CN114561005B - Polymerizable thioxanthone aqueous photoinitiator and preparation method and application thereof - Google Patents
Polymerizable thioxanthone aqueous photoinitiator and preparation method and application thereof Download PDFInfo
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- CN114561005B CN114561005B CN202210375363.8A CN202210375363A CN114561005B CN 114561005 B CN114561005 B CN 114561005B CN 202210375363 A CN202210375363 A CN 202210375363A CN 114561005 B CN114561005 B CN 114561005B
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- thioxanthone
- structural unit
- photoinitiator
- aqueous
- polyaminoamine
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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 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 26
- 150000001412 amines Chemical class 0.000 claims abstract description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 15
- 238000006845 Michael addition reaction Methods 0.000 claims description 14
- 125000002947 alkylene group Chemical group 0.000 claims description 14
- 239000000853 adhesive Substances 0.000 claims description 13
- 230000001070 adhesive effect Effects 0.000 claims description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- 125000004386 diacrylate group Chemical group 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 229920000768 polyamine Polymers 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 claims description 4
- LUHPUPVJIVTJOE-UHFFFAOYSA-N 1-phosphonoethenylphosphonic acid Chemical compound OP(O)(=O)C(=C)P(O)(O)=O LUHPUPVJIVTJOE-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000001723 curing Methods 0.000 abstract description 25
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 239000003513 alkali Substances 0.000 abstract description 8
- 238000000016 photochemical curing Methods 0.000 abstract description 7
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 125000005395 methacrylic acid group Chemical group 0.000 abstract description 5
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 abstract description 5
- 239000004952 Polyamide Substances 0.000 abstract description 4
- 238000005580 one pot reaction Methods 0.000 abstract description 4
- 229920002647 polyamide Polymers 0.000 abstract description 4
- 239000012434 nucleophilic reagent Substances 0.000 abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 59
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 24
- 239000003999 initiator Substances 0.000 description 22
- 239000005700 Putrescine Substances 0.000 description 12
- IPUAADANTWKVJD-UHFFFAOYSA-N 2-[1-di(propan-2-yloxy)phosphorylethenyl-propan-2-yloxyphosphoryl]oxypropane Chemical compound CC(C)OP(=O)(OC(C)C)C(=C)P(=O)(OC(C)C)OC(C)C IPUAADANTWKVJD-UHFFFAOYSA-N 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 7
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920000671 polyethylene glycol diacrylate Polymers 0.000 description 5
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- -1 ethenylene bisphosphonate Chemical class 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- ANHLDZMOXDYFMQ-UHFFFAOYSA-N 2-hydroxythioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(O)=CC=C3SC2=C1 ANHLDZMOXDYFMQ-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- MLLATHOAJYDJLT-UHFFFAOYSA-N C=C1OP(=O)OP(=O)O1 Chemical compound C=C1OP(=O)OP(=O)O1 MLLATHOAJYDJLT-UHFFFAOYSA-N 0.000 description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- RNHDAKUGFHSZEV-UHFFFAOYSA-N 1,4-dioxane;hydrate Chemical compound O.C1COCCO1 RNHDAKUGFHSZEV-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- UJHYZJSRAHZNFM-UHFFFAOYSA-N O=P1OCCOP(=O)O1 Chemical compound O=P1OCCOP(=O)O1 UJHYZJSRAHZNFM-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012038 nucleophile Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000003335 secondary amines Chemical group 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- FODCFYIWOJIZQL-UHFFFAOYSA-N 1-methylsulfanyl-3,5-bis(trifluoromethyl)benzene Chemical compound CSC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 FODCFYIWOJIZQL-UHFFFAOYSA-N 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical group S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229940122361 Bisphosphonate Drugs 0.000 description 1
- VDGFDTXXOJHDPC-UHFFFAOYSA-N C=C(OP(O)=O)OP(O)=O Chemical compound C=C(OP(O)=O)OP(O)=O VDGFDTXXOJHDPC-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- AAVREKMBILLYIS-UHFFFAOYSA-N P(O)(O)=O.P(O)(O)=O.C=C.C=C.C=C.C=C Chemical compound P(O)(O)=O.P(O)(O)=O.C=C.C=C.C=C.C=C AAVREKMBILLYIS-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013036 cure process Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012781 shape memory material Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The invention belongs to the technical field of high molecular materials, and particularly relates to a polymerizable aqueous thioxanthone photoinitiator, and a preparation method and application thereof. The thioxanthone water-based photoinitiator takes linear polyamino amine as a macromolecular main chain, the macromolecular main chain simultaneously contains linear polyamide, phosphate groups, thioxanthone and amine structures, the curing sites are more, and the curing degree is more efficient. Moreover, the thioxanthone aqueous photoinitiator can participate in two stages of a one-pot dual-curing process in an acrylic/methacrylic UV (ultraviolet) photo-curing system, not only can be used as a nucleophilic reagent and alkali in the first-stage reaction, but also can induce free radical polymerization in the second-stage reaction.
Description
Technical Field
The invention relates to the technical field of high polymer materials, and particularly relates to a polymerizable thioxanthone aqueous photoinitiator, and a preparation method and application thereof.
Background
The Photoinitiator (PI) plays an important role in photopolymerization. With conventional small molecule PI, photolytic fragments or residual PI easily migrate to the surface of the final product, causing odor or toxicity problems, which limit their application in food packaging and biomedical materials. Polymeric photoinitiators are of interest because of some of the advantages associated with their macromolecular nature, and in particular polymeric photoinitiators reduce migration of the film surface, thereby reducing the tendency to yellow and reducing odor and toxicity problems. These advantages stem from the fact that: the production/release of easily migrating molecules is minimized. There is also an increasing demand for water-soluble photoinitiating systems since water is a green solvent, has no emission of Volatile Organic Compounds (VOCs), and has no odor or toxicity problems.
Acrylic/methacrylic based UV photo-curing systems are common photo-curing systems. The polymerization of acrylate monomers involves two stages, in the first stage, the acrylic/methacrylic monomers and nucleophiles undergo Michael addition under alkaline conditions, and in the second stage, the photoinitiator is used to induce radical polymerization. However, the existing aqueous photoinitiator generally only plays a role in photoinduced free radical polymerization in the process of initiating the polymerization of acrylate monomers, so that an amine substance is required to be specially added as a nucleophilic reagent and alkali in the first stage, and PI is added in the second stage, so that the raw material cost is high, and the curing efficiency is low.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a polymerizable thioxanthone aqueous photoinitiator, which can participate in two stages of a one-pot dual-curing process in an acrylic group/methacrylic group UV (ultraviolet) photo-curing system, has more efficient curing degree and saves the adding procedures of amine and PI (polyimide); meanwhile, the thioxanthone aqueous photoinitiator has small surface mobility in an acrylate polymerization system, so that the problems of peculiar smell and toxicity of the polymer are reduced.
Meanwhile, the invention also provides a preparation method and application of the thioxanthone aqueous photoinitiator.
Specifically, the invention adopts the following technical scheme:
the first aspect of the invention provides a thioxanthone aqueous photoinitiator, which comprises a polyaminoamine structural unit, a thioxanthone structural unit and a phosphoric acid structural unit, wherein the polyaminoamine structural unit is
The structural unit of thioxanthone is
The phosphoric acid structural unit is
Wherein R is selected from C1-C6 alkylene and-R a -NH-R b -，R a 、R b Independently selected from C1 to C6 alkylene or absent; r' is selected from-NH-R a1 -NH-、-O-R a1 -O-，R a1 Selected from C1-C6 alkylene; r' is selected from C1-C6 alkyl; n is more than or equal to 1 and less than 3;
the thioxanthone structural unit and the phosphoric acid structural unit are randomly connected with N in the polyaminoamine structural unit, and the thioxanthone structural unit and the phosphoric acid structural unit are not connected with the same N at the same time.
Compared with the conventional common micromolecular photoinitiator, the thioxanthone water-based photoinitiator takes linear polyamino amine as a macromolecular main chain, the macromolecular main chain simultaneously contains linear polyamide, phosphate groups, thioxanthone and amine structures, so that the thioxanthone water-based photoinitiator has more curing sites and more efficient curing degree, can overcome oxygen inhibition and has no induction period. The maximum absorption peak of the thioxanthone structure appears in the range of 380-420 nm, and the thioxanthone water-based photoinitiator has a wider ultraviolet absorption wavelength range, so that the thioxanthone water-based photoinitiator has higher photoinitiation efficiency.
Moreover, the thioxanthone aqueous photoinitiator can participate in two stages of a one-pot dual-curing process in an acrylic group/methacrylic group UV (ultraviolet) photocuring system, not only can be used as a nucleophilic reagent and alkali in the first stage reaction, but also can induce free radical polymerization in the second stage reaction, so that the adding procedures of amine and PI are saved.
In some embodiments of the invention, R is selected from C4-C6 alkylene, -R a -NH-R b -，R a 、R b Independently selected from C2 to C4 alkylene; r' is selected from-NH-R a1 -NH-、-O-R a1 -O-，R a1 Selected from C2 to C6 alkylene; r' is selected from C2-C4 alkyl.
In some embodiments of the invention, R is selected from C4 alkylene; r' is selected from-NH-R a1 -NH-，R a1 Selected from C2 alkylene; r' is selected from C2 alkyl.
In some embodiments of the invention, R is selected from C4 alkylene; r' is selected from-O-R a1 -O-，R a1 Selected from C6 alkylene; r' is selected from C2 alkyl.
In some embodiments of the invention, R is selected from-R a -NH-R b -，R a 、R b Independently is C2 alkylene; r' is selected from-O-R a1 -O-，R a1 Selected from C6 alkylene; r' is selected from C2 alkyl.
In some embodiments of the invention, the molar ratio of polyaminoamine structural units to thioxanthone structural units is 1: (0.2 to 1), preferably 1: (0.3 to 0.8), more preferably 1:0.5.
in some embodiments of the invention, the molar ratio of polyaminoamine structural units to phosphoric acid structural units is 1: (2.5 to 4), preferably 1: (3 to 3.5), more preferably 1:3.
the second aspect of the present invention provides a preparation method of the above thioxanthone aqueous photoinitiator, comprising the following steps:
reacting diacrylate or bisacrylamide with polyamine to obtain polyaminoamine;
subjecting the polyaminoamine to a Michael addition reaction with an acrylate-functionalized thioxanthone to obtain an intermediate I;
and (3) reacting the intermediate I with vinylidene diphosphonic acid tetraalkyl ester to obtain the thioxanthone aqueous photoinitiator.
One synthetic route in the preparation process is as follows:
it should be noted that the above synthetic route is only one of several possibilities, and that the acrylate-functionalized thioxanthone and the vinylidene-diphosphonate tetraalkyl ester can be randomly attached to any N of the polyaminoamine (both not simultaneously attached to the same N).
In some embodiments of the invention, the mole ratio of the bisacrylate or bisacrylamide to polyamine is 1: (1.1-1.3).
In some examples of the invention, the bisacrylamide comprises N, N' -methylenebisacrylamide and the bisacrylate comprises 1,6-hexanediol diacrylate.
In some examples of the invention, the polyamine comprises at least one of 1,4-diaminobutane, diethylenetriamine, hyperbranched amines. In which the hyperbranched amines are highly branched organic amines, e.g.
In some embodiments of the invention, the reaction of the bisacrylate or bisacrylamide with the polyamine is specifically: the diacrylate or bisacrylamide and the polyamine are dissolved in the organic solvent and reacted with stirring. After the reaction is finished, the polyaminoamine is obtained through purification, filtration, drying and separation. Wherein the organic solvent comprises at least one of methanol, ethanol and n-butanol; the reaction temperature is 20-60 ℃, preferably 20-50 ℃, and more preferably 35-45 ℃; the reaction time is 10 to 20 hours, preferably 12 to 15 hours.
In some embodiments of the invention, the acrylate-functionalized thioxanthone has the formula
The acrylate functionalized thioxanthone is obtained by reacting 2-hydroxy thioxanthone with acryloyl chloride. The preparation method specifically comprises the following steps: dissolving 2-hydroxy thioxanthone in an alkali solution, and then adding acryloyl chloride for reaction to obtain the acrylate functionalized thioxanthone.
The synthetic route for acrylate-functionalized thioxanthones is:
wherein the temperature at which the acrylate-functionalized thioxanthone is prepared is less than 0 ℃. The alkali solution is obtained by dissolving alkali in a solvent, wherein the alkali comprises at least one of sodium hydroxide, potassium hydroxide, ammonia water and triethylamine, and the solvent comprises at least one of water and 1,4-dioxane. Preferably, the alkali solution is a solution of sodium hydroxide or potassium hydroxide in water-1,4-dioxane. After dissolving 2-hydroxythioxanthone in an alkaline solution, a deep red color is produced due to the formation of phenoxide of thioxanthone. Acryloyl chloride is then added and the red colour disappears after the reaction is complete. After the reaction was complete, a yellow residue was filtered, washed with water, and then recrystallized from a 1,4-dioxane/water mixture to give an acrylate-functionalized thioxanthone.
In some embodiments of the invention, the polyaminoamine and the acrylate-functionalized thioxanthone are present in a molar ratio of 1: (0.2 to 1), preferably 1: (0.3 to 0.8), more preferably 1:0.5.
in some embodiments of the invention, the Michael addition reaction temperature of the polyaminoamine with an acrylate-functionalized thioxanthone is from 50 to 80 deg.C, preferably from 65 to 75 deg.C; the reaction time is 30 to 60 hours, preferably 45 to 50 hours. The acrylate-functionalized thioxanthone is polymerized onto the secondary amine group of the polyaminoamine by a michael addition reaction.
In some embodiments of the invention, the Michael addition reaction of the polyaminoamine with an acrylate-functionalized thioxanthone is carried out in a protective atmosphere, for example, a nitrogen, argon atmosphere.
In some embodiments of the invention, the solvent employed in the Michael addition reaction system of the polyaminoamine and the acrylate-functionalized thioxanthone comprises at least one of methanol, ethanol, and n-butanol.
In some embodiments of the invention, after the reaction of the polyaminoamine with the acrylate-functionalized thioxanthone is complete, the resulting mixed solution is added to diethyl ether and isolated to provide intermediate I.
In some embodiments of the invention, the molar ratio of intermediate I to vinylidene diphosphonate tetraalkyl ester is 1: (2.5 to 4), preferably 1: (3 to 3.5), more preferably 1:3.
in some embodiments of the present invention, the alkyl group of the vinylidene diphosphonic acid tetraalkyl ester is selected from C1-C6 alkyl groups. Preferably, the tetraethylene bisphosphonate includes tetraethyl ethenylene bisphosphonate.
In some embodiments of the invention, the temperature at which intermediate I is reacted with the tetraethylene diphosphonate tetraalkyl ester is from 10 to 50 ℃, preferably from 20 to 30 ℃; the reaction temperature is 30 to 60 hours, preferably 45 to 50 hours. In this reaction, tetraethyl vinylidene bisphosphonate is polymerized onto the secondary amine group of intermediate I (or onto the terminal if the terminal of intermediate I is a primary amine).
In some embodiments of the invention, after the reaction of intermediate I with the tetraalkyl vinylidene diphosphonate is complete, the solvent is removed and the product is washed with a diethyl ether/petroleum ether mixture to remove excess tetraalkyl vinylidene diphosphonate. Wherein in the diethyl ether/petroleum ether mixture, the volume ratio of diethyl ether/petroleum ether is (0.5-1.5)/1, preferably 1/1.
The third aspect of the invention provides the application of the thioxanthone aqueous photoinitiator in initiating the polymerization of acrylic and/or acrylate monomers.
The fourth aspect of the invention provides a light-cured adhesive, wherein the raw materials of the light-cured adhesive comprise acrylic acid and/or acrylate monomers and the thioxanthone water-based photoinitiator.
In some examples of the present invention, the acrylate monomer includes at least one of polyethylene glycol diacrylate (PEGDA), 2-hydroxyethyl methacrylate (HEMA), methyl acrylate, ethyl acrylate, 2-methyl methacrylate, and 2-ethyl methacrylate.
In some embodiments of the present invention, the initiator is present in the photocurable glue stock in an amount of 0.1% to 2%, preferably 0.5% to 1.5% by weight.
In some embodiments of the present invention, the raw materials of the photocurable glue include 2-hydroxyethyl methacrylate (HEMA), polyethylene glycol diacrylate (PEGDA) and the above-mentioned aqueous thioxanthone photoinitiator.
In some examples of the present invention, the raw materials of the light-curable adhesive include, by mass:
50-75 parts of methacrylic acid-2-Hydroxyethyl Ester (HEMA)
25 to 50 portions of polyethylene glycol diacrylate (PEGDA)
0.5-1.5 parts of thioxanthone aqueous photoinitiator.
In some examples of the present invention, the raw material of the photocurable glue further comprises additives, which may include neutralizing agents (e.g., triethanolamine), other types of photoinitiators (e.g., bis- (4-tert-butylphenyl) -iodonium hexafluorophosphate, etc.). The mass percentage of the additive in the light-cured adhesive raw material is 0.1-5%, preferably 0.5-3%, and more preferably 1-3%.
The fifth aspect of the present invention provides a method for using a photo-curing adhesive, comprising the following steps: mixing acrylic acid and/or acrylic ester monomers and a thioxanthone aqueous photoinitiator, carrying out Michael addition reaction, and then carrying out light curing.
In some embodiments of the invention, the temperature of the Michael addition reaction is from 10 to 40 ℃, preferably from 20 to 30 ℃; the Michael addition reaction time is 5 to 20min, preferably 5 to 15min, and more preferably 10min.
In some embodiments of the present invention, the light in the light curing process is ultraviolet light, and the light curing time is 2 to 10min, preferably 5min.
Compared with the prior art, the invention has the following beneficial effects:
the initiator takes linear polyamino amine as a macromolecular main chain, the macromolecular main chain simultaneously contains linear polyamide, phosphate groups, thioxanthone and amine structures, the curing sites are more, the curing degree is more efficient, meanwhile, the oxygen inhibition can be overcome, and no induction period exists. And the maximum absorption peak of the thioxanthone structure appears in the range of 380-420 nm, and has a wider ultraviolet absorption wavelength range, so that the initiator has higher photoinitiation efficiency.
The initiator of the invention can effectively initiate the polymerization reaction of the UV photocuring system of acrylic acid group/acrylic ester. In the acrylic group/acrylate UV light curing system, the initiator can generate efficient dual-curing reaction for the UV light curing system. Specifically, the initiator not only can initiate photopolymerization, but also can participate in two stages of a one-pot dual-curing process: in a first stage, an initiator reacts with an acrylate as a nucleophile and base for the michael addition reaction in the presence of an acrylate (formed from the acrylate); in the second stage, the initiator acts as a photoinitiator for the radical polymerization, photoinduced for the radical polymerization. Thus, unlike other dual cure processes today, the process does not require the addition of an amine in the first stage and does not require the addition of additional PI in the second stage. The dual curing process of two sequential curing reactions can result in the formation of an interpenetrating polymer network, and the initiator can participate in the resulting interpenetrating polymer network, which will reduce the migration of the initiator on the surface.
Meanwhile, the phosphate group in the initiator provides a contribution to the water solubility of the initiator on the one hand, and can be combined with calcium ions on the other hand, so that the initiator can be possibly used in the aspect of biomedicine.
By using the inherent flexibility of the two polymerization stages, the method brings many advantages in terms of product performance, and therefore tailored materials can be designed for many different application areas, such as shape memory materials, holographic materials, protective coatings, photolithography, optical materials.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples. The starting materials used in the following examples, unless otherwise specified, are available from conventional commercial sources; the adopted process adopts the conventional process in the field if no special specification exists; unless otherwise specified, room temperature means 25. + -. 5 ℃.
Example 1
A preparation method of a thioxanthone aqueous photoinitiator comprises the following steps:
(1) The molar ratio of N, N '-methylenebisacrylamide (2.6 mmol) and 1,4-diaminobutane (2.9 mmol), N, N' -methylenebisacrylamide and 1,4-diaminobutane was 1:1.1, dissolved in methanol (1.5 mL) and stirred at 40 ℃ for 12 h. The pure polymer was then isolated by precipitation into diethyl ether and dried by filtration under vacuum to give the polyaminoamine.
(2) Polyaminoamine (0.1g, 0.02mmol) and acrylate-functionalized Thioxanthone (TXA) (0.028g, 0.01mmol) were dissolved in methanol (2.5 mL) and stirred under nitrogen at 70 ℃ for 48 hours. When the reacted solution was added to 10mL of diethyl ether, the pure polymer was isolated as an orange solid in 50% yield.
(3) The product of step (2) (0.015g, 0.055mmol) and tetraethyl vinylidene diphosphonate (0.05g, 0.166mmol) were stirred in chloroform (0.5 mL) at room temperature for 48h. After removal of the solvent, the product was washed with a diethyl ether/petroleum ether (1/1,v/v) mixture to remove excess tetraethyl vinylidene diphosphonate to give the aqueous thioxanthone photoinitiator.
One reaction mechanism in the preparation process is as follows:
it should be noted that the above reaction mechanism is only one of several possibilities, and that the acrylate functionalized thioxanthone and tetraethyl vinylidene diphosphonate are not necessarily attached to the N at the a and b positions, respectively. The acrylate functionalized thioxanthone and the ethylene diphosphonate tetraethyl ester can be respectively and independently connected to any one of N at a-d positions, and the acrylate functionalized thioxanthone and the ethylene diphosphonate tetraethyl ester are not connected with the same N at the same time.
Example 2
A preparation method of thioxanthone aqueous photoinitiator is different from that of example 1 in that: the molar amount of 1,4-diaminobutane was increased to 3.4mmol so that the molar ratio of N, N' -methylenebisacrylamide to 1,4-diaminobutane became 1:1.3.
the method specifically comprises the following steps:
(1) N, N' -methylenebisacrylamide (2.6 mmol) and 1,4-diaminobutane (3.4 mmol) were dissolved in methanol (1.5 mL) and stirred at 40 ℃ for 12 hours. The pure polymer was then isolated by precipitation into ether and dried by filtration under vacuum to give the polyaminoamine.
(2) Polyaminoamine (0.1g, 0.02mmol) and acrylate-functionalized Thioxanthone (TXA) (0.028g, 0.01mmol) were dissolved in methanol (2.5 mL) and stirred under nitrogen at 70 ℃ for 48 hours. When this solution was added to an excess of diethyl ether, the pure polymer was isolated as an orange solid in 50% yield.
(3) The product of step (2) (0.015g, 0.055mmol) and tetraethyl vinylidene diphosphonate (0.05g, 0.166mmol) were stirred in chloroform (0.5 mL) at room temperature for 48h. After removal of the solvent, the product was washed with a diethyl ether/petroleum ether (1/1 v/v) mixture to remove excess tetraethyl vinylidene diphosphonate and to give the aqueous thioxanthone photoinitiator.
Example 3
A preparation method of thioxanthone aqueous photoinitiator is different from that of example 1 in that: the N, N' -methylenebisacrylamide was replaced with an equimolar amount of 1,6-hexanediol diacrylate.
The method specifically comprises the following steps:
(1) 1,6-hexanediol diacrylate (2.6 mmol) and 1,4-diaminobutane (2.9 mmol) were dissolved in methanol (1.5 mL) and stirred at 40 ℃ for 12 h. The pure polymer was then isolated by precipitation into ether and dried by filtration under vacuum to give the polyaminoamine.
(2) Polyaminoamine (0.1g, 0.02mmol) and acrylate-functionalized Thioxanthone (TXA) (0.028g, 0.01mmol) were dissolved in methanol (2.5 mL) and stirred under nitrogen at 70 ℃ for 48 hours. When this solution was added to an excess of diethyl ether, the pure polymer was isolated as an orange solid in 50% yield.
(3) The product of step (2) (0.015g, 0.055mmol) and tetraethyl vinylidene diphosphonate (0.05g, 0.166mmol) were stirred in chloroform (0.5 mL) at room temperature for 48h. After removal of the solvent, the product was washed with a diethyl ether/petroleum ether (1/1 v/v) mixture to remove excess tetraethyl vinylidene diphosphonate and to give the aqueous thioxanthone photoinitiator.
According to the reaction raw materials and the reaction mechanism, one structure of the obtained thioxanthone aqueous photoinitiator can be judged to be as follows:
in the aqueous thioxanthone photoinitiator, acrylate functionalized thioxanthone can also be attached to the N at the b-position, while tetraethyl vinylidene diphosphonate is attached to the N at the a-position.
Example 4
A method for preparing a thioxanthone aqueous photoinitiator is different from that in example 3 in that: 1,4-diaminobutane was replaced with an equimolar amount of diethylenetriamine.
The method specifically comprises the following steps:
(1) 1,6-hexanediol diacrylate (2.6 mmol) and diethylenetriamine (2.9 mmol) were dissolved in methanol (1.5 mL) and stirred at 40 ℃ for 12 hours. The pure polymer was then isolated by precipitation into ether and dried by filtration under vacuum to give the polyaminoamine.
(2) Linear polyaminoamine (0.1g, 0.02mmol) and acrylate-functionalized Thioxanthone (TXA) (0.028g, 0.01mmol) were dissolved in methanol (2.5 mL) and stirred under nitrogen at 70 ℃ for 48 hours. When this solution was added to an excess of diethyl ether, the pure polymer was isolated as an orange solid in 50% yield.
(3) The product of step (2) (0.015g, 0.055mmol) and tetraethyl vinylidene diphosphonate (0.05g, 0.166mmol) were stirred in chloroform (0.5 mL) at room temperature for 48h. After removal of the solvent, the product was washed with a diethyl ether/petroleum ether (1/1 v/v) mixture to remove excess tetraethyl vinylidene diphosphonate and to give the aqueous thioxanthone photoinitiator.
According to the reaction raw materials and the reaction mechanism, one structure of the obtained thioxanthone aqueous photoinitiator can be judged as follows:
in the aqueous thioxanthone photoinitiator, acrylate functionalized thioxanthone can also be attached to N at the b or c position, while tetraethyl vinylidene diphosphonate can be attached to N at the a or b position.
Comparative example 1
The only difference between this comparative example and example 1 is that: the molar amount of 1,4-diaminobutane was 2.6mmol. The molar ratio of N, N' -methylenebisacrylamide and 1,4-diaminobutane becomes 1:1.
comparative example 2
The only difference between this comparative example and example 3 is that: 1,4-diaminobutane molar mass was 3.8mmol. The molar ratio of N, N' -methylenebisacrylamide and 1,4-diaminobutane became 1:1.46.
the initiator obtained in examples 1 to 4 and comparative examples 1 and 2, the commercial thioxanthone initiator, HEMA, PEGDA and additives were formulated into a photocurable adhesive according to the formulation shown in Table 1 below.
TABLE 1 light curing glue formulation (parts by mass)
Wherein the commercial thioxanthone initiator is isopropyl thioxanthone and the additive is triethanolamine.
The preparation method of the light-cured adhesive comprises the following steps: the initiator and additives were first mixed with HEMA, the desired amount of PEGDA was added with rapid stirring to perform the michael addition reaction (10 minutes), followed by uv irradiation at 30 ℃ for 5 minutes.
The performance test of the light curing adhesive prepared by different initiators is carried out, and the test method comprises the following steps:
odor: the lower the odor, the less migration is indicated, as evaluated by the direct fan-smelling method.
Mobility: and (3) soaking the sample to be tested in acetonitrile for 24h in a 40 ℃ oven, preparing the same concentration, and testing the molar absorption coefficient of the sample under the corresponding photoinitiator by using an ultraviolet-visible spectrometer. Migration representation method: 5 is optimal (not easily migrated) and 1 is worst (easily migrated).
Degree of curing: the degree of curing of the light-cured glue was detected by means of fourier infrared, photo-DSC (differential scanning calorimetry).
Degree of yellowing: and (4) visual inspection.
The results of the performance test of the photocurable adhesive are shown in table 2.
TABLE 2 testing results of the properties of the photocurable adhesive
As can be seen from Table 2, the initiators of examples 1-4 are more difficult to migrate due to the presence of their macromolecular chains, making them significantly less odorous and more environmentally friendly than the current commercial thioxanthone initiators; and a higher degree of cure under the same curing conditions. The reason for this analysis is: in the embodiments 1-4, the macromolecular chain of the initiator contains linear polyamide, phosphate group, thioxanthone and amine structure, so that the curing sites are more, the curing degree is more efficient, and no induction period (overcoming oxygen inhibition) exists.
The results of the performance tests also show that the molar ratio of diacrylate to polyamine in comparative examples 1, 2 is either too high or too low, which, although not affecting the initiator mobility, significantly reduces the degree of cure.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.
Claims (10)
1. A thioxanthone aqueous photoinitiator is characterized in that: the aqueous thioxanthone photoinitiator contains a polyaminoamine structural unit, a thioxanthone structural unit and a phosphoric acid structural unit, wherein the polyaminoamine structural unit is
The thioxanthone structural unit is
The phosphoric acid structural unit is
Wherein R is selected from C1-C6 alkylene and-R a -NH-R b -，R a 、R b Independently selected from C1 to C6 alkylene; r' is selected from-NH-R a1 -NH-、-O-R a1 -O-，R a1 Selected from C1-C6 alkylene; r' is selected from C1-C6 alkyl; n is more than or equal to 1 and less than 3;
the thioxanthone structural unit and the phosphoric acid structural unit are randomly connected with N in the polyaminoamine structural unit, and the thioxanthone structural unit and the phosphoric acid structural unit are not connected with the same N at the same time.
2. The aqueous thioxanthone photoinitiator according to claim 1, characterised in that: r is selected from C4-C6 alkylene and-R a -NH-R b -，R a 、R b Independently selected from C2 to C4 alkylene; r' is selected from-NH-R a1 -NH-、-O-R a1 -O-，R a1 Selected from C2 to C6 alkylene; r' is selected from C2-C4 alkyl.
3. The aqueous thioxanthone photoinitiator according to claim 1 or 2, characterized in that: the molar ratio of the polyaminoamine structural unit to the thioxanthone structural unit is 1: (0.2-1).
4. The aqueous thioxanthone photoinitiator according to claim 3, characterised in that: the molar ratio of the polyaminoamine structural unit to the phosphoric acid structural unit is 1: (2.5-4).
5. A process for the preparation of the aqueous thioxanthone photoinitiator according to any one of claims 1 to 4, characterised in that: the method comprises the following steps:
reacting diacrylate or bisacrylamide with polyamine to obtain polyaminoamine;
carrying out Michael addition reaction on the polyamino amine and acrylate functionalized thioxanthone to obtain an intermediate I;
and (3) reacting the intermediate I with vinylidene diphosphonic acid tetraalkyl ester to obtain the thioxanthone aqueous photoinitiator.
6. The method according to claim 5, wherein: the molar ratio of the diacrylate or bisacrylamide to the polyamine is 1: (1.1-1.3).
7. The method according to claim 5, wherein: the Michael addition reaction temperature of the polyamino amine and the acrylate functionalized thioxanthone is 50-80 ℃.
8. Use of the thioxanthone aqueous photoinitiator according to any one of claims 1 to 4 for initiating the polymerisation of acrylic and/or acrylic monomers.
9. A light-cured adhesive is characterized in that: the raw materials of the light-cured adhesive comprise acrylic acid and/or acrylate monomers and the thioxanthone water-based photoinitiator according to any one of claims 1 to 4.
10. The method of using the light-curable adhesive of claim 9, wherein: the method comprises the following steps: mixing acrylic acid and/or acrylate monomers and a thioxanthone aqueous photoinitiator, carrying out Michael addition reaction, and then carrying out light curing.
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