CN109970696B - Coumarin oxime ester photoinitiator - Google Patents
Coumarin oxime ester photoinitiator Download PDFInfo
- Publication number
- CN109970696B CN109970696B CN201910288916.4A CN201910288916A CN109970696B CN 109970696 B CN109970696 B CN 109970696B CN 201910288916 A CN201910288916 A CN 201910288916A CN 109970696 B CN109970696 B CN 109970696B
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- oxime ester
- alkyl
- alkenyl
- molar ratio
- Prior art date
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- -1 Coumarin oxime ester Chemical class 0.000 title claims abstract description 49
- 238000010146 3D printing Methods 0.000 claims abstract description 15
- 238000000016 photochemical curing Methods 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 238000007639 printing Methods 0.000 claims abstract description 7
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 5
- 230000005855 radiation Effects 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 34
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- 230000015572 biosynthetic process Effects 0.000 claims description 27
- 238000003786 synthesis reaction Methods 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 19
- 125000003342 alkenyl group Chemical group 0.000 claims description 19
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 claims description 13
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 13
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 10
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 claims description 10
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 claims description 5
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229920002866 paraformaldehyde Polymers 0.000 claims description 5
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- 239000012312 sodium hydride Substances 0.000 claims description 4
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 4
- 235000010288 sodium nitrite Nutrition 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 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
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 claims description 2
- CBZMQWPBAUBAPO-UHFFFAOYSA-N 4-ethenyl-n,n-diethylaniline Chemical compound CCN(CC)C1=CC=C(C=C)C=C1 CBZMQWPBAUBAPO-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 150000001263 acyl chlorides Chemical class 0.000 claims description 2
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000004820 halides Chemical group 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- CBCACOCJKPPSMS-UHFFFAOYSA-N n,n-diethyl-4-ethynylaniline Chemical group CCN(CC)C1=CC=C(C#C)C=C1 CBCACOCJKPPSMS-UHFFFAOYSA-N 0.000 claims description 2
- ZBRJXVVKPBZPAN-UHFFFAOYSA-L nickel(2+);triphenylphosphane;dichloride Chemical compound [Cl-].[Cl-].[Ni+2].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 ZBRJXVVKPBZPAN-UHFFFAOYSA-L 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 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
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical group OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 239000003999 initiator Substances 0.000 abstract description 8
- 230000000977 initiatory effect Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000012545 processing Methods 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 12
- 238000012512 characterization method Methods 0.000 description 11
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 239000011734 sodium Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000012467 final product Substances 0.000 description 7
- 238000010898 silica gel chromatography Methods 0.000 description 7
- 239000012043 crude product Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010025 steaming Methods 0.000 description 4
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229960000956 coumarin Drugs 0.000 description 3
- 235000001671 coumarin Nutrition 0.000 description 3
- 125000000332 coumarinyl group Chemical group O1C(=O)C(=CC2=CC=CC=C12)* 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- ZWMAYLMVFSCMMS-UHFFFAOYSA-N 4-ethynyl-n,n-dimethylaniline Chemical compound CN(C)C1=CC=C(C#C)C=C1 ZWMAYLMVFSCMMS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 1
- 229940018563 3-aminophenol Drugs 0.000 description 1
- FXTKWBZFNQHAAO-UHFFFAOYSA-N 3-iodophenol Chemical compound OC1=CC=CC(I)=C1 FXTKWBZFNQHAAO-UHFFFAOYSA-N 0.000 description 1
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 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
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- QBAZWXKSCUESGU-UHFFFAOYSA-N yttrium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBAZWXKSCUESGU-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
-
- 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
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
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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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polymerisation Methods In General (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a coumarin oxime ester photoinitiator and a preparation method thereof, and the molecular structure general formula is shown as formula (I). The photoinitiator initiates photocuring under the radiation wavelength of 360-450nm, and is applied to the fields of single photon 3D printing, two-photon 3D printing, printing ink, photoresist and the like. The photoinitiator provided by the invention can be used as both an LED photoinitiator and a two-photon initiator, has good initiation activity, and can save the manufacturing cost to a certain extent by using one agent for two purposes.
Description
Technical Field
The invention relates to the field of photoinitiators, in particular to a photoinitiator containing coumarin units and oxime ester units and a preparation method thereof.
Background
With the increasingly outstanding social environment and energy problems, the light-cured material is widely concerned by people because of the advantage that no or little solvent is volatilized in the curing process.
The photoinitiator is an essential component in the photocuring technology, plays a crucial role in the photocuring process, plays a decisive role in the photocuring speed, and even influences the performance of the photocuring material. The photoinitiator is excited by a light source to generate photolysis reaction to generate free radicals or ions with reaction activity, and further initiate the polymerization reaction of monomers, so that a cross-linked polymer network structure is formed, and the photoinitiator is widely applied to the fields of coatings, printing ink, 3D printing and the like.
In recent years, 3D printing materials based on photopolymerization (DLP 3D printing, two-photon 3D printing) have attracted more and more attention because of their advantages such as environmental friendliness and high precision. The DLP 3D printing takes ultraviolet or visible light LED lamps as light sources, and a three-dimensional structure is prepared in a layer-by-layer overlapping mode, so that the DLP 3D printing precision is high. However, due to factors such as light scattering and initiator diffusion, the technology has poor precision in the manufacture of micro-nano structures. The two-photon polymerization is to initiate a photocuring system to polymerize by a two-photon photoinitiator at a focus through ultrashort pulse laser, and a complex three-dimensional micro-nano structure is formed by superposition and has extremely high precision. The defects in the traditional DLP 3D printing are made up to a certain extent, but the two-photon printing realizes curing at a focal point, and the printing speed is relatively slow, so that the development of a high-performance two-photon photoinitiator is very important. So far, radical type two-photon polymerization is mainly based on an intermolecular electron transfer mechanism, such as a dye/amine system, i.e., under two-photon excitation, a dye absorbs energy and then transfers electrons to amine molecules to generate active amine, and then initiates polymerization, but the system has the defects of reverse electron transfer, low initiation efficiency and the like; the other mechanism is that light-induced direct cracking generates active species, and commercial photoinitiators such as Irgacure 369 and TPO are also applied to two-photon polymerization, and because the two-photon absorption cross section is small, the activity under two-photon laser is not good, but the absorption cross section is small. At present, LED photoinitiators are developed towards visible light, for example, CN109305951A discloses a coumarin compound and preparation and application thereof, and the coumarin compound is used as a visible light LED initiator, but the structure cannot realize multifunctional (such as two-photon initiation activity) and high-efficiency utilization.
Therefore, it is economically important to develop an initiator having good initiation performance under both two-photon laser and LED light source.
Disclosure of Invention
Aiming at the problems, the invention provides a long conjugated coumarin oxime ester photoinitiator and a preparation method thereof. The coumarin group of visible light is used as chromophore, the length of a conjugated chain is prolonged at the 7 th position of the chromophore to enlarge a two-photon absorption section, and the oxime ester group capable of being rapidly cracked is introduced to the 3 th position and the 4 th position of the coumarin to be used as an active center, so that the dual-purpose photoinitiator capable of being rapidly cracked under the visible light and the two-photon laser is obtained.
A coumarin oxime ester photoinitiator has the following molecular structure general formula:
wherein the content of the first and second substances,
R 1 Included
R 3 represents a hydrogen atom, C 1 -C 20 Alkyl radical, C 3 -C 20 Cycloalkyl or C 2 -C 20 Alkenyl of (a);
wherein the aforementioned hydrogen atom, C 1 -C 20 Alkyl radical, C 3 -C 20 Cycloalkyl or C 2 -C 20 The alkenyl group of (a) may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, cyano, hydroxy, mono (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 6 Alkyl of (C) 1 -C 6 Alkoxy group of (1), C 1 -C 6 Alkylthio of, C 2 -C 6 An alkenyl group;
R 2 represents C 1 -C 20 Alkyl radical, C 3 -C 20 Cycloalkyl radical, C 4 -C 20 Alkylcycloalkyl of (A), C 4 -C 20 Cycloalkylalkyl of (C) 2 -C 20 Alkenyl of, C 3 -C 20 Cycloalkenyl group of (A), C 4 -C 20 Alkyl cycloalkenyl of (A), C 4 -C 20 Cycloalkenylalkyl of (1), C 6 -C 20 Aryl or C of 7 -C 20 Aralkyl of (4);
wherein the aforementioned R 2 C in (1) 1 -C 20 Alkyl radical, C 3 -C 20 Cycloalkyl radical, C 4 -C 20 Alkylcycloalkyl of (C) 4 -C 20 Cycloalkylalkyl of (C) 2 -C 20 Alkenyl of (C) 3 -C 20 Cycloalkenyl group of (A), C 4 -C 20 Alkyl cycloalkenyl of (A), C 4 -C 20 Cycloalkenylalkyl of (A), C 6 -C 20 Aryl or C of 7 -C 20 The aralkyl group of (a) may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, mono (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, nitro, cyano, hydroxy, C 1 -C 6 Alkyl of (C) 1 -C 6 Alkoxy group of (C) 1 -C 6 Alkylthio of, C 2 -C 6 An alkenyl group;
R 4 represents a hydrogen atom, C 1 -C 20 Alkyl radical, C 2 -C 20 Alkenyl of (C) 3 -C 20 Cycloalkyl radical, C 4 -C 20 Alkylcycloalkyl of (A), C 2 -C 20 Alkenyl of (C) 6 -C 20 Aryl or C of 7 -C 20 An aralkyl group of (2).
Preferably, a coumarin oxime ester photoinitiator,
r is as described 3 Represents a hydrogen atom, C 1 -C 12 Alkyl of (C) 4 -C 10 Cycloalkylalkyl of (C) 2 -C 10 Alkenyl of (a);
the aforementioned R of 3 C in (1) 1 -C 12 Alkyl of (C) 4 -C 10 Cycloalkylalkyl of (C) 2 -C 10 May be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, cyano, hydroxy, mono (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 6 Alkyl of (C) 1 -C 6 Alkoxy group of (C) 1 -C 6 Alkylthio of, C 2 -C 6 An alkenyl group;
said R 3 Represents a hydrogen atom, C 1 -C 12 Alkyl of (C) 4 -C 10 Cycloalkylalkyl of (C) 2 -C 10 Alkenyl of (a);
r is as described 2 、R 3 、R 4 In the structure of (1), an arbitrary CH 2 Is unsubstituted or substituted by O, S, C = O or NH, any CH is unsubstituted or substituted by N, any C is unsubstituted or substituted by Si or Ge, and any H is unsubstituted or substituted by halogen, nitro, hydroxy, cyano or amino.
Preferably, R is 2 Represents C 1 -C 12 Alkyl radical, C 4 -C 10 Alkylcycloalkyl or cycloalkylalkyl of (C) 2 -C 10 Alkenyl of (C) 3 -C 12 Cycloalkenyl group of (A), C 4 -C 12 Cycloalkenylalkyl or alkylcycloalkenyl, C 6 -C 10 Aryl of (C) 7 -C 10 Aralkyl group of (1);
wherein the foregoing C 1 -C 12 Alkyl radical, C 4 -C 10 Alkylcycloalkyl or cycloalkylalkyl of C 2 -C 10 Alkenyl of (C) 3 -C 12 Cycloalkenyl group of (1), C 4 -C 12 Cycloalkenylalkyl or alkylcycloalkenyl of (A), C 6 -C 10 Aryl of, C 7 -C 10 The aralkyl group of (a) may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, mono (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, nitro, cyano, hydroxy, C 1 -C 6 Alkyl of (C) 1 -C 6 Alkoxy group of (1), C 1 -C 6 Alkylthio of, C 2 -C 6 An alkenyl group;
said R 2 In the structure of any CH 2 Is an unsubstituted group or a group substituted with O, S, C = O or NH, any CH is an unsubstituted group or a group substituted with N, any C is an unsubstituted group or a group substituted with Si or Ge; any H is an unsubstituted group or substituted by halogen, phenyl, nitro, hydroxy, sulfoAcid, cyano or amino substituted groups.
Preferably, R is 4 Represents a hydrogen atom, C 1 -C 10 Alkyl radical, C 2 -C 4 Alkenyl of (C) 3 -C 10 Heteroaryl of (1), C 6 -C 10 Aryl or C of 7 -C 12 Aralkyl group of (2).
Preferably, the photoinitiator is selected from the following:
a method for preparing coumarin oxime ester photoinitiator comprises the following steps:
(1) A synthesis: a and ethyl acetoacetate are subjected to the action of a catalyst to obtain A, wherein the molar ratio of the a to the ethyl acetoacetate is 1-1;
(2) B, synthesis: a reacts with sodium nitrite in a strong acid environment at low temperature, and the product thereof reacts with M to obtain B, wherein the molar ratio of A to sodium nitrite is 1-1, and the molar ratio of A to M is 1; m is halide, including potassium iodide, potassium bromide, preferably potassium iodide; x represents any one of Br or I;
(3) C, synthesis: dispersing 3-halophenol, anhydrous magnesium chloride, triethylamine and paraformaldehyde in an organic solvent to obtain C; x represents any one of Br or I;
(4) D, synthesis: in the presence of aliphatic amine, reacting C with ethyl acetoacetate at room temperature to obtain D, wherein the molar ratio of C to ethyl acetoacetate is 1-1;
(5) E, synthesis: in the presence of selenium dioxide, B is oxidized into E, and the molar ratio of B to selenium dioxide is 1-1;
(6) F, synthesis: dispersing D or E and D in an organic solvent in the presence of a catalyst and an acid-binding agent to react to obtain F, wherein the molar ratio of D or E to D is 1-1 1 The corresponding structures, preferably 4-diethylaminophenylacetylene and 4-diethylaminostyrene; said R is 1 、R 3 、R 4 As defined in any one of claims 1 to 4;
(7) G synthesis: in the presence of an acid-binding agent, F and hydroxylamine hydrochloride react in an ethanol solution to obtain G, wherein the molar ratio of F to hydroxylamine hydrochloride is (1-1); said R is 1 、R 4 As defined in any one of claims 1 to 4;
(8) And (3) synthesis of a photoinitiator: in the presence of an acid binding agent, G and e react in an organic solvent to obtain the coumarin oxime ester photoinitiator formula (I), wherein the raw material e is an acyl chloride compound corresponding to R 2 The structure (2) of (a) is,the molar ratio of G to e is 1-1, and the molar ratio of G to acid-binding agent is 1.
Further, the reaction temperature of the step (1) is 70-100 ℃, and the reaction time is 1-10 hours.
Further, the low temperature of the step (2) is-20 to 20 ℃, and the reaction time is 1 to 10 hours.
Further, in the step (3), the addition amount of paraformaldehyde, magnesium chloride and triethylamine is 3-10 equivalents, the reaction temperature is 70-200 ℃, and the reaction is carried out for 24 hours.
Further, in the step (4), the aliphatic amine comprises piperidine, the reaction temperature is 0-50 ℃, and the reaction time is 1-10 hours.
Further, in the step (5), the reaction temperature is 50-200 ℃ and the reaction time is 20-60 hours.
Further, in the step (6), the catalyst used is any one or more of the following: cuprous iodide, palladium bis (triphenylphosphine) dichloride, palladium acetate, triphenylphosphine, nickel bis (triphenylphosphine) dichloride; the reaction is carried out under the anaerobic condition; the reaction temperature is 20-200 ℃.
Further, in the step (7), the molar ratio of the intermediate F to the acid-binding agent is 1.
Further, in the step (8), the reaction temperature is 0-30 ℃ and the reaction time is 0.5-5 hours.
Further, the acid scavenger comprises one or more of the following components: triethylamine, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydroxide, sodium hydride, sodium acetate and piperidine.
Further, the organic solvent includes any one or more of: dichloromethane, chloroform, methanol, ethanol, toluene, tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide, xylene, p-xylene, acetonitrile and triethylamine.
The compound of the formula (I) can be used as a photoinitiator for application in the fields of photocuring coating, 3D printing, high-density optical information storage, micro-nano optical devices, microfluid device processing or biological scaffold construction and the like.
In the above preparation methods, the starting materials used are all compounds known in the art and commercially available.
The beneficial technical effects of the invention are as follows:
(1) The coumarin oxime ester photoinitiator has high initiating activity in a visible light range, is high in curing speed, and has a good application prospect in visible light polymerization forming.
(2) The prepared two-photon photoinitiator has a large two-photon absorption cross section, is a good two-photon photoinitiator, and has a good application prospect in the aspect of micro-nano structure manufacturing.
(3) The photoinitiator provided by the invention can be used as both an LED photoinitiator and a two-photon initiator, has good initiation activity, and can save the manufacturing cost to a certain extent by using one agent for two purposes.
(4) The photoinitiator provided by the invention has a lower threshold value, not only can save energy, but also can improve the processing speed and improve the efficiency; in addition, laser beam splitting processing is facilitated, and efficiency is further improved.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings.
FIG. 1 is a chart of UV-VIS absorption spectra of compounds H1 and H2 in example 3 of the present invention;
FIG. 2 is a graph of the real-time infrared conversion of double bonds in the acrylate system of example 4 of the present invention;
FIG. 3 is a digital photograph of a 3D printing and forming structure in example 5 of the present invention;
FIG. 4 is a scanning electron microscope image of a circular microstructure formed in example 6 of the present invention;
FIG. 5 is a scanning electron micrograph of a 24-sided structure formed in example 6 of the present invention;
FIG. 6 is a graph of the energy distribution of two-photon printing of H2 and M2CMK of a comparative structure in a comparative example of the invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are commercially available, and are not indicated by manufacturers.
Example 1
The coumarin oxime ester photoinitiator H1 is prepared by the following specific steps:
(1) Synthesis of A1
In a 50ml single neck round bottom flask, 3.37g (30.9 mmol) of 3-aminophenol and 1.25g of yttrium nitrate hexahydrate (Y (NO) 3 ) 3 ·6H 2 O) (3.3 mmol) and 4.82g (37.1 mmol) of ethyl acetoacetate at 90 ℃ for 2 hours, then cooled to room temperature, the reaction mass was dissolved in 50ml of ethanol, then poured into a large amount of water and filtered with suction to give a yellow solid which was dried in a vacuum oven at 40 ℃ to give 2.58g of the final product in 50% yield.
Nuclear magnetic characterization of A1: 1 H NMR(400MHz,Chloroform-d)δ7.39(dd,J＝2.3,1.2Hz,1H),6.61(d,J＝2.3Hz,1H),6.59(d,J＝1.2Hz,1H),6.05(q,J＝1.2Hz,1H),4.17(s,2H),2.38(d,J＝1.2Hz,3H)。
(2) Synthesis of B1
3.25g (18.6 mmol) of A1 is dispersed in 90ml of water, 7ml of concentrated sulfuric acid is added dropwise, and then 1.54g (22.6 mmol) of NaNO is added dropwise when the reaction temperature is reduced to-10 to-5 DEG C 2 (dissolved in 12ml of water) and 5.43g (32.7 mmol) of KI (dissolved in 12ml of water) were reacted at room temperature for 4 hours; then, the reaction solution was extracted with ethyl acetate, 25% (W/V) Na was added 2 S 2 O 3 Washing with 1N HCl,2N NaOH and saturated saline respectively, and washing with anhydrous Na 2 SO 4 Drying, rotary evaporation to remove solvent, and silica gel column chromatography to purify the crude product to obtain 1.66g of final product with 31% yield.
B1 nuclear magnetism characterization: 1 H NMR(400MHz,Chloroform-d)δ7.74(d,J＝1.6Hz,1H),7.65(dd,J＝8.3,1.7Hz,1H),7.32(d,J＝8.3Hz,1H),6.34(q,J＝1.3Hz,1H),2.44(d,J＝1.2Hz,3H)。
(3) Synthesis of E1
In a 250ml single neck round bottom flask, 2.80g (9.8 mmol) of B1 and 2.22g (20.0 mmol) of selenium dioxide were dissolved in 150ml of p-xylene and reacted at 140 ℃ for 48 hours; and (3) cooling the reaction liquid to room temperature, filtering to remove solid impurities, performing rotary evaporation to obtain a crude product, and finally performing separation and purification by using a silica gel column chromatography to obtain 1.2g of a final product with the yield of 35%.
E1 nuclear magnetic characterization: 1 H NMR(400MHz,Chloroform-d)δ10.11(s,1H),8.33(s,1H),7.81(d,J＝1.6Hz,2H),7.71(s,1H),6.94(s,1H)。
(4) Synthesis of F1
Under nitrogen protection, 400.2mg (1.3 mmol) of E1 and 11.3mg of Pd (P (Ph) were added to a 50ml reaction flask 3 ) 4 Cl 2 (0.02 mmol), 7.3mg of CuI (0.04 mmol) and 250.5mg (1.72 mmol) of 4-ethynyl-N, N-dimethylaniline, followed by addition of 8ml of oxygen-free tetrahydrofuran and 2ml of oxygen-free triethylamine, and reaction at 53 ℃ for 5 hours; then cooling to room temperature, pouring the reaction liquid into a large amount of water, extracting for 3-5 times by using dichloromethane, combining organic phases, and using anhydrous Na 2 SO 4 The solvent was removed by rotary evaporation and the crude product was finally isolated and purified by silica gel column chromatography to give 245mg of final product in 57% yield.
F1 nuclear magnetic characterization: 1 H NMR(400MHz,Chloroform-d)δ10.14(s,1H),8.55(d,J＝8.3Hz,1H),7.51–7.45(m,4H),6.87(s,1H),6.77(d,J＝8.3Hz,2H),3.06(s,6H)。
(5) Synthesis of G1
In a 50ml single-neck round-bottom flask, 133.3mg (0.42 mmol) of F1, 62.2mg (0.9 mmol) of hydroxylamine hydrochloride and 80mg (0.98 mmol) of sodium acetate were dispersed in 18ml of an anhydrous ethanol solution and reacted at 80 ℃ for 2 hours; cooling the reaction solution to room temperature, pouring into a large amount of water, extracting with dichloromethane for 3 times, and adding anhydrous Na 2 SO 4 Drying, rotary evaporation to remove solvent, and silica gel column chromatography to separate and purify the crude product to obtain 121mg of final product with 87% yield.
G1 nuclear magnetic characterization: 1 H NMR(400MHz,Chloroform-d)δ8.31(s,1H),8.20(d,J＝8.4Hz,1H),8.09(s,1H),7.48(s,3H),7.42(d,J＝9.4Hz,1H),6.74(d,J＝8.2Hz,2H),6.60(s,1H),3.05(s,6H)。
(6) Synthesis of H1
In a 25ml single neck round bottom flask, 123mg (0.39 mmol) G1 and 13mg (0.54 mmol) sodium hydride are dissolved in 15ml anhydrous tetrahydrofuran, stirred at 0 ℃ for 30min under nitrogen atmosphere, 62. Mu.l benzoyl chloride is added and stirring is continued for 20min; the reaction was then quenched with 5% sodium bicarbonate solution and extracted with dichloromethane, anhydrous Na 2 SO 4 Drying, rotary steaming to obtain red solid, and performing column chromatography for separation and purification to obtain 210mg final product with yield of 74%.
H1 nuclear magnetic characterization: 1 H NMR(400MHz,Chloroform-d)δ8.69(s,1H),8.51(d,J＝8.8Hz,1H),8.19(d,2H),7.72–7.67(m,1H),7.56(t,J＝7.8Hz,2H),7.51–7.46(m,4H),6.72(d,J＝1.9Hz,2H),6.70(s,1H),3.05(s,6H)。
example 2
The synthesis of H2 comprises the following specific steps:
(1) Synthesis of C1
In a 100ml reaction flask, 1.5g (6.8 mmol) of 3-iodophenol and 2g (21.1 mmol) of anhydrous magnesium chloride were dissolved in a solution of 50ml of anhydrous acetonitrile and 6ml (43.2 mmol) of triethylamine, followed by addition of 2g (66.7 mmol) of paraformaldehyde, and reaction at 85 ℃ for 24 hours; the reaction was cooled to room temperature, then neutralized with 1N HCl solution, extracted three times with dichloromethane, anhydrous Na 2 SO 4 Drying, rotary steaming to obtain crude product, and separating and purifying with silica gel column chromatography to obtain 0.69g product with yield of 40%.
C1 nuclear magnetic characterization: 1 H NMR(400MHz,Chloroform-d)δ11.05(s,1H),9.87(s,1H),7.46(s,1H),7.42(dd,J＝8.1,1.5Hz,1H),7.26(d,J＝8.1Hz,1H)。
(2) Preparation of D1
In a 50ml single neck round bottom flask, 0.67g (2.7 mmol) of C1 was dissolved in 20ml of anhydrous ethanol, followed by addition of 0.5ml (3.7 mmol) of ethyl acetoacetate, then the temperature was cooled to 0 ℃ and 50. Mu.l (0.5 mmol) of piperidine was added and reacted at room temperature for 4 hours; the reaction solution was poured into a large amount of water, filtered with suction, and dried in a vacuum oven to obtain 0.54g of a pale yellow solid with a yield of 60%.
D1 nuclear magnetic characterization: 1 H NMR(400MHz,Chloroform-d)δ8.46(s,1H),7.80(s,1H),7.71(dd,J＝8.2,1.6Hz,1H),7.36(d,J＝8.2Hz,1H),2.74(s,3H)。
(3) Synthesis of F2
In a 50ml reaction flask, 488mg (1.56 mmol) of D1, 269mg (1.86 mmol) of 4-ethynyl-N, N-dimethylaniline, 13.4mg (0.02 mmol) of Pd (PPh) 3 ) 4 Cl 2 And 9.3mg (0.05 mmol) of cuprous iodide were dissolved in 15ml of deoxygenated tetrahydrofuran, and then 2ml of deoxygenated triethylamine was added and reacted at 53 ℃ for 5 hours; after the reaction was cooled to room temperature, it was poured into a large amount of water, extracted 3 times with dichloromethane, anhydrous Na 2 SO 4 Drying, removing solvent by rotary evaporation, and separating and purifying by silica gel column chromatography to obtain 439mg red solid with 86% yield.
F2 nuclear magnetic characterization: 1 H NMR(400MHz,Chloroform-d)δ8.50(s,1H),7.59(d,J＝8.1Hz,1H),7.49–7.41(m,4H),6.70(d,2H),3.05(s,6H),2.75(s,3H)。
(4) Synthesis of G2
In a 50ml single neck round bottom flask, 196mg (0.59 mmol) F2, 85mg (1.23 mmol) hydroxylamine hydrochloride and 97mg (1.18 mmol) sodium acetate were dispersed in 10ml ethanol, reacted at 80 ℃ for 2 hours, then the reaction was cooled to room temperature, to a large amount of water, extracted three times with 80ml dichloromethane, and the organic phase was extracted with anhydrous Na 2 SO 4 Drying, rotary steaming to obtain crude product, and separating and purifying by silica gel column chromatography to obtain 75mg of target product with 37% yield.
G2 nuclear magnetic characterization: 1 H NMR(400MHz,DMSO-d6)δ11.48(s,1H),8.11(s,1H),7.80(d,J＝8.1Hz,1H),7.50(s,1H),7.47–7.38(m,3H),6.74(d,J＝8.9Hz,2H),2.98(s,6H),2.09(s,3H)。
(5) Synthesis of H2
In a 25ml single neck round bottom flask, 6 is placed8.4mg (0.2 mmol) of G2 and 12.8mg (0.53 mmol) of sodium hydride are dissolved in 4ml of anhydrous tetrahydrofuran and stirred at 0 ℃ for 30min under nitrogen, followed by addition of 34. Mu.l (0.37 mmol) of benzoyl chloride and stirring is continued for 20min; after-treatment, the reaction was quenched with 5% sodium bicarbonate solution, extracted with dichloromethane, anhydrous Na 2 SO 4 Drying, rotary steaming to obtain red solid, and finally performing column chromatography separation and purification to obtain 60.7mg of final product with the yield of 67%.
H2 nuclear magnetic characterization: 1H NMR (400mhz, chloroform-d) δ 8.19 (s, 1H), 8.18-8.14 (m, 2H), 7.69-7.63 (m, 1H), 7.54 (dd, J =6.8,1.3hz, 2h), 7.52 (s, 1H), 7.46 (d, J =8.8hz, 3h), 7.43 (dd, J =8.0,1.5hz, 1h), 6.71 (d, J =8.5hz, 2h), 3.04 (s, 6H), 2.59 (s, 3H).
Example 3
The compound H1 and the compound H2 prepared in example 1 and example 2 were respectively subjected to performance measurement, and the absorption wavelength band was 360 to 450nm as measured by an ultraviolet-visible spectrophotometer, and the ultraviolet-visible absorption spectrum thereof is shown in fig. 1, and it was found that the maximum absorption wavelength thereof was around 405nm and matched with the wavelength of the longest LED lamp of 405 nm.
Example 4
The infrared conversion rate of the long conjugated coumarin oxime ester photoinitiator in the cured resin of a resin system
Respectively preparing a curing resin of an acrylate system (acrylate) under the condition of keeping out light: the 10mg compounds H1 and H2 were added to 1g monomer TMPTA/TMP3EOTA (molar ratio 1. The structural formula of the monomer used in the system is as follows:
example 5
Application of long conjugated coumarin oxime ester photoinitiator in 3D printing
Under the dark condition, 900mg of compound H2, 45g of trimethylolpropane triacrylate and 45g of ethoxylated trimethylolpropane triacrylate are added into a glass container provided with a stirrer, stirring and oscillation are carried out for 24 hours, so that the compound H2 is completely dissolved, the photocuring material for 3D printing can be obtained, the photocuring material is poured into a printer resin tank, the wavelength of a light source used by a printer is 405nm, a 3D model to be printed is called, the printer automatically prints a three-dimensional structure, and as shown in figure 3, the long conjugated coumarin oxime ester initiator designed by the invention is proved to print a good three-dimensional structure under a visible light LED lamp.
Example 6
Application of long conjugated coumarin oxime ester photoinitiator in structural processing
Preparing a two-photon photoresist: under the dark condition, 5mg of the compound H2, 500mg of trimethylolpropane triacrylate and 500mg of ethoxylated trimethylolpropane triacrylate in example 1 are added into a glass container with a stirrer, and the mixture is stirred and oscillated for 24 hours to completely dissolve the compound H2, so that the two-photon photoresist can be obtained;
processing a microstructure: coating the two-photon photoresist on a glass slide, processing a microstructure under the conditions of 800nm wavelength femtosecond laser, 80fs pulse femtosecond laser and 100 mu m/s printing speed, wherein the processed structure is a circular matrix, and obtaining a microstructure with better precision (the narrowest line width is about 150nm, and the widest line width is not more than 300 nm) as shown in figure 4; FIG. 4 is a scanning electron microscope image of a partially circular structure, with an energy range of 8-30mW and a processing speed of 100 μm/s.
And (3) processing a three-dimensional structure: when the microstructure shown in FIG. 4 is processed, the laser focus is focused in the resin, one energy is fixed, a row of circular structures are processed, the laser energy is increased, another row of circular structures are processed, the circular structures are processed, and the like, from bottom to top, the energy is gradually increased, and the threshold value of the initiator is measured; in addition, a more complex 24-sided structure was formed above the threshold, as in FIG. 5; FIG. 5 shows a 24-sided microstructure, with an energy of 15mW and a processing speed of 100 μm/s.
Therefore, the long conjugated coumarin oxime ester photoinitiator provided by the invention has a low threshold value of 8mW, saves energy, and can improve the processing speed and efficiency; in addition, the low threshold value is beneficial to laser beam splitting processing, and the efficiency is further improved. Further, the photoinitiator has good stability and photosensitivity and high initiation efficiency.
Comparative example
The long conjugated coumarin oxime ester photoinitiator is compared with a reported high-performance two-photon initiator (M2 CMK)
Under the condition of keeping away from light, 5mg of the compound H2 in example 1, 500mg of trimethylolpropane triacrylate and 500mg of ethoxylated trimethylolpropane triacrylate are added into a glass container provided with a stirring rod, the compound H2 is completely dissolved by stirring and oscillating for 24H, and under the same condition, an M2CMK system with the same concentration as H2 is prepared and tested for the two-photon absorption energy range, as shown in FIG. 6, wherein the polymerization threshold value of H2 is 10mW, the processing window is 10-30mW, the processing window of M2CMK is 12mW, and the processing window is 12-32mW, in contrast, the long conjugated oxime ester two-photon photoinitiator designed by the invention can realize polymerization at lower energy and is a more efficient two-photon photoinitiator.
While embodiments of the present invention have been described above, the above description is illustrative, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (17)
1. The coumarin oxime ester photoinitiator is characterized by having the following molecular structure general formula:
wherein the content of the first and second substances,
R 1 Included
said R 3 Represents a hydrogen atom, C 1 -C 12 Alkyl of (C) 4 -C 10 Cycloalkylalkyl of (C) 2 -C 10 Alkenyl of (a);
the aforementioned R 3 C in (1) 1 -C 12 Alkyl of (C) 4 -C 10 Cycloalkylalkyl of (C) 2 -C 10 May be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, cyano, hydroxy, mono (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, C 1 -C 6 Alkyl of (C) 1 -C 6 Alkoxy group of (1), C 1 -C 6 Alkylthio of, C 2 -C 6 An alkenyl group;
R 2 represents C 1 -C 20 Alkyl radical, C 3 -C 20 Cycloalkyl, C 4 -C 20 Alkylcycloalkyl of (A), C 4 -C 20 Cycloalkylalkyl of (C) 2 -C 20 Alkenyl of, C 3 -C 20 Cycloalkenyl group of (1), C 4 -C 20 Alkyl cycloalkenyl of (A), C 4 -C 20 Cycloalkenylalkyl of (A), C 6 -C 20 Aryl or C of 7 -C 20 Aralkyl group of (1);
wherein the aforementioned R 2 C in (1) 1 -C 20 Alkyl radical, C 3 -C 20 Cycloalkyl radical, C 4 -C 20 Alkylcycloalkyl of (A), C 4 -C 20 Cycloalkylalkyl of (C) 2 -C 20 Alkenyl of (C) 3 -C 20 Cycloalkenyl group of (1), C 4 -C 20 Alkyl cycloalkenyl of (1), C 4 -C 20 Cycloalkenylalkyl of (A), C 6 -C 20 Aryl or C of 7 -C 20 The aralkyl group of (a) may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, mono (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, nitro, cyano, hydroxy, C 1 -C 6 Alkyl of (C) 1 -C 6 Alkoxy group of (1), C 1 -C 6 Alkylthio of, C 2 -C 6 An alkenyl group;
R 4 represents a hydrogen atom, C 1 -C 20 Alkyl radical, C 2 -C 20 Alkenyl of (C) 3 -C 20 Cycloalkyl radical, C 4 -C 20 Alkylcycloalkyl of (C) 2 -C 20 Alkenyl of (C) 6 -C 20 Aryl or C of 7 -C 20 An aralkyl group of (2).
2. The coumarin oxime ester photoinitiator according to claim 1,
said R 2 、R 3 、R 4 In the structure of (1), any CH 2 Is unsubstituted or substituted by O, S, C = O or NH, any CH is unsubstituted or substituted by N, any C is unsubstituted or substituted by Si or Ge, and any H is unsubstituted or substituted by halogen, nitro, hydroxy, cyano or amino.
3. The coumarin oxime ester photoinitiator as claimed in claim 1, wherein R is 2 Represents C 1 -C 12 Alkyl radical, C 4 -C 10 Alkylcycloalkyl or cycloalkylalkyl of (C) 2 -C 10 Alkenyl of (C) 3 -C 12 Cycloalkenyl group of (A), C 4 -C 12 Cycloalkenylalkyl or alkylcycloalkenyl of (A), C 6 -C 10 Aryl of (C) 7 -C 10 Aralkyl of (4);
wherein the foregoing C 1 -C 12 Alkyl radical, C 4 -C 10 Alkylcycloalkyl or cycloalkylalkyl of (C) 2 -C 10 Alkenyl of (C) 3 -C 12 Cycloalkenyl group of (1), C 4 -C 12 Cycloalkenylalkyl or alkylcycloalkenyl of (A), C 6 -C 10 Aryl of (C) 7 -C 10 The aralkyl group of (a) may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, mono (C) 1 -C 6 Alkyl) amino, di (C) 1 -C 6 Alkyl) amino, nitro, cyano, hydroxy, C 1 -C 6 Alkyl of (C) 1 -C 6 Alkoxy group of (1), C 1 -C 6 Alkylthio of, C 2 -C 6 An alkenyl group;
said R 2 In the structure of any CH 2 Is an unsubstituted group or a group substituted with O, S, C = O or NH, any CH is an unsubstituted group or a group substituted with N, any C is an unsubstituted group or a group substituted with Si or Ge; any H is an unsubstituted group or a group substituted with halogen, phenyl, nitro, hydroxyl, sulfonic acid, cyano, or amino.
4. The coumarin oxime ester photoinitiator as claimed in claim 1, wherein R is 4 Represents a hydrogen atom, C 1 -C 10 Alkyl radical, C 2 -C 4 Alkenyl of (C) 3 -C 10 Heteroaryl of (A), C 6 -C 10 Aryl or C of 7 -C 12 An aralkyl group of (2).
5. The coumarin oxime ester photoinitiator according to any one of claims 1 to 4, wherein the photoinitiator is selected from the group consisting of:
6. a process for the preparation of a coumarin oxime ester photoinitiator according to any one of claims 1 to 4, comprising the steps of:
(1) A synthesis: a and ethyl acetoacetate under the action of a catalyst to obtain A, wherein the molar ratio of the a to the ethyl acetoacetate is 1-1, preferably the molar ratio of the a to the catalyst is 1;
(2) B, synthesis: a reacts with sodium nitrite in a strong acid environment at low temperature, and the product thereof reacts with M to obtain B, wherein the molar ratio of A to sodium nitrite is 1-1, and the molar ratio of A to M is 1; m is halide, including potassium iodide, potassium bromide, preferably potassium iodide; x represents any one of Br or I;
(3) C, synthesis: dispersing 3-halophenol, anhydrous magnesium chloride, triethylamine and paraformaldehyde in an organic solvent to obtain C; x represents any one of Br or I;
(4) D, synthesis: in the presence of aliphatic amine, reacting C with ethyl acetoacetate at room temperature to obtain D, wherein the molar ratio of C to ethyl acetoacetate is 1-1;
(5) E, synthesis: in the presence of selenium dioxide, B is oxidized into E, and the molar ratio of B to selenium dioxide is 1-1;
(6) F, synthesis: dispersing D or E and D in an organic solvent in the presence of a catalyst and an acid-binding agent to react to obtain F, wherein the molar ratio of D or E to D is 1-1, the ratio of D or E to the catalyst is 1.01-1 1 The corresponding structure is as follows,
preferably 4-diethylaminophenylacetylene and 4-diethylaminostyrene; the R is 1 、R 3 、R 4 As defined in any one of claims 1 to 4;
(7) G synthesis: in the presence of an acid binding agent, F and hydroxylamine hydrochloride react in an ethanol solution to obtain G, wherein the molar ratio of F to hydroxylamine hydrochloride is 1-1; said R is 1 、R 4 As defined in any one of claims 1 to 4;
(8) And (3) synthesis of a photoinitiator: in the presence of an acid binding agent, G and e react in an organic solvent to obtain the coumarin oxime ester photoinitiator formula (I), wherein the raw material e is an acyl chloride compound corresponding to R 2 The molar ratio of G to e is 1-1, and the molar ratio of G to acid-binding agent is 1.
7. The method for preparing coumarin oxime ester photoinitiator according to claim 6, wherein the reaction temperature in step (1) is 70-100 ℃ and the reaction time is 1-10 hours.
8. The method for preparing coumarin oxime ester photoinitiator according to claim 6, wherein the low temperature in the step (2) is-20 ℃, and the reaction time is 1-10 hours.
9. The method for preparing coumarin oxime ester photoinitiators according to claim 6, wherein in step (3), the addition amounts of paraformaldehyde, magnesium chloride and triethylamine are 3-10 equivalents, the reaction temperature is 70-200 ℃, and the reaction is carried out for 24 hours.
10. The method for preparing coumarin oxime ester photoinitiator according to claim 6, wherein in the step (4), the aliphatic amine comprises piperidine, the reaction temperature is 0-50 ℃, and the reaction time is 1-10 hours.
11. The method for preparing coumarin oxime ester photoinitiator according to claim 6, wherein in the step (5), the reaction temperature is 50-200 ℃ and the reaction time is 20-60 hours.
12. The method for preparing coumarin oxime ester photoinitiator according to claim 6, wherein in the step (6), the catalyst is any one or more of the following: cuprous iodide, palladium bis (triphenylphosphine) dichloride, palladium acetate, triphenylphosphine, and nickel bis (triphenylphosphine) dichloride; the reaction is carried out under the anaerobic condition; the reaction temperature is 20-200 ℃.
13. The method for preparing coumarin oxime ester photoinitiator according to claim 6, wherein in the step (7), the molar ratio of the intermediate F to the acid-binding agent is 1.
14. The method for preparing coumarin oxime ester photoinitiator according to claim 6, wherein in the step (8), the reaction temperature is 0-30 ℃ and the reaction time is 0.5-5 hours.
15. The method for preparing coumarin oxime ester photoinitiator according to claim 6 or 12, wherein the acid-binding agent comprises any one of the following: triethylamine, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydroxide, sodium hydride, sodium acetate and piperidine.
16. The method for preparing coumarin oxime ester photoinitiators according to claim 6, wherein the organic solvent comprises one or more of the following: dichloromethane, chloroform, methanol, ethanol, toluene, tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide, xylene, p-xylene, acetonitrile and triethylamine.
17. The use of the coumarin oxime ester photoinitiator according to claim 1, wherein the photoinitiator initiates photocuring at a radiation wavelength of 360-450nm, and is applied to the fields of single photon 3D printing, two-photon 3D printing, printing ink, photoresist and the like.
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