CN108586639B - Photopolymerisable thioxanthone photoinitiator containing coinitiator amine and preparation method thereof - Google Patents
Photopolymerisable thioxanthone photoinitiator containing coinitiator amine and preparation method thereof Download PDFInfo
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- CN108586639B CN108586639B CN201810447481.9A CN201810447481A CN108586639B CN 108586639 B CN108586639 B CN 108586639B CN 201810447481 A CN201810447481 A CN 201810447481A CN 108586639 B CN108586639 B CN 108586639B
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- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 150000001412 amines Chemical class 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 238000009835 boiling Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical class O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 239000012046 mixed solvent Substances 0.000 claims description 17
- -1 alcohol amine Chemical class 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000012024 dehydrating agents Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000002390 rotary evaporation Methods 0.000 claims description 9
- LCPDWSOZIOUXRV-UHFFFAOYSA-N phenoxyacetic acid Chemical compound OC(=O)COC1=CC=CC=C1 LCPDWSOZIOUXRV-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 7
- 239000000852 hydrogen donor Substances 0.000 claims description 7
- 239000013067 intermediate product Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- LBEMXJWGHIEXRA-UHFFFAOYSA-N 2-[(2-carboxyphenyl)disulfanyl]benzoic acid Chemical compound OC(=O)C1=CC=CC=C1SSC1=CC=CC=C1C(O)=O LBEMXJWGHIEXRA-UHFFFAOYSA-N 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 5
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical group C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 230000000171 quenching effect Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 150000003512 tertiary amines Chemical class 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- BCLSJHWBDUYDTR-UHFFFAOYSA-N 2-(propylamino)ethanol Chemical compound CCCNCCO BCLSJHWBDUYDTR-UHFFFAOYSA-N 0.000 claims description 3
- SXERGJJQSKIUIC-UHFFFAOYSA-N 2-Phenoxypropionic acid Chemical compound OC(=O)C(C)OC1=CC=CC=C1 SXERGJJQSKIUIC-UHFFFAOYSA-N 0.000 claims description 3
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 3
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 3
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 claims description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 2
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- RILLZYSZSDGYGV-UHFFFAOYSA-N 2-(propan-2-ylamino)ethanol Chemical compound CC(C)NCCO RILLZYSZSDGYGV-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- RBLLZFKXJIFDCL-UHFFFAOYSA-N 3-(aminomethyl)-n-propan-2-ylbenzenesulfonamide Chemical compound CC(C)NS(=O)(=O)C1=CC=CC(CN)=C1 RBLLZFKXJIFDCL-UHFFFAOYSA-N 0.000 claims description 2
- BUSOTUQRURCMCM-UHFFFAOYSA-N 3-Phenoxypropionic acid Chemical compound OC(=O)CCOC1=CC=CC=C1 BUSOTUQRURCMCM-UHFFFAOYSA-N 0.000 claims description 2
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-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
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 2
- 150000001718 carbodiimides Chemical class 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 8
- ILROLYQPRYHHFG-UHFFFAOYSA-N 1-$l^{1}-oxidanylprop-2-en-1-one Chemical group [O]C(=O)C=C ILROLYQPRYHHFG-UHFFFAOYSA-N 0.000 claims 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical group C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000013508 migration Methods 0.000 abstract description 5
- 238000000016 photochemical curing Methods 0.000 abstract description 5
- 230000005012 migration Effects 0.000 abstract description 4
- 230000000977 initiatory effect Effects 0.000 abstract description 3
- 238000004377 microelectronic Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 150000002366 halogen compounds Chemical class 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- 238000004806 packaging method and process Methods 0.000 abstract description 2
- 231100000614 poison Toxicity 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000003440 toxic substance Substances 0.000 abstract description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 238000001723 curing Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- GJZFGDYLJLCGHT-UHFFFAOYSA-N 1,2-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3SC2=C1 GJZFGDYLJLCGHT-UHFFFAOYSA-N 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- GOVVHAHLSILYMB-UHFFFAOYSA-N 1-propoxythioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2OCCC GOVVHAHLSILYMB-UHFFFAOYSA-N 0.000 description 1
- ANHLDZMOXDYFMQ-UHFFFAOYSA-N 2-hydroxythioxanthen-9-one Chemical group C1=CC=C2C(=O)C3=CC(O)=CC=C3SC2=C1 ANHLDZMOXDYFMQ-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 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
- 238000010521 absorption reaction Methods 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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- 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
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
- C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
- C07D335/12—Thioxanthenes
- C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
- C07D335/16—Oxygen atoms, e.g. thioxanthones
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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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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Abstract
The invention discloses a photopolymerizable thioxanthone photoinitiator containing co-initiator amine and a preparation method thereof, wherein the photopolymerizable thioxanthone photoinitiator containing co-initiator amine has the following structural general formula:
the molecular structure of the thioxanthone photoinitiator simultaneously contains the terminal groups of the photoinitiator, the amine as the auxiliary initiator and the acryloxy bond, has high initiating activity, can participate in photopolymerization without migration, and can be used as a monomer for synthesizing a macromolecular photoinitiator. The product has the advantages of easily obtained raw materials, mild reaction process, no toxic substances such as halogen compounds and the like and no high-boiling point solvent, is green and environment-friendly, and is suitable for industrial production. The invention has good matching property with UV-LED light source, and can be used for photocuring molding in the fields of coating, microelectronics, packaging and the like.
Description
Technical Field
The invention relates to a substituted derivative of thioxanthone, which can be used as a photoinitiator and a photosensitizer for free radical curing, in particular to a photopolymerizable thioxanthone photoinitiator containing auxiliary initiator amine and a preparation method thereof.
Background
The photopolymerization (photocuring) technology is a process of rapidly converting a liquid substance with chemical reaction activity into a solid substance by utilizing ultraviolet light or visible light, has the advantages of energy conservation, environmental protection, high efficiency and the like compared with the traditional thermal polymerization, and has wide application in the fields of coatings, printing ink, microelectronics, photoresists, dental materials and the like. The photoinitiator in the photopolymerization system is a key component, the thioxanthone derivative is a valuable photoinitiator, and has the advantages of strong ultraviolet absorption, wide peak shape and strong hydrogen-capturing capability, the thioxanthone derivative (such as isopropyl thioxanthone and diethyl thioxanthone) which is commercially used as the photoinitiator in a large amount needs to be matched with hydrogen donors such as co-initiator amines for use, and unreacted thioxanthone derivative inevitably exists in the curing process, and the two small molecular compounds have post-migration in the curing system, thereby bringing safety and toxicity problems.
In order to improve the compatibility of thioxanthone photoinitiators with cured resin systems, patent US 9278949B 2 discloses polyfunctional thioxanthone initiators, which are polyfunctional modified with 2-hydroxy thioxanthone as a raw material, and the molecular structure of which does not contain amine-assisted initiators and polymerizable double bonds. The co-initiator amine is introduced into the molecular structure of the photoinitiator, and the process of generating free radicals under the excitation of ultraviolet belongs to intramolecular energy transfer, so that the photoinitiation efficiency can be improved, and the toxicity problem of small molecular amine can be solved. Wangbaohe et al (journal of radiation research and radiation technology, 2013,31(1):000031-35) prepare amine-containing thioxanthone photoinitiator 2- [ 2-hydroxy-3- (2-hydroxyethyl-2-methyl) amino ] propoxy thioxanthone through the ring-opening reaction of epoxy groups, and research results show that the whole system has higher polymerization reaction rate, but the structure does not contain polymerizable groups, and the document does not report the mobility of the photoinitiator. Patent CN 1594370A discloses a preparation method of a thioxanthone photoinitiator containing auxiliary initiator amino, which utilizes the reaction of thioxanthone containing double epoxy groups and auxiliary initiator containing secondary amine or primary amine, namely, one thioxanthone molecular structure corresponds to two molecules of auxiliary initiator amine. To reduce the mobility and volatility of the photoinitiating system, it is an effective method to introduce free radical polymerizable unsaturated groups into the molecular structure of the photoinitiator. WO 2014/009194A1 discloses a process for the preparation of polymerizable thioxanthones by further modification of hydroxy-containing thioxanthones, the molecular structure of which employs an amide group containing a secondary amine as a hydrogen donor. Wu Q et al (Macromolecular Chemistry & Physics,2017,218(6):1600484) prepared three small molecule photoinitiators whose end groups are double bonds and whose molecular structure contains thioxanthone and tertiary amine hydrogen donor, and the research results showed that the photocuring reaction activity is high and the migration stability is good. The preparation route is mainly based on the nucleophilic substitution reaction of chlorine atoms on a thioxanthone ring to introduce tertiary amine groups, and then utilizes acryloyl chloride to introduce double bonds. The polymerizable thioxanthone containing co-initiator disclosed in patent CN 102212150A adopts flammable liquid halopropene with high toxicity as a synthetic raw material, and the process route is complex. The preparation routes all have the problem of great synthetic pollution and are difficult to popularize in practical application.
Disclosure of Invention
The invention aims to provide a photopolymerisable thioxanthone photoinitiator containing co-initiator amine and a preparation method thereof, which are used for overcoming the problems of migration, yellowing and toxicity of the traditional micromolecule photoinitiator and can also be used as a monomer for synthesizing a macromolecular photoinitiator.
The thioxanthone photoinitiator is a substituted derivative of thioxanthone, the molecular structure simultaneously contains thioxanthone, a co-initiator of a tertiary amine hydrogen donor and an end group of an acryloyl oxygen bond, the molecular structure simultaneously contains the photoinitiator and the hydrogen donor, the process of generating free radicals under the excitation of ultraviolet light belongs to intramolecular energy transfer, more generated active groups are obtained, the initiation efficiency is high, and the advantage of less consumption of small molecular initiators is reserved; the acryloyl oxygen bond at the end group of the molecule can participate in photopolymerization, and the polymerization activity is far higher than that of a common double bond.
The photopolymerizable thioxanthone photoinitiator containing co-initiator amine has the following structural general formula:
wherein: r1Selected from methylene, ethylene, dimethylene or trimethylene; r2Selected from dimethylene-CH2CH2-, trimethylene-CH2CH2CH2-, 1, 2-propylene-CH (CH)3)CH2-, 1, 2-butylene-CH (CH)2CH3)CH2-, 2-methyl-1, 2-propylene-C (CH)3)2CH2-；R3Selected from hydrogen, methyl, propyl, isopropyl or
R4Selected from hydrogen or methyl.
The preparation method of the photopolymerisable thioxanthone photoinitiator containing coinitiator amine comprises the steps of firstly preparing the thioxanthone containing carboxyl, modifying the thioxanthone, introducing a hydrogen donor containing tertiary amine and an acryloyloxy group capable of participating in photopolymerization, and preparing the thioxanthone photoinitiator.
The preparation method of the photopolymerisable thioxanthone photoinitiator containing coinitiator amine comprises the following steps (in parts by mass):
step 1: uniformly mixing 1 part of 2, 2' -dithiosalicylic acid and 2-20 parts of concentrated sulfuric acid (the mass concentration is 98%), controlling the reaction temperature at 0-4 ℃ by using an ice salt bath, adding 1-10 parts of phenoxy acid compounds in batches, stirring and reacting for 2-20 hours under the ice salt bath, quenching with ice water, carrying out suction filtration and drying, and recrystallizing the obtained crude product with a mixed solvent of alcohol and water to obtain carboxyl-containing thioxanthone;
step 2: adding 4 parts of carboxyl-containing thioxanthone prepared in the step 1 and 1-5 parts of monohydroxy-containing alcohol amine into 10-50 parts by mass of an organic solvent, then adding 0.2-1.0 part of a dehydrating agent/catalyst system, reacting for 8-12 hours at 0-50 ℃, cooling after the reaction is finished, filtering the reaction liquid through thin-layer activated carbon, removing the solvent and unreacted alcohol amine through rotary evaporation, adding the organic solvent and water into the solid residue, performing liquid separation extraction, drying the organic phase through anhydrous calcium chloride, and removing the organic solvent through rotary evaporation to obtain an initial product; recrystallizing the primary product in a mixed solvent of alcohol and water to obtain an esterified intermediate product;
and step 3: and (3) adding 3 parts of esterified intermediate product prepared in the step (2) and 1-5 parts of glycidyl ester monomer containing an acryloyloxy bond group into 10-50 parts of organic solvent, reacting for 5-10 h at 50-90 ℃, cooling and filtering after the reaction is finished, boiling the product in water, heating and refluxing for 1-10 h, cooling, filtering, drying, and recrystallizing by using a mixed solvent of alcohol and water to obtain the target product.
In the step 1, the phenoxy acid compound is selected from phenoxyacetic acid, 2-phenoxypropionic acid, 3-phenoxypropionic acid or 4-phenoxybutyric acid.
In step 2, the monohydroxy alcohol amine is selected from ethanolamine, propanolamine, monoisopropanolamine, butanolamine, isobutanolamine, N-methyl monoethanolamine, 2- (propylamino) ethanol or 2- (isopropylamino) ethanol.
In step 2, the dehydrating agent/catalyst system is selected from dicyclohexylcarbodiimide/4-dimethylaminopyridine, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide/4-dimethylaminopyridine or (1-ethyl-3 (3-dimethylpropylamine) carbodiimide)/1-hydroxybenzotriazole; the molar ratio between the dehydrating agent and the catalyst was 3: 2.
In step 2, the organic solvent is selected from acetone, butanone, cyclohexanone, tetrahydrofuran, acrylic acid, toluene, xylene or ethyl acetate.
In the step 3, the glycidyl ester monomer containing the acryloyloxy group is selected from glycidyl acrylate or glycidyl methacrylate.
In the step 1, the step 2 and the step 3, the volume ratio of the alcohol to the water in the mixed solvent of the alcohol and the water is 4: 1; the alcohol is selected from methanol, ethanol or propanol.
The preparation route of the invention is as follows:
the photopolymerizable amine-containing thioxanthone photoinitiators of the invention can be used in any of the known photopolymerization reactions, and are particularly useful in a variety of acrylic resins.
The molecular structure of the photopolymerisable thioxanthone photoinitiator containing the co-initiator amine simultaneously contains the photoinitiator, the co-initiator amine and the terminal group of an acryloyloxy bond, has high initiating activity, and can participate in a curing reaction without migration.
The synthetic route of the invention does not relate to toxic substances such as halogen compounds and the like and high-boiling point solvents, is green and environment-friendly, and is suitable for industrial production. The invention has good matching property with UV-LED light source, and can be used for photocuring molding in the fields of coating, microelectronics, packaging and the like.
Drawings
FIG. 1 is an infrared spectrum of O- (thioxanthone- [2] -yl) -oxyacetic acid, an intermediate prepared in example 1 and example 3.
Detailed Description
The invention will be further illustrated by the following non-limiting examples.
Example 1:
1. uniformly mixing 4.7g (0.015mol) of 2, 2' -dithiosalicylic acid with 28mL (0.50mol) of concentrated sulfuric acid, controlling the reaction temperature in an ice salt bath at 0-5 ℃, adding 6.1g (0.04mol) of phenoxyacetic acid, stirring for reacting for 8 hours, quenching with ice water, filtering, and drying. The crude product is recrystallized by a mixed solvent of ethanol and water (volume ratio is 4:1) to obtain the product O- (thioxanthone- [2] -yl) -oxyacetic acid with the yield of 78 percent.
2. Placing 2.89g (0.01mol) of O- (thioxanthone- [2] -yl) -oxyacetic acid, 0.75g (0.01mol) of propanolamine and 30mL of acetone solvent into a three-neck flask, adding 0.62g of dicyclohexylcarbodiimide dehydrating agent and 0.24g of 4-dimethylaminopyridine catalyst, reacting for 4 hours at room temperature, cooling, filtering by using thin-layer activated carbon, evaporating to remove acetone, dissolving by using diluted hydrochloric acid, washing by using toluene, adjusting the pH value to 8-9 by using ammonia water, extracting by using ethyl acetate, drying an organic phase by using anhydrous calcium chloride, performing rotary evaporation to remove ethyl acetate, and recrystallizing by using a mixed solvent of ethanol and water (volume ratio of 4:1) in a refrigerator overnight to obtain the product. The yield was 81%.
3. Placing the 2.1g (0.005mol) of esterified intermediate product, 0.72g (0.01mol) of glycidyl acrylate monomer and 30mL of tetrahydrofuran solvent into a three-neck flask, reacting at 60 ℃ for 7h, removing the solvent by rotary evaporation, adding water, boiling the product for 2h, cooling, performing suction filtration and drying, and recrystallizing by using a mixed solvent (volume ratio of 4:1) of alcohol and water to obtain the photopolymerizable thioxanthone photoinitiator containing the co-initiator amine, wherein the yield is 67%.
The structural formula of the target product obtained in this example is:
example 2:
1. uniformly mixing 4.7g (0.015mol) of 2, 2' -dithiosalicylic acid with 28mL (0.50mol) of concentrated sulfuric acid, controlling the reaction temperature of an ice salt bath at 0-5 ℃, adding 6.7g (0.04mol) of 2-phenoxypropionic acid, stirring for reacting for 8 hours, quenching with ice water, carrying out suction filtration, and drying. The crude product is recrystallized by a mixed solvent of ethanol and water (volume ratio is 4:1) to obtain the product O- (thioxanthone- [2] -yl) -oxopropanoic acid with the yield of 72 percent.
2. Placing 3.03g (0.01mol) of O- (thioxanthone- [2] -yl) -oxopropanoic acid, 1g (0.01mol) of 2- (propylamino) ethanol and 30mL of acetone solvent into a three-neck flask, adding 0.45g of dicyclohexylcarbodiimide dehydrating agent and 0.18g of 4-dimethylaminopyridine catalyst, reacting at room temperature for 5h, cooling, filtering with thin-layer activated carbon, evaporating to remove acetone, dissolving with diluted hydrochloric acid, washing with toluene, adjusting pH to 8-9 with ammonia water, extracting with ethyl acetate, drying the organic phase with anhydrous calcium chloride, evaporating to remove ethyl acetate, and recrystallizing the solid residue with a mixed solvent of ethanol and water (volume ratio 4:1) in a refrigerator overnight to obtain the product with a yield of 75%.
3. Placing the 2.11g (0.005mol) of esterified intermediate product, 0.36g (0.005mol) of glycidyl methacrylate monomer and 30mL of tetrahydrofuran solvent into a three-neck flask, reacting at 60 ℃ for 6h, removing the solvent by rotary evaporation, adding water product, boiling for 2h, cooling, performing suction filtration and drying, and recrystallizing by using a mixed solvent (volume ratio of 4:1) of alcohol and water to obtain the thioxanthone photoinitiator capable of photopolymerizing the amine containing the co-initiator with the yield of 73%.
The structural formula of the target product obtained in this example is:
example 3:
1. uniformly mixing 4.7g (0.015mol) of 2, 2' -dithiosalicylic acid with 28mL (0.50mol) of concentrated sulfuric acid, controlling the reaction temperature in an ice salt bath at 0-5 ℃, adding 6.1g (0.04mol) of phenoxyacetic acid, stirring for reacting for 8 hours, quenching with ice water, filtering, and drying. The crude product is recrystallized by a mixed solvent of ethanol and water (volume ratio is 4:1) to obtain the product O- (thioxanthone- [2] -yl) -oxyacetic acid with the yield of 78 percent.
2. Placing 2.89g (0.01mol) of O- (thioxanthone- [2] -yl) -oxyacetic acid, 0.76g (0.01mol) of N-methyl monoethanolamine and 30mL of acetone solvent into a three-neck flask, adding 0.62g of dicyclohexylcarbodiimide dehydrating agent and 0.24g of 4-dimethylaminopyridine catalyst, reacting for 4 hours at room temperature, cooling, filtering by using thin-layer activated carbon, evaporating to remove acetone, dissolving by using diluted hydrochloric acid, washing by using toluene, adjusting the pH value to 8-9 by using ammonia water, extracting by using ethyl acetate, drying an organic phase by using anhydrous calcium chloride, performing rotary evaporation to remove ethyl acetate, and recrystallizing by using a mixed solvent of ethanol and water (volume ratio of 4:1) in a refrigerator overnight to obtain the product with the yield of 79%.
3. Placing 2.1g (0.005mol) of the esterified intermediate product, 0.78g (0.005mol) of glycidyl ethacrylate monomer and 30mL of tetrahydrofuran solvent into a three-neck flask, reacting at 60 ℃ for 6h, removing the solvent by rotary evaporation, adding water product, boiling for 2h, cooling, carrying out suction filtration and drying, and recrystallizing by using a mixed solvent (volume ratio of 4:1) of alcohol and water to obtain the thioxanthone photoinitiator capable of photopolymerizing the amine containing the co-initiator with the yield of 74%.
The structural formula of the target product obtained in this example is:
example 4:
under the dark condition, the final product prepared in example 1 is used as a photoinitiator, and is uniformly dispersed with acrylate resin, trimethylolpropane triacrylate and modified polysiloxane to prepare a UV-LED photocuring coating, the thickness of the coating is controlled to be 60 mu m by a coating device, and then a UV-LED light source with the dominant wavelength of 395nm and the energy of the light source is 35mW cm-2The irradiation height was 10cm, and the irradiation time was 120 seconds to obtain a cured film. The pencil hardness of the cured film is tested by referring to GB/T6739-. The transfer amount of the photoinitiator in the cured film was 0.05 mg/kg.
In the application, the formula of the UV-LED photocureable coating is as follows:
the method for measuring and calculating the mobility of the photoinitiator comprises the following steps: weighing 1g of a solidified membrane sample in a 50mL conical flask, weighing 30mL of acetonitrile solution, adding the acetonitrile solution into the conical flask, extracting for 30min by ultrasonic wave, transferring the extract liquid into the flask, placing the flask on a rotary evaporator to evaporate to dryness, adding about 1-2 mL of acetonitrile to dissolve extraction residues, absorbing 1mL of acetonitrile solution dissolved with an extract, filtering the solution by a 0.45-micron filter membrane, collecting the filtrate, analyzing by a gas chromatography-mass spectrometry (GC-MS), and testing the conditions by the GC-MS: GC conditions were as follows: the chromatographic column is HP-5MS (30m × 0.25mm × 0.25 μm), the heating rate is 10 deg.C/min to 280 deg.C, the temperature is kept for 2min, the carrier gas is helium, the flow rate is 1.0mL/min, and the sample injection amount is 1 μ L. MS conditions: the electrons bombard the ion source, the electron energy is 70eV, the ion source temperature is 230 ℃, and the solvent delay is 5 min.
Claims (10)
1. A photopolymerizable thioxanthone photoinitiator containing co-initiator amine is characterized by having the following structural general formula:
wherein: r1Selected from methylene, ethylene or trimethylene; r2Selected from dimethylene-CH2CH2-, trimethylene-CH2CH2CH2-, 1, 2-propylene-CH (CH)3)CH2-, 1, 2-butylene-CH (CH)2CH3)CH2-, 2-methyl-1, 2-propylene-C (CH)3)2CH2-；R3Selected from hydrogen, methyl, propyl, isopropyl or
R4Selected from hydrogen or methyl.
2. A process for preparing a photopolymerizable co-initiator amine-containing thioxanthone photoinitiator according to claim 1, characterized in that: firstly, preparing thioxanthone containing carboxyl, modifying the thioxanthone, introducing hydrogen donor containing tertiary amine and acryloyl oxygen group capable of participating in photopolymerization, and preparing the thioxanthone photoinitiator.
3. The method of claim 2, comprising the steps of:
step 1: uniformly mixing 1 part of 2, 2' -dithiosalicylic acid and 2-20 parts of concentrated sulfuric acid, controlling the reaction temperature at 0-4 ℃ by using an ice salt bath, adding 1-10 parts of phenoxy acid compounds in batches, stirring and reacting for 2-20 hours under the ice salt bath, quenching with ice water, carrying out suction filtration and drying, and recrystallizing the obtained crude product with a mixed solvent of alcohol and water to obtain carboxyl-containing thioxanthone;
step 2: adding 4 parts of carboxyl-containing thioxanthone prepared in the step 1 and 1-5 parts of monohydroxy-containing alcohol amine into 10-50 parts by mass of an organic solvent, then adding 0.2-1.0 part of a dehydrating agent/catalyst system, reacting for 8-12 hours at 0-50 ℃, cooling after the reaction is finished, filtering the reaction liquid through thin-layer activated carbon, removing the solvent and unreacted alcohol amine through rotary evaporation, adding the organic solvent and water into the solid residue, performing liquid separation extraction, drying the organic phase through anhydrous calcium chloride, and removing the organic solvent through rotary evaporation to obtain an initial product; recrystallizing the primary product in a mixed solvent of alcohol and water to obtain an esterified intermediate product;
and step 3: and (3) adding 3 parts of esterified intermediate product prepared in the step (2) and 1-5 parts of glycidyl ester monomer containing an acryloyloxy bond group into 10-50 parts of organic solvent, reacting for 5-10 h at 50-90 ℃, cooling and filtering after the reaction is finished, boiling the product in water, heating and refluxing for 1-10 h, cooling, filtering, drying, and recrystallizing by using a mixed solvent of alcohol and water to obtain the target product.
4. The production method according to claim 3, characterized in that:
in the step 1, the phenoxy acid compound is selected from phenoxyacetic acid, 2-phenoxypropionic acid, 3-phenoxypropionic acid or 4-phenoxybutyric acid.
5. The production method according to claim 3, characterized in that:
in step 2, the monohydroxy alcohol amine is selected from ethanolamine, propanolamine, monoisopropanolamine, butanolamine, isobutanolamine, N-methyl monoethanolamine, 2- (propylamino) ethanol or 2- (isopropylamino) ethanol.
6. The production method according to claim 3, characterized in that:
in step 2, the dehydrating agent/catalyst system is selected from dicyclohexylcarbodiimide/4-dimethylaminopyridine, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide/4-dimethylaminopyridine or (1-ethyl-3 (3-dimethylpropylamine) carbodiimide)/1-hydroxybenzotriazole; the molar ratio between the dehydrating agent and the catalyst was 3: 2.
7. The production method according to claim 3, characterized in that:
in step 2, the organic solvent is selected from acetone, butanone, cyclohexanone, tetrahydrofuran, acrylic acid, toluene, xylene or ethyl acetate.
8. The production method according to claim 3, characterized in that:
in the step 3, the glycidyl ester monomer containing the acryloyloxy group is selected from glycidyl acrylate or glycidyl methacrylate.
9. The production method according to claim 3, characterized in that:
in the step 1, the step 2 and the step 3, the volume ratio of the alcohol to the water in the mixed solvent of the alcohol and the water is 4: 1.
10. The production method according to claim 3 or 9, characterized in that:
the alcohol is selected from methanol, ethanol or propanol.
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| CN111087494B (en) * | 2019-12-31 | 2022-04-22 | 阜阳欣奕华材料科技有限公司 | Polymerizable photoinitiator and preparation method and application thereof |
| CN111072794B (en) * | 2019-12-31 | 2022-03-25 | 阜阳欣奕华材料科技有限公司 | Polymerizable photoinitiator and preparation method and application thereof |
| CN113292528B (en) * | 2021-06-10 | 2022-06-03 | 贵州师范学院 | Thioxanthone photoinitiator with high migration stability, preparation method and application |
| CN113583202A (en) * | 2021-08-05 | 2021-11-02 | 英德科迪颜料技术有限公司 | Thioxanthone polyurethane modified epoxy acrylate LED-UV water-based resin |
| CN114561005B (en) * | 2022-04-11 | 2023-01-17 | 中山大学 | Polymerizable thioxanthone aqueous photoinitiator and preparation method and application thereof |
| CN114805296B (en) * | 2022-05-10 | 2024-07-19 | 艾坚蒙(安庆)科技发展有限公司 | Thioxanthone derivative, preparation method and application thereof |
| CN116589618B (en) * | 2023-05-22 | 2024-01-26 | 江苏集萃光敏电子材料研究所有限公司 | Single-component macromolecular photoinitiator and preparation method thereof |
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