到2-(3-氯-4-甲酰基苯基)-2-氧乙酸甲酯;
(2)将0.48mol的2-(3-氯-4-甲酰基苯基)-2-氧乙酸甲酯与0.24mol环己酮加入200ml异丙醇中溶解,以质量浓度为10wt%二异丙基氨基锂环己烷溶液为催化剂,调节pH=13左右,35℃下反应0.1h后,旋蒸至粘稠状,分别加入二氯甲烷和饱和食盐水反复萃取,将萃取液再次旋蒸得到固体产物,将固体产物用少量石油醚洗涤、真空干燥,最终得到长波长苯甲酰甲酸甲酯类光引发剂,反应方程式如下:
所制备的新型苯甲酰甲酸甲酯光引发剂的结构通过1H-NMR和MS得到确认,1H-NMR(d-DMSO,400MHz):δ(ppm)1.47(m,2H),2.81(t,4H),3.61(s,6H),7.47(m,2H),7.64(s,2H),7.68(m,2H),7.75(s,2H);MS(m/z):514(M+1)+;
所制备的长波长苯甲酰甲酸甲酯类光引发剂的最大吸收波长为367nm(见说明书附图8),在波长为365nm的LED点光源照射下,引发剂浓度为质量分数1w%,聚合单体1,6-己二醇二丙烯酸酯在250s内的双键转化率为79%。
实施例8
将0.05mol的2-(4-甲酰基苯基)-2-氧乙酸甲酯与0.05molN-乙烯基吡咯烷酮加入150mL乙醇中溶解,以质量浓度为2wt%叔丁醇钾乙醇溶液为催化剂,调节pH=10左右,10℃下反应5h后,以1:1的乙酸乙酯饱和食盐水多次萃取反应产物,将乙酸乙酯相旋蒸得到固体产物,将固体产物用正己烷洗涤、真空干燥,最终得到长波长苯甲酰甲酸甲酯类光引发剂,反应方程式如下:
所制备的新型苯甲酰甲酸甲酯光引发剂的结构通过1H-NMR和MS得到确认,1H-NMR(d-DMSO,400MHz):δ(ppm)2.81(m,2H),3.00(m,2H),3.61(s,3H),4.68(d,1H),6.10(d,1H),7.26(s,1H),7.33(t,1H),7.53(d,2H),7.80(d,2H);MS(m/z):285(M+1)+;
所制备的长波长苯甲酰甲酸甲酯类光引发剂的最大吸收波长为369nm(见说明书附图9),在波长为365nm的LED点光源照射下,引发剂浓度为质量分数1w%,聚合单体1,6-己二醇二丙烯酸酯在250s内的双键转化率为78%。
实施例9
(1)2-(3-氰基-4-甲酰基苯基)-2-氧乙酸甲酯
将0.2mol的2-(4-甲酰基-3-甲氧基苯基)-2-氧乙酸甲酯溶于300mL质量浓度为50%的乙醇水溶液中,不断通入氯气,在1g FeCl3的催化下反应,反应0.25h,加入1g FeCl3后,反应0.25h,再加入0.2mol***,反应0.5h,旋蒸除去乙醇,过滤得到2-(3-氰基-4-甲酰基苯基)-2-氧乙酸甲酯;
(2)将0.11mol的2-(3-氰基-4-甲酰基苯基)-2-氧乙酸甲酯与0.1molN-甲基吡咯烷酮加入200ml四氢呋喃中溶解,以质量浓度为1wt%氢氧化钾乙醇溶液为催化剂,调节pH=8.5左右,30℃下反应4h后,停止加热,室温冷却,发现有固体析出,将固体过滤、用少量甲醇洗涤、重结晶、真空干燥,最终得到长波长苯甲酰甲酸甲酯类光引发剂,反应方程式如下:
所制备的新型苯甲酰甲酸甲酯光引发剂的结构通过1H-NMR和MS得到确认,1H-NMR(d-DMSO,400MHz):δ(ppm)2.81(t,2H),3.27(s,3H),3.48(t,2H),3.61(s,3H),7.48(s,1H),7.71(m,1H),8.08(m,1H),8.29(d,1H);MS(m/z):298(M+1)+;
所制备的长波长苯甲酰甲酸甲酯类光引发剂的最大吸收波长为375nm(见说明书附图10),在波长为365nm的LED点光源照射下,引发剂浓度为质量分数1w%,聚合单体1,6-己二醇二丙烯酸酯在250s内的双键转化率为74%。
实施例10
(1)2-(2-乙基-4-甲酰基苯基)-2-氧乙酸甲酯
将0.2mol的2-(4-甲酰基-3-甲氧基苯基)-2-氧乙酸甲酯溶于200ml 80%质量分数乙醇水溶液中,加入0.2mol氯代乙烷和2.5gAlCl3,反应2h,旋蒸除去乙醇,过滤得到2-(2-乙基-4-甲酰基苯基)-2-氧乙酸甲酯;
(2)将0.11mol的2-(2-乙基-4-甲酰基苯基)-2-氧乙酸甲酯与0.1mol丙酮加入75mL质量浓度为80%的乙醇水溶液溶解,以质量浓度为2wt%叔丁醇钾乙醇溶液为催化剂,调节pH=11左右,25℃下反应2h后,旋蒸得到粘稠状固体,用甲醇洗涤,用乙醇重结晶、过滤,再次用甲醇洗涤,真空干燥,最终得到长波长苯甲酰甲酸甲酯类光引发剂,反应方程式如下:
所制备的新型苯甲酰甲酸甲酯光引发剂的结构通过1H-NMR和MS得到确认,1H-NMR(d-DMSO,400MHz):δ(ppm)1.18(t,6H),2.71(m,4H),3.61(s,6H),7.03(d,2H),7.41(m,4H),7.80(m,2H),7.82(t,2H);
MS(m/z):462(M+1)+;
所制备的长波长苯甲酰甲酸甲酯类光引发剂的最大吸收波长为366nm(见说明书附图11),在波长为365nm的LED点光源照射下,引发剂浓度为质量分数1w%,聚合单体1,6-己二醇二丙烯酸酯在250s内的双键转化率为81%。
对比例1
传统商业MBF光引发剂的最大吸收波长为255nm(见说明书附图1),在波长为365nm的LED点光源照射下,引发剂浓度为质量分数1w%,聚合单体1,6-己二醇二丙烯酸酯在250s内的双键转化率为10%。
以上述依据本发明的理想实施例为启示,通过上述的说明内容,相关工作人员完全可以在不偏离本项发明技术思想的范围内,进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容,必须要根据权利要求范围来确定其技术性范围。
Claims (9)
1.一种长波长苯甲酰甲酸甲酯类光引发剂,其特征在于,具有通式Ⅰ、Ⅱ、Ⅲ、Ⅳ所示的分子结构:
上述通式中:
4R1表示苯环上4个任意空位上的取代基;
R1是氢原子、烷基、烯基、烷氧基、炔基、羟基、硝基、卤素、磺酸基以及被杂原子,卤素、烯基、炔基、硝基、氰基、磺酸基取代的烷基、烯基、烷氧基或炔基中的任意一种;
R2是烷基、含杂原子的烷基以及被杂原子,卤素、烯基、炔基、硝基、氰基、磺酸基取代的烷基中的任意一种;
R3和R4是氢原子、烷基、烷氧基以及被杂原子、卤素、烯基、炔基、硝基、氰基、磺酸基、芳香基、杂环芳香基取代的烷基或烷氧基中的任意一种;
R5是烷基、烷氧基以及被杂原子、卤素、烯基、炔基、硝基、氰基、磺酸基取代的烷基中的任意一种;
R6是烷基、烷氧基以及被杂原子、卤素、烯基、炔基、硝基、氰基、磺酸基、芳香基、杂环芳香基取代的烷基或烷氧基中的任意一种;
R7可以为氢原子、烷基、烷氧基以及被杂原子、卤素、烯基、炔基、硝基、氰基、磺酸基、芳香基、杂环芳香基取代的烷基或烷氧基中的任意一种。
3.一种长波长苯甲酰甲酸甲酯类光引发剂的制备方法,其特征在于:按照以下步骤制备:
(1)首先制备醛基和/或R1官能化的苯甲酰甲酸甲酯衍生物;
(2)醛基和/或R1官能化的苯甲酰甲酸甲酯衍生物与含有αH原子的酮类化合物进行缩合反应,将反应得到的固体产物纯化后,即得到长波长苯甲酰甲酸甲酯类光引发剂。
5.根据权利要求3所述的一种长波长苯甲酰甲酸甲酯类光引发剂的制备方法,其特征在于,所述含有αH原子的酮类化合物为丙酮、3-戊酮、环己酮、4,4-二甲基环己酮、苯乙酮、N-甲基吡咯烷酮、N-乙烯基吡咯烷酮、2-乙酰基-1-甲基吡咯或2-戊酮。
6.根据权利要求3所述的一种长波长苯甲酰甲酸甲酯类光引发剂的制备方法,其特征在于:所述缩合反应中醛基和/或R1官能化的苯甲酰甲酸甲酯衍生物与含有αH原子的酮类化合物的摩尔比为1-2:1。
7.根据权利要求3所述的一种长波长苯甲酰甲酸甲酯类光引发剂的制备方法,其特征在于:所述缩合反应的温度为0-80℃,反应时间为0.05-5h,pH=8-13。
8.根据权利要求3所述的一种长波长苯甲酰甲酸甲酯类光引发剂的制备方法,其特征在于:所述缩合反应的溶剂为甲醇、乙醇、异丙醇、叔丁醇、四氢呋喃、二甲基甲酰胺或二甲基亚砜。
9.根据权利要求3所述的一种长波长苯甲酰甲酸甲酯类光引发剂的制备方法,其特征在于:所述缩合反应的催化剂为氢氧化钠、氢氧化钾、叔丁醇钠、叔丁醇钾、碳酸氢钠、二异丙胺、吡啶、二异丙基氨基锂、三乙醇胺、甲基二乙醇胺或六甲基二硅基氨基锂。
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