CN114478436B - Alpha-aminoketone photoinitiator modified by containing polymerizable itaconic acid group, and preparation method and application thereof - Google Patents
Alpha-aminoketone photoinitiator modified by containing polymerizable itaconic acid group, and preparation method and application thereof Download PDFInfo
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- CN114478436B CN114478436B CN202210248583.4A CN202210248583A CN114478436B CN 114478436 B CN114478436 B CN 114478436B CN 202210248583 A CN202210248583 A CN 202210248583A CN 114478436 B CN114478436 B CN 114478436B
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- China
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- itaconic acid
- photoinitiator
- polymerizable
- preparation
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- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical group OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 3
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 10
- BURSQOWDCOMQCI-UHFFFAOYSA-N 2-methyl-2-morpholin-4-yl-1-phenylpropan-1-one Chemical class C=1C=CC=CC=1C(=O)C(C)(C)N1CCOCC1 BURSQOWDCOMQCI-UHFFFAOYSA-N 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 238000003847 radiation curing Methods 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 230000005284 excitation Effects 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims description 4
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims description 3
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 claims description 2
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 claims description 2
- NXLHCZSMKCSROC-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpentan-3-one Chemical class CCC(=O)C(C)(C)N1CCOCC1 NXLHCZSMKCSROC-UHFFFAOYSA-N 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 150000002989 phenols Chemical group 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 238000000016 photochemical curing Methods 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- 150000003384 small molecules Chemical class 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 25
- 239000000543 intermediate Substances 0.000 description 22
- 150000001875 compounds Chemical class 0.000 description 11
- 239000003999 initiator Substances 0.000 description 8
- 230000037230 mobility Effects 0.000 description 8
- 238000001723 curing Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 239000003814 drug Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- -1 small molecule compound Chemical class 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- JYMPIDPBGZJAJB-UHFFFAOYSA-N 1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-2-morpholin-4-ylpropan-1-one Chemical compound C=1C=C(OCCO)C=CC=1C(=O)C(C)(C)N1CCOCC1 JYMPIDPBGZJAJB-UHFFFAOYSA-N 0.000 description 1
- IVSZAIOOHWNQPC-UHFFFAOYSA-N 1-[4-(2-hydroxyethylsulfanyl)phenyl]-2-methyl-2-morpholin-4-ylpropan-1-one Chemical compound C=1C=C(SCCO)C=CC=1C(=O)C(C)(C)N1CCOCC1 IVSZAIOOHWNQPC-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- 125000006016 2-bromoethoxy group Chemical group 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 101000769438 Aspergillus terreus Aristolochene synthase Proteins 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 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 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- XZPVPNZTYPUODG-UHFFFAOYSA-M sodium;chloride;dihydrate Chemical class O.O.[Na+].[Cl-] XZPVPNZTYPUODG-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms
- C07D295/104—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
-
- 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
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/16—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising curable or polymerisable compounds
Abstract
The invention discloses an alpha-aminoketone photoinitiator modified by a polymerizable itaconic acid group, and a preparation method and application thereof, belonging to the technical field of new material organic chemicals. A modified alpha-aminoketone photoinitiator containing a polymerizable itaconic acid group, the molecular structural formula of the modified alpha-aminoketone photoinitiator I of itaconic acid containing a polymerizable group is shown as follows: Wherein X is an S atom or an O atom. The photoinitiator I provided by the invention can replace the photoinitiator 907, and can obviously reduce the mobility of residual small molecules in a photocuring system.
Description
Technical Field
The invention relates to the technical field of new material organic chemicals, in particular to an alpha-aminoketone photoinitiator modified by a polymerizable itaconic acid group and a preparation method thereof.
Background
The photo-curing technology is a process of polymerizing liquid photosensitive resin into solid under the induction of light, has the characteristics of high efficiency, high speed, economy, energy conservation, environment friendliness and the like, and is widely applied to the fields of adhesives, photo-curing coatings, printing ink, photoresist, 3D micro-construction, biological medicine and the like. Photoinitiators are key factors in controlling the overall photopolymerization process, and their reactivity directly affects the rate of photocuring, the extent of curing, and the end product properties. In particular, food and medicine packages, children toys, etc. which are in direct contact with the human body have higher requirements on migration, smell, etc. of the residual photoinitiator. Therefore, photoinitiators with excellent properties have been the target of industry development, and more environmental protection and safer are constantly pursued.
Photocuring can be classified into radical type photocuring and cationic type photocuring, wherein the radical type photocuring is essentially that a photoinitiator is rapidly decomposed under the irradiation of light to generate active radicals, and chain reaction polymerization crosslinking of the photocuring resin with double bonds and an active diluent is initiated. Among the various photoinitiators, α -aminoketone photoinitiators are one of the photoinitiators used widely due to their good initiation effect, simple structure, and ease of synthesis, and representative initiators are 907:
In the photo-curing process, the photo-curing agent has good compatibility with other materials and is widely applied to various industries such as ink, paint, cosmetics and the like. However, like most small organic molecule compounds, there is more or less certain toxicity, especially in the packaging and printing fields of foods, medicines, sanitary products and the like, after photo-curing is completed, a part of the photoinitiator is physically entrapped in an acrylate crosslinked network to become a residual photoinitiator, and when the photoinitiator contacts with hot water, solvents, grease and other substances, migration, permeation or extraction of molecules occurs, so that certain health and safety hazards are caused.
Biomass-based photocurable materials have received increasing attention since the 21 st century. Itaconic acid is a small molecule compound with an unsaturated double bond and a terminal carboxyl group, and due to its scalability, sustainability and non-toxicity, the renewable energy laboratory in the united states energy country has promulgated itaconic acid as one of the first twelve renewable chemicals available as biomass energy. Itaconic acid is named as methylene succinic acid and methylene succinic acid, is the fifth largest organic acid in the world (citric acid, gluconic acid, lactic acid and malic acid in sequence in the first four positions), and is an unsaturated binary organic acid. The itaconic acid is considered as a biomass renewable raw material, and is prepared by taking agricultural and sideline products such as starch, sucrose, molasses, wood dust, straw and the like as raw materials, taking aspergillus terreus as a strain for fermentation for two days, and then filtering, concentrating, decolorizing, crystallizing and drying.
The present invention is directed to providing a modified photoinitiator to solve the above-mentioned technical problems, and to providing a preparation method and specific applications thereof.
Disclosure of Invention
1. Technical problem to be solved
Aiming at the problems in the prior art, the invention aims to provide an alpha-aminoketone photoinitiator modified by a polymerizable itaconic acid group and a preparation method thereof, and the photoinitiator I provided by the invention can replace a photoinitiator 907 and can obviously reduce the mobility of residual small molecules in a photocuring system.
2. Technical proposal
In order to solve the problems, the invention adopts the following technical scheme.
A modified alpha-aminoketone photoinitiator containing a polymerizable itaconic acid group, the molecular structural formula of the modified alpha-aminoketone photoinitiator I of itaconic acid containing a polymerizable group is shown as follows:
Wherein X is an S atom or an O atom.
A preparation method of an alpha-aminoketone photoinitiator modified by a polymerizable itaconic acid group,
The method comprises the steps of taking 2-morpholinyl-2-methyl propiophenone derivative (I) -a or intermediate (I) -b as a starting raw material to prepare a polymerizable itaconic acid group-containing modified alpha-aminoketone photoinitiator shown in a formula I;
The preparation method comprises the following steps:
Dissolving 2-morpholinyl-2-methyl propiophenone derivative (I) -a in a first solvent, dropwise adding a halogenated reagent into a mixed solution of the 2-morpholinyl-2-methyl propiophenone derivative (I) -a and an organic solvent under the protection of nitrogen atmosphere, reacting the halogenated reagent with the 2-morpholinyl-2-methyl propiophenone derivative (I) -a for 0.5-12h, controlling the reaction temperature to be between-10 and 20 ℃, and extracting, washing with alkaline water and evaporating to obtain an intermediate (I) -b after the reaction is finished;
And (2) dispersing itaconic acid, alkali and polymerization inhibitor in a second solvent to prepare a first system solution, adding an intermediate (I) -b into the first system solution after the neutralization of the itaconic acid and alkali is completed, reacting the salt formed by the itaconic acid and alkali with the intermediate (I) -b at 20-100 ℃ for 3-24h, washing with water, and drying to obtain the alpha-aminoketone photoinitiator modified by the polymerizable itaconic acid groups.
Preferably, in step (1), the molar ratio of 2-morpholino-2-methylpropionone derivative to halogenated agent is 1:1.0-1.2; and/or the number of the groups of groups,
In the step (1), the halogenated reagent is selected from one or more of thionyl chloride, phosphorus tribromide and phosphorus pentachloride; and/or the number of the groups of groups,
In the step (1), the first solvent is selected from one or two of toluene and methylene dichloride; and/or the number of the groups of groups,
In the step (1), the mass concentration of the alkaline water is 0.1-1mol/L, and the alkaline water is one or two of sodium bicarbonate aqueous solution or sodium hydroxide aqueous solution; and/or the number of the groups of groups,
In the step (2), the molar ratio of the intermediate (I) -b to the itaconic acid to the alkali is 2:1:2; and/or the number of the groups of groups,
In the step (2), the alkali is organic alkali or inorganic alkali; and/or the number of the groups of groups,
In the step (2), the polymerization inhibitor is a phenolic compound; and/or the number of the groups of groups,
In the step (2), the mass ratio of the polymerization inhibitor to the itaconic acid is 1% -3%:1, a step of; and/or the number of the groups of groups,
In the step (2), the second solvent is a polar solvent.
Preferably, the organic base includes, but is not limited to, sodium methoxide, sodium ethoxide, potassium tert-butoxide, triethylamine, tetramethylguanidine or 1, 5-diazabicyclo [4.3.0] non-5-ene; and/or the number of the groups of groups,
Inorganic bases include, but are not limited to, sodium hydride, potassium carbonate, sodium hydroxide, or potassium hydroxide; and/or the number of the groups of groups,
Polar solvents include, but are not limited to, methanol, ethanol, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), or acetonitrile;
polymerization inhibitors include, but are not limited to, hydroquinone, 2, 6-di-tert-butylphenol or 2, 4-di-tert-butylphenol.
Use of an alpha-aminoketone photoinitiator modified with polymerisable itaconic acid groups as a radiation curing photoinitiator or as an intermediate or starting material or reagent in chemical synthesis.
Preferably, the excitation light source of the radiation curing photoinitiator is selected from one or more of ultraviolet light and visible light.
Preferably, the radiation curing photoinitiator comprises 0.01 to 30 parts by weight of an alpha-aminoketone photoinitiator modified with a polymerizable itaconic acid group and 100 parts by weight of an ethylenically unsaturated compound;
preferably, the radiation-curable photoinitiator comprises 0.5 to 10 parts by weight of an alpha-aminoketone photoinitiator modified with polymerizable itaconic acid groups and 100 parts by weight of an ethylenically unsaturated compound.
Preferably, the radiation-curable photoinitiator further comprises an auxiliary agent, the weight ratio of the ethylenically (c=c) unsaturated compound to the auxiliary agent being 100:0-4.5.
Preferably, the specific steps for using the radiation curing photoinitiator are as follows:
Step (1): mixing an ethylenically unsaturated compound, a radiation curing photoinitiator and an auxiliary agent, and fully stirring to form a polymerization system, wherein the mass ratio of the ethylenically unsaturated compound to the radiation curing photoinitiator to the auxiliary agent is 100:0.5-1:0-4.5;
Step (2): irradiating the polymerization system with a radiation curing photoinitiator excitation light source;
step (3): polymerization conversion was studied by the change of its characteristic peak using a spectroscopic analysis method.
Preferably, the ethylenically unsaturated compound refers to a compound or mixture of ethylenically unsaturated compounds that are crosslinked by free radical polymerization.
Preferably, the ethylenically unsaturated compound is selected from monomers, oligomers or prepolymers, or mixtures or copolymers of the three, or aqueous dispersions of the three.
Preferably, the adjuvants include, but are not limited to, one or more of inorganic fillers, organic fillers, colorants, solvents, and other additives.
Preferably, the other additives include ultraviolet light absorbers, light stabilizers, flame retardants, leveling agents or defoamers; and/or the pigment is selected from pigments or dyes.
Preferably, monomers include, but are not limited to, (meth) acrylates, acrolein, olefins, conjugated dienes, styrene, maleic anhydride, fumaric anhydride, vinyl acetate, vinyl pyrrolidone, vinyl imidazole, (meth) acrylic acid derivatives such as (meth) acrylamides or vinyl halides and vinylidene halides.
Preferably, the prepolymers and oligomers include, but are not limited to, (meth) acrylic copolymers of (meth) acryl functional groups, urethane (meth) acrylates, polyester (meth) acrylates, unsaturated polyesters, polyether (meth) acrylates, silicone (meth) acrylates, epoxy (meth) acrylates, and water soluble or water dispersible analogs of the foregoing.
3. Advantageous effects
Compared with the prior art, the invention has the advantages that:
(1) The method introduces the itaconic acid into the 2-morpholinyl-2-methyl propiophenone derivative to prepare the photoinitiator I, the preparation process of the photoinitiator I is simple, the itaconic acid raw material is easy to obtain, and the preparation method of the photoinitiator I is easy for industrial production.
(2) The photoinitiator I prepared by the invention has the same photoinitiation performance as the photoinitiator 907, has lower migration volatility, is suitable for the fields with higher biotoxicity requirements, such as food and medicine packaging coatings, contact biomedical materials and the like, and has strong application prospects.
(3) The photoinitiator I prepared by the method contains itaconic acid unsaturated double bonds, and when the photoinitiator I initiates cross-linking polymerization of resin and monomer in a curing system, the photoinitiator I can also generate macromolecules with the cross-linking polymerization of the resin and monomer in the system, so that the photoinitiator I has the advantages of low mobility and low volatility.
Drawings
FIG. 1 is a 1 H NMR spectrum of intermediate (I) -b in CDCl 3 in example 1 of the invention.
Detailed Description
The invention is further illustrated by the following examples.
Example 1: preparation of intermediate (I) -b and photoinitiator I-1 of target product
1) Preparation of intermediate (I) -b:
30.9 g of 2-morpholino-4' - (2-hydroxyethylthio) -2-methyl propiophenone (I) -a (0.1 mol) and 300 ml of anhydrous dichloromethane are added into a double-layer reaction bottle, the low-temperature circulation is started, the temperature of the reaction system is reduced to 0 ℃, 50ml of dichloromethane solution of phosphorus tribromide is dropwise added under the protection of nitrogen atmosphere, the adding amount of the phosphorus tribromide is 0.105mol, the temperature of the reaction system can be immediately increased, the dropwise adding temperature is controlled to be lower than 5 ℃, the dropwise adding is completed for about 30 minutes, the stirring is carried out at a low temperature for 30 minutes, and the reaction is carried out again for 2 hours after the temperature is increased to room temperature; the reaction is monitored by a dot plate until the reaction is finished, the dot plate is washed by 0.1mol/L sodium bicarbonate or sodium hydroxide solution, the dot plate is washed by saturated sodium chloride aqueous solution and deionized water for two times, the solvent is directly dried by spin after drying, a viscous light yellow sample is obtained after a vacuum oven is used for 24 hours, and the product yield of the intermediate (I) -b is 90 percent.
The 1 H NMR spectrum of intermediate (I) -b is shown in FIG. 1: MS (C 16H22BrNO2 S): m/e:373.05; experimental results: 374.06 (M+H +).
1H NMR(400MHz,CDCl3):δ8.52(d,J＝8.0Hz,2H);7.33(d,J＝8.0Hz,2H);3.69(m,4H);3.52(m,2H);3.41(m,4H);2.56(m,4H);1.28(s,6H).
2) Preparation of the target product (I) -1:
To a 100 mL three-necked flask were added 3.73 g (I) -b (10 mmol), 1.38 g potassium carbonate (10 mmol) and 0.65 g itaconic acid (5 mmol), and 40 g DMF was added for dissolution; under the protection of nitrogen atmosphere, the three-mouth bottle is placed in an oil bath at 100 ℃ for stirring reaction for 5 hours, TLC monitors the reaction until the reaction is finished, 300 ml of water is added into the reaction system, ethyl acetate extraction, saturated saline water and deionized water are used for washing, anhydrous sodium sulfate is used for drying, and the pale yellow product is obtained after evaporation to dryness. The yield of the target product (I) -1 was 73%.
1 H NMR spectra of pale yellow products: MS (C 37H48N2O8S2): m/e:712.92; experimental results: 713.93 (M+H +).
1H NMR(CDCl3,400MHz)：8.51(d,J＝8.6Hz,2H);8.49(d,J＝8.6Hz,2H);8.35(d,J＝8.6Hz,2H);8.33(d,J＝8.6Hz,2H);6.35(d,J＝1.6Hz,2H);5.86(d,J＝1.6Hz,2H);4.54(d,J＝7.0Hz,2H);4.34(d,J＝7.0Hz,2H);4.12(s,2H);3.69(s,8H);3.33(d,J＝7.0Hz,2H);3.26(d,J＝7.0Hz,2H);2.56(s,8H);1.30(s,12H). Of these, 6.35ppm and 5.86ppm are signal peaks for hydrogen on double bonds, further indicating that the product has been successfully synthesized.
Example 2: preparation of target product photoinitiator I by using chlorinated intermediate
For all procedures, reference is made to example 1, using thionyl chloride or phosphorus pentachloride as the halogenating agent to prepare chlorinated intermediates in 89% yield; then the procedure of example 1 was used to prepare the desired product using the chlorinated intermediate, which was identical except that the intermediate was different from the intermediate in the preparation of the desired product in example 1; the yield of the target product photoinitiator I was 70%.
Example 3: preparation of target product by using tetramethyl guanidine as alkali
To a 100 ml three-necked flask, 0.65 g of itaconic acid (5 mmol) and 30 g of DMSO were added, 1.14 g of tetramethylguanidine (10 mmol) was added, stirring was performed at room temperature (25 ℃) for 10 minutes, 10mmol of the chloro or bromo intermediate was dissolved in 10 g of DMSO, dropwise added to the reaction system under the protection of nitrogen, stirring was performed at room temperature for 5 hours, after TLC monitoring the reaction to completion, 300 ml of water was added to the reaction system, extraction was performed with ethyl acetate, washing with saturated brine and deionized water, drying over anhydrous sodium sulfate, and column chromatography was performed after evaporation to dryness to obtain a pale yellow product.
The yield of the target product prepared from the chlorinated intermediate is 84%; the yield of the desired product was 86% using the brominated intermediate.
Example 4: preparation of 2-morpholinyl-4' - (2-bromoethoxy) -2-methylpropionne and target product (I) -2
1) Preparation of intermediate bromo (I) -d:
29.3 g of 2-morpholino-4' - (2-hydroxyethoxy) -2-methyl propiophenone (I) -c (0.1 mol) and 300 ml of anhydrous dichloromethane are added into a double-layer reaction bottle, a low-temperature cycle is started, the temperature of the reaction system is reduced to 0 ℃,50 ml of dichloromethane solution of phosphorus tribromide (0.0105 mol) is added dropwise under the protection of nitrogen atmosphere, the temperature of the system is immediately increased, the dropwise adding temperature is controlled to be lower than 5 ℃, the dropwise adding temperature is controlled to be lower than 30 minutes, stirring is carried out for 30 minutes at a low temperature, and the reaction is carried out for 2 hours after the mixture is cooled to room temperature; the reaction is monitored by a dot plate until the reaction is finished, the dot plate is washed by 0.1mol/L sodium bicarbonate or sodium hydroxide solution, the dot plate is washed by saturated sodium chloride aqueous solution and deionized water for two times, the solvent is directly dried by spin, and a viscous light yellow sample is obtained after a vacuum oven for 24 hours and can be directly used.
The product yield of intermediate bromo (I) -d was 92%.
MS (C 16H22BrNO3): m/e:355.08; experimental results: 356.08 (M+H +).
2) Preparing a target product (I) -2:
3.55 g of intermediate (10 mmol), 1.38 g (10 mmol) of potassium carbonate and 0.65 g of itaconic acid (5 mmol) are added into a 100ml three-port bottle, 40 g of DMF is added for dissolution, the three-port bottle is placed into an oil bath at 100 ℃ under the protection of nitrogen, stirring is carried out for 5 hours, TLC monitors the reaction till the reaction is finished, 300 ml of water is added into the reaction system, ethyl acetate is used for extraction, saturated saline water and deionized water are used for washing, anhydrous sodium sulfate is used for drying, and column chromatography is carried out after evaporation to dryness, thus obtaining a pale yellow product; the yield of the target product was 83%.
MS (C 37H48N2O10): m/e:680.33; experimental results: 681.33 (M+H +).
Experiments were performed on the target product prepared in the examples
< Experiment >
The following experiments were performed with the products of the above examples, respectively.
< Experiment 1>
Photo-curing test of the initiator prepared in examples
The photoinitiator (I) -1 or photoinitiator (I) -2 or photoinitiator 907 was formulated as follows in mass percent, respectively:
Difunctional monomer (TPGDA): 97%
Photoinitiators ((I) -1 or (I) -2 or 907): 2%
Leveling agent: 0.5%
Defoaming agent: 0.5%
The three solutions prepared above are respectively coated on cardboard to form a coating of about 30-35 microns, an LED light source (3 cm wide and 80 cm long LED surface light source) with the emission wavelength of 365 nanometers and the unit power of 2000mW/cm 2 produced by Guangzhou and Guangdong corporation is used as an excitation light source, and the excitation light source is placed on a variable speed conveyor belt, and mark is not generated by repeated embossing scraping of nails as a criterion for finishing photopolymerization curing.
The results indicate that the curing speed of photoinitiator (I) -1 or photoinitiator (I) -2 and photoinitiator 907 in the monomers did not show variability.
< Experiment 2>
Migration test of photo-cured product of photoinitiator (I) -1 or photoinitiator (I) -2
The trimethylolpropane triacrylate solution of each 1% of photoinitiator (I) -1 or photoinitiator (I) -2 and photoinitiator 907 is prepared respectively, and is respectively smeared on a glass slide, the thickness of the film body is generally 30-35 mu m, the film is coated in air, an LED light source (3 cm wide and 80 cm long LED surface light source) with the emission wavelength of 365 nm and produced by Guangzhou and Guangdong company and the unit power of 200mW/cm 2 is used as an excitation light source, and the excitation light source is placed on a variable-speed conveyor belt to be solidified for 5 times, and the speed of the conveyor belt is 30 m/s. The cured films were then peeled off, sheared, 100 milligrams each, immersed in 20mL of acetonitrile, after 24 hours the supernatant was taken to test the uv-vis absorbance spectrum, the absorbance at the maximum absorbance peak of the α -aminoketone initiator at 307nm was recorded, three parallel samples were tested, and the average was taken.
The relative mobilities of the photoinitiator and 907 of the two initiators I in the present invention can be calculated from the following formula.
c＝A/(ε·b)
R＝c(I)/c(907)
The specific concentration of the photoinitiator in the extract is shown in the formula, and the unit is mol/L; a is absorbance; epsilon is the molar absorptivity of the initiator at 307nm, the unit being L/(mol cm); b is the thickness of the sample cell in cm; c (I) is the concentration of photoinitiator I in the extract; c (907) is the concentration of 907 photoinitiator in the extract; r is the relative mobility of I and 907 compared, and the experimental result is: a ((I) -1) is 0.162; a ((I) -2) is 0.152; a (907) is 0.975; the mobility of the two initiators I connected with itaconic acid is 15-16% of 907, and experimental results show that the mobility of the alpha-aminoketone photoinitiator modified by the polymerizable itaconic acid group is only about one sixth of 907, and the amplitude reduction is remarkable.
It can be found from experiments 1 and 2 that not only has the photoinitiating property of the photoinitiator 907, but also the mobility of the photoinitiator I is far lower than that of the photoinitiator 907 when the modified initiator initiates the curing of the curing system; comparing the structure of the alpha-aminoketone photoinitiator I modified by the polymerizable itaconic acid group with that of the photoinitiator 907, the structural formula of the photoinitiator I is provided with a polymerizable group carbon-carbon double bond, which is unstable and easy to undergo addition reaction, so that the photoinitiator I can undergo free polymerization reaction, and meanwhile, the photoinitiator I can undergo polymerization reaction with an ethylenically unsaturated compound in a curing system, so that the photoinitiator I becomes a macromolecular structure, the photoinitiator I has low mobility and low volatility, the photoinitiator I is superior to the initiator 907, and the photoinitiator I is suitable for fields with higher requirements on biological toxicity, such as food and medicine packaging coatings, contact biological medicine materials and the like, and has a strong application prospect.
Claims (6)
1. An α -aminoketone photoinitiator modified with polymerizable itaconic acid groups, characterized by: the molecular structural formula of the photoinitiator is shown as a formula (I):
Wherein X is an S atom or an O atom.
2. A process for the preparation of a α -aminoketone photoinitiator modified with polymerizable itaconic acid groups as defined in claim 1, wherein:
The preparation method comprises the steps of taking 2-morpholinyl-2-methyl propiophenone derivative (I) -a as a starting material to prepare an alpha-aminoketone photoinitiator which is shown in a formula I and contains a polymerizable itaconic acid group modification;
The preparation method comprises the following steps:
Dissolving 2-morpholinyl-2-methyl propiophenone derivative (I) -a in a first solvent, dropwise adding a halogenated reagent into a mixed solution of the 2-morpholinyl-2-methyl propiophenone derivative (I) -a and an organic solvent under the protection of nitrogen atmosphere, reacting the halogenated reagent with the 2-morpholinyl-2-methyl propiophenone derivative (I) -a for 0.5-12h, controlling the reaction temperature to be between-10 and 20 ℃, and extracting, washing with alkaline water and evaporating to obtain an intermediate (I) -b after the reaction is finished;
And (2) dispersing itaconic acid, alkali and polymerization inhibitor in a second solvent to prepare a first system solution, adding an intermediate (I) -b into the first system solution after the neutralization of the itaconic acid and alkali is completed, reacting the salt formed by the itaconic acid and alkali with the intermediate (I) -b at 20-100 ℃ for 3-24h, washing with water, and drying to obtain the alpha-aminoketone photoinitiator modified by the polymerizable itaconic acid groups.
3. A process for the preparation of a α -aminoketone photoinitiator modified with polymerizable itaconic acid groups as claimed in claim 2, wherein: in step (1), the molar ratio of the 2-morpholino-2-methylpropionone derivative to the halogenated agent is 1:1.0-1.2; and/or the number of the groups of groups,
In the step (1), the halogenated reagent is selected from one or more of thionyl chloride, phosphorus tribromide and phosphorus pentachloride; and/or the number of the groups of groups,
In the step (1), the first solvent is selected from one or two of toluene and methylene dichloride; and/or the number of the groups of groups,
In the step (1), the mass concentration of the alkaline water is 0.1-1mol/L, and the alkaline water is one or two of sodium bicarbonate aqueous solution or sodium hydroxide aqueous solution; and/or the number of the groups of groups,
In the step (2), the molar ratio of the intermediate (I) -b to the itaconic acid to the alkali is 2:1:2; and/or the number of the groups of groups,
In the step (2), the alkali is organic alkali or inorganic alkali; and/or the number of the groups of groups,
In the step (2), the polymerization inhibitor is a phenolic compound; and/or the number of the groups of groups,
In the step (2), the mass ratio of the polymerization inhibitor to the itaconic acid is 1% -3%:1, a step of; and/or the number of the groups of groups,
In the step (2), the second solvent is a polar solvent.
4. A process for the preparation of a α -aminoketone photoinitiator modified with polymerizable itaconic acid groups as claimed in claim 3, wherein:
The organic base is any one of sodium methoxide, sodium ethoxide, potassium tert-butoxide, triethylamine, tetramethyl guanidine or 1, 5-diazabicyclo [4.3.0] non-5-ene; and/or the number of the groups of groups,
The inorganic base is any one of sodium hydride, potassium carbonate, sodium hydroxide or potassium hydroxide; and/or the number of the groups of groups,
The polar solvent is any one of methanol, ethanol, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO) or acetonitrile;
the polymerization inhibitor is any one of hydroquinone, 2, 6-di-tert-butylphenol or 2, 4-di-tert-butylphenol.
5. Use of a α -aminoketone photoinitiator modified with a polymerizable itaconic acid group as described in claim 1 as a radiation curing photoinitiator.
6. Use according to claim 5, characterized in that: the excitation light source of the radiation curing photoinitiator is selected from one or more of ultraviolet light and visible light.
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