CN113651904B - Photopolymerizable single-component thioxanthone photoinitiator - Google Patents
Photopolymerizable single-component thioxanthone photoinitiator Download PDFInfo
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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 35
- 238000000016 photochemical curing Methods 0.000 claims abstract description 20
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 16
- OEZKDMYTQDZSAZ-UHFFFAOYSA-N 1-hydroxythioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2O OEZKDMYTQDZSAZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 claims abstract description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 9
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 239000011737 fluorine Substances 0.000 claims abstract description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 89
- 238000003756 stirring Methods 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 36
- 239000013067 intermediate product Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000000047 product Substances 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 239000011248 coating agent Substances 0.000 claims description 24
- 238000000576 coating method Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 21
- 239000012074 organic phase Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- 238000010025 steaming Methods 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000004925 Acrylic resin Substances 0.000 claims description 8
- 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 claims description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- IHYAGCYJVNHXCT-UHFFFAOYSA-N 3,3,4,4,5,5-hexafluorooxane-2,6-dione Chemical compound FC1(F)C(=O)OC(=O)C(F)(F)C1(F)F IHYAGCYJVNHXCT-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- ZLVLNNCBGQYRAB-UHFFFAOYSA-N 3,3,4,4-tetrafluorooxolane-2,5-dione Chemical group FC1(F)C(=O)OC(=O)C1(F)F ZLVLNNCBGQYRAB-UHFFFAOYSA-N 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052625 palygorskite Inorganic materials 0.000 claims description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 4
- 239000011973 solid acid Substances 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004383 yellowing Methods 0.000 abstract description 15
- 230000000977 initiatory effect Effects 0.000 abstract description 13
- 238000013508 migration Methods 0.000 abstract description 11
- 230000005012 migration Effects 0.000 abstract description 11
- 239000003999 initiator Substances 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 238000010146 3D printing Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000004593 Epoxy Substances 0.000 abstract description 2
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 230000032050 esterification Effects 0.000 abstract description 2
- 238000005886 esterification reaction Methods 0.000 abstract description 2
- 238000003541 multi-stage reaction Methods 0.000 abstract description 2
- 238000007142 ring opening reaction Methods 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 125000006414 CCl Chemical group ClC* 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000005286 illumination Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- -1 acrylic ester Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 239000000852 hydrogen donor Substances 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
- 150000003254 radicals Chemical class 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- SJMYMKPBODEZSH-DEDYPNTBSA-N (2e)-2-[(2,5-dimethyl-1-phenylpyrrol-3-yl)methylidene]-[1,3]thiazolo[3,2-a]benzimidazol-1-one Chemical compound CC1=CC(\C=C\2C(N3C4=CC=CC=C4N=C3S/2)=O)=C(C)N1C1=CC=CC=C1 SJMYMKPBODEZSH-DEDYPNTBSA-N 0.000 description 2
- 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 2
- 101001053401 Arabidopsis thaliana Acid beta-fructofuranosidase 3, vacuolar Proteins 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000005323 thioketone group Chemical group 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ZZIZZTHXZRDOFM-XFULWGLBSA-N tamsulosin hydrochloride Chemical compound [H+].[Cl-].CCOC1=CC=CC=C1OCCN[C@H](C)CC1=CC=C(OC)C(S(N)(=O)=O)=C1 ZZIZZTHXZRDOFM-XFULWGLBSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 238000011179 visual inspection 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
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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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)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention belongs to the field of photo-curing materials. The invention relates to a photo-polymerizable single-component thioxanthone photoinitiator, which is prepared from hydroxy thioxanthone, bromoethanol, fluorine-containing anhydride, 4-hydroxymethyl-1, 3-dioxy-2-thioketone, epichlorohydrin and acryloyl chloride by coupling, esterification, epoxy ring opening, epoxidation and other multi-step reactions. The novel photoinitiator not only effectively solves the problems of yellowing and the like caused by low initiation efficiency of the bi-component photoinitiator and the need of adding the auxiliary initiator in the prior art, but also has the advantages of difficult migration, wide application, environmental protection and the like, and the novel material is particularly suitable for the fields of 3C products, 3D printing and the like.
Description
Technical Field
The invention relates to a photopolymerizable single-component thioxanthone photoinitiator. The invention belongs to the field of photo-curing materials.
Background
Photocuring (photopolymerization) refers to a process in which a photoinitiator is stimulated to be finally converted into active species such as free radicals with photoinitiating activity under illumination, so that crosslinking polymerization of the active species is initiated. The photocuring paint is developed for the first time from German Bayer company, and the photocuring technology realizes industrialization and is rapidly developed and applied. Compared with thermal curing, the photo-curing technology has the following characteristics: the method has the advantages of no solvent, high curing speed, energy conservation, environmental protection, good product performance, suitability for high-speed automatic production lines, and wide application in the fields of coating, paint, printing ink, electronic communication, adhesives, dental curing, 3D printing and the like.
The photo-curing material mainly comprises functionalized oligomer, monomer, photoinitiator and the like. Photoinitiators are important components of the photocurable system and, although they are present in small proportions, they play a decisive role in the speed of photocuring. The photoinitiator absorbs light energy to generate active species with polymerization initiating capability, thereby initiating the crosslinking polymerization of the active species. The actual types of photoinitiators in the present stage are more and mainly divided into free radicals and cationic. The free radical type has strong application universality and can be mainly divided into a hydrogen abstraction type and a cracking type. Wherein, the cracking photoinitiator has the problem of oxygen polymerization inhibition in the use process; hydrogen abstraction type photoinitiators are required to be used in combination with co-initiators, tertiary amines being the most commonly used co-initiators.
The existing hydrogen abstraction type photoinitiator belongs to a small molecular photoinitiator, and has the defects of high viscosity, easy yellowing, easy migration, easy volatilization, low initiation efficiency, odor and the like. In order to solve the problems, CN105693888B discloses a polymerizable thioxanthone visible light initiator containing acrylic ester or methacrylic ester and a preparation method thereof, which have good compatibility with a photocuring system, do not need to add any solvent or auxiliary agent in the use process, have the advantages of high initiation efficiency, green and environment-friendly performance, low energy consumption and the like, but the problem of yellowing is not solved by using tertiary amine as a hydrogen donor. The preparation method comprises the steps of preparing 2-hydroxy thioxanthone from 2, 2-dithiodibenzoic acid and phenol serving as raw materials by using 9-13 of Shortui and the like (coating industry, 2020,50 (1)), then reacting the 2- (2, 3-glycidoxy) -thioxanthone with epichlorohydrin, and then reacting the 2- (3-diallyl amino-2-hydroxy propoxy) -thioxanthone with DAA monomer to obtain 2- (3-diallyl amino-2-hydroxy propoxy) -thioxanthone (marked as DAHTX), wherein the ultraviolet absorption peak is red-shifted by 15-20nm, and the mobility of the 2-hydroxy thioxanthone is reduced from 17.6% to 6.2%. The problem of yellowing is likewise not solved.
In view of the above, the development of an environmentally friendly photoinitiator with low migration, high initiation, low or no yellowing is a current development hotspot.
Disclosure of Invention
The invention aims to solve the problems of low initiation efficiency of a bi-component photoinitiator, yellowing caused by adding an auxiliary initiator and the like in the prior art, and provides a photopolymerizable single-component thioxanthone type photoinitiator. The photo-polymerizable single-component thioxanthone photoinitiator material is prepared from the raw materials of hydroxythioxanthone, bromoethanol, fluorine-containing anhydride, 4-hydroxymethyl-1, 3-dioxy-2-thioketone, epichlorohydrin and acryloyl chloride through multi-step reactions such as coupling, esterification, epoxy ring opening, epoxidation and the like, has the advantages of high photo-initiation efficiency, no yellowing, difficult migration, wide application, environmental protection and the like, and is particularly suitable for the fields of 3C products, 3D printing and the like.
The technical scheme adopted for solving the technical problems is as follows:
a photopolymerizable single-component thioxanthone photoinitiator has the following structural formula:
wherein, -R-is-CF 2 -or-C 2 F 4 -。
A method for preparing a photopolymerizable single-component thioxanthone photoinitiator, comprising the following steps:
(1) Adding 1mol of hydroxythioxanthone, 1-1.2mol of bromoethanol and 1-1.2mol of potassium carbonate into 50mol of DMF, heating to 110-130 ℃ and stirring strongly for 1-3h, cooling, standing, and concentrating the solution in vacuum to enrich residual components; slowly adding 60mol of water, stirring for 30min, adding 50mol of DMSO, stirring for 30min, standing for layering, drying the organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain an intermediate product I;
(2) Adding 1mol of I, 1.1-1.4mol of fluorine-containing anhydride and 0.5-4wt% of catalyst into 50mol of DMSO, introducing nitrogen, heating to 80-110 ℃ and stirring for 3-15h, cooling, and standing for later use to obtain an intermediate product II;
the catalyst is used in an amount which is the percentage of the total mass of I and fluorine-containing anhydride;
(3) 1mol of 4-hydroxymethyl-1, 3-dioxo-2-thione is added to a solution containing 0.5-3wt% BF 3 Heating 1-1.2mol of ethyl ether in epichlorohydrin to 40-80 ℃ for 2-8h; standing, and distilling under reduced pressure at 40 ℃ to obtain an intermediate product III;
the BF 3 The consumption of the diethyl ether is 0.5-3wt% of the mass of the epichlorohydrin;
(4) Adding 1-1.2mol of sodium hydroxide into 1mol of III, stirring for 0.5-5h at 40-80 ℃, and washing with deionized water for 3 times to obtain an epoxidation product; 1 weight part of epoxidation product is taken, 1 to 5 weight parts of 0.5 to 10 percent aqueous solution of sodium hydroxide is added, and the mixture is stirred for 0.5 to 10 hours at the temperature of 30 to 90 ℃ to obtain an intermediate product IV;
(5) Dropwise adding 1-1.1mol of II into 30mol of DMSO containing 1mol of IV, introducing nitrogen, heating to 170-200 ℃, stirring for 1-6h, cooling, standing, and concentrating in vacuum; slowly adding 90 ℃ deionized water, stirring for 10min, standing for layering, drying an organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain an intermediate product V;
(6) Adding 1mol of V and 1.1-1.5mol of triethylamine into 50mol of DMSO, carrying out ice water bath, stirring, slowly dripping 1.1-1.5mol of acryloyl chloride into the solution, and stirring for 6-12h; washing with 1M dilute hydrochloric acid solution, deionized water, saturated sodium bicarbonate solution and saturated saline respectively, separating, drying the organic phase with anhydrous sodium sulfate, filtering, and vacuum drying to obtain the photopolymerisable single-component thioxanthone photoinitiator, namely the target product VI.
Preferably, the fluorine-containing anhydride is tetrafluorosuccinic anhydride or perfluoro glutaric anhydride.
Preferably, the catalyst is tetrabutyl titanate, p-toluenesulfonic acid, palygorskite solid acid or sodium aluminate.
A photo-curing coating is prepared from the following raw materials in parts by weight: 65-69 parts of acrylate resin, 10 parts of TMPTA, 8 parts of TPGDA, 12 parts of butyl acrylate and 1-5 parts of target product VI.
Preferably, the preparation method of the photo-curing coating comprises the following steps: mixing the raw materials in parts by weight, coating on PET containing the base coat, and irradiating for 30-180s under UV light to obtain a coating with a dry film thickness of 2 μm.
The preparation process of the novel photopolymerisable single-component thioxanthone photoinitiator provided by the invention is as follows:
the invention has the beneficial effects that:
(1) The photopolymerizable single-component thioxanthone photoinitiator provided by the invention can be used in all currently known photopolymerization systems, and has the advantage of wide applicability.
(2) The invention provides a photopolymerizable single-component thioxanthone photoinitiator. The single-component thioxanthone photoinitiator simultaneously contains a thioxanthone initiator, a hydrogen donor penta-membered ring thioketone structure and an acryloyloxy group, so that the inherent problem of reverse electron transfer of a conventional double-component system is avoided, and the yellowing problem caused by common auxiliary initiator amine is avoided while the efficient initiation efficiency is realized; in addition, the acryloyloxy group can directly participate in the reaction, and enter the system in a chemical bond form, so that the problem of migration of the initiator does not exist.
(3) The photopolymerisable single-component thioxanthone photoinitiator provided by the invention has the structure containing the F element, wherein the F element has lower atomic surface energy and the characteristic of migrating to the surface of a system, and can play a role in overcoming oxygen polymerization inhibition and dirt resistance.
(4) The photopolymerizable single-component thioxanthone photoinitiator provided by the invention has wide applicability in UV-LEDs, and can be widely applied to the fields of 3C, 3D printing, microelectronics and the like.
The specific embodiment is as follows:
the present invention will be described in detail with reference to examples. It is to be understood that the following examples are illustrative of embodiments of the present invention and are not intended to limit the scope of the invention.
Example 1
A method for preparing a photopolymerizable single-component thioxanthone photoinitiator, comprising the following steps:
(1) Adding 1mol of hydroxythioxanthone, 1.2mol of bromoethanol and 1.2mol of potassium carbonate into 50mol of DMF, heating to 110 ℃, stirring strongly for 3 hours, cooling, standing, and concentrating the solution in vacuum to enrich the residual components; slowly adding 60mol of water, stirring for 30min, adding 50mol of DMSO, stirring for 30min, standing for layering, drying the organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain an intermediate product I;
the infrared data are as follows: 3512cm -1 : -OH is present; 1562cm -1 、1250cm -1 、762cm -1 : the benzene ring exists; 1723cm -1 : -c=o present; 988cm -1 : -C-S-present; 582cm -1 : -C-Br is absent.
(2) Adding 1mol of I, 1.2mol of perfluoro-glutaric anhydride and 0.5wt% of tetrabutyl titanate into 50mol of DMSO, introducing nitrogen, heating to 110 ℃, stirring for 3h, cooling, and standing for later use to obtain an intermediate product II;
the dosage of the tetrabutyl titanate is the percentage of the total mass of the fluorine-containing anhydride;
the infrared data are as follows: 3483cm -1 : -OH is present; 1562cm -1 、1250cm -1 、762cm -1 : the benzene ring exists; 1723cm -1 : -c=o present; 988cm -1 : -C-S-present; 1187cm -1 : -C-F is present.
(3) 1mol of 4-hydroxymethyl-1, 3-dioxo-2-thione was added to a solution containing 3wt% BF 3 Heating 1mol of epoxy chloropropane in diethyl ether to 80 ℃ for 2h; standing, and steaming at 40deg.C under reduced pressureDistilling to obtain an intermediate product III;
the BF 3 The consumption of the diethyl ether is 3 weight percent of the mass of the epichlorohydrin;
the infrared data are as follows: 3512cm -1 : -OH is present; 1162cm -1 : -c=s present; 910cm -1 : the epoxy group is absent; 741cm -1 : -C-Cl is present.
(4) Adding 1.2mol of sodium hydroxide into 1mol of III, stirring for 2 hours at 60 ℃, and washing with deionized water for 3 times to obtain an epoxidation product; taking 1 part by weight of an epoxidation product, adding 4 parts by weight of a 2% sodium hydroxide aqueous solution, and stirring for 5 hours at 60 ℃ to obtain an intermediate product IV;
the infrared data are as follows: 3512cm -1 : -OH is present; 1162cm -1 : -c=s present; 741cm -1 : the C-Cl disappeared.
(5) 1.1mol of II is added into 30mol of DMSO containing 1mol of IV in a dropwise manner, nitrogen is introduced, the mixture is heated to 200 ℃ and stirred for 1 hour, cooled, stood still and concentrated in vacuum; slowly adding 90 ℃ deionized water, stirring for 10min, standing for layering, drying an organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain an intermediate product V;
the infrared data are as follows: 3501cm -1 : -OH is present; 1562cm -1 、1250cm -1 、762cm -1 : the benzene ring exists; 1723cm -1 : -c=o present; 988cm -1 : -C-S-present; 1187cm -1 : -C-F is present; 1162cm -1 : -c=s is present.
(6) 1mol of V and 1.4mol of triethylamine are added into 50mol of DMSO, the solution is stirred in an ice water bath, 1.4mol of acryloyl chloride is slowly added into the solution in a dropwise manner, and the solution is stirred for 8 hours; washing with 1M dilute hydrochloric acid solution, deionized water, saturated sodium bicarbonate solution and saturated saline respectively, separating, drying the organic phase with anhydrous sodium sulfate, filtering, and vacuum drying to obtain the photopolymerisable single-component thioxanthone photoinitiator, namely the target product VI.
The infrared data are as follows: 3501cm -1 : -OH vanishes; 1562cm -1 、1250cm -1 、762cm -1 : the benzene ring exists; 1723cm -1 : -c=o present; 988cm -1 : -C-S-present; 1187cm -1 : -C-F is present; 1162cm -1 : -c=s present; 1611cm -1 、810cm -1 : -c=c-present.
The nuclear magnetic hydrogen spectrum data are as follows: 1 h NMR (400 mhz, dmso, delta ppm): 7.2-8.5 (14H, benzene ring); 4.02 (2H, -CH) 2 -)；4.23(2H，-CH 2 -)；3.64(6H，-CH 2 -)；4.41(2H，-CH-)；3.05(2H，-CH 2 -)；5.96(1H，-CH＝)；5.61/6.30(2H，CH 2 ＝)。
Example 2
A method for preparing a photopolymerizable single-component thioxanthone photoinitiator, comprising the following steps:
(1) Adding 1mol of hydroxythioxanthone, 1mol of bromoethanol and 1mol of potassium carbonate into 50mol of DMF, heating to 130 ℃, stirring strongly for 1h, cooling, standing, and concentrating the solution in vacuum to enrich the residual components; slowly adding 60mol of water, stirring for 30min, adding 50mol of DMSO, stirring for 30min, standing for layering, drying the organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain an intermediate product I;
the infrared data are as follows: 3511cm -1 : -OH is present; 1561cm -1 、1250cm -1 、761cm -1 : the benzene ring exists; 1721cm -1 : -c=o present; 988cm -1 : -C-S-present; 582cm -1 : -C-Br is absent.
(2) Adding 1mol of I, 1.4mol of tetrafluorosuccinic anhydride and 2wt% of p-toluenesulfonic acid into 50mol of DMSO, introducing nitrogen, heating to 100 ℃, stirring for 5 hours, cooling, and standing for later use to obtain an intermediate product II;
the dosage of the catalyst p-toluenesulfonic acid is the percentage of the total mass of I and tetrafluorosuccinic anhydride;
the infrared data are as follows: 3481cm -1 : -OH is present; 1561cm -1 、1250cm -1 、761cm -1 : the benzene ring exists; 1720cm -1 : -c=o present; 988cm -1 : -C-S-present; 1187cm -1 : -C-F is present.
(3) 1mol of 4-hydroxymethyl-1, 3-dioxo-2-thione was addedTo contain 0.5wt% BF 3 Heating 1.2mol of ethyl ether in 1.2mol of epichlorohydrin to 40 ℃ for reaction for 8 hours; standing, and distilling under reduced pressure at 40 ℃ to obtain an intermediate product III;
the BF 3 The consumption of the diethyl ether is 0.5 weight percent of the mass of the epichlorohydrin;
the infrared data are as follows: 3509cm -1 : -OH is present; 1161cm -1 : -c=s present; 910cm -1 : the epoxy group is absent; 740cm -1 : -C-Cl is present.
(4) Adding 1.1mol of sodium hydroxide into 1mol of III, stirring for 0.5h at 80 ℃, and washing with deionized water for 3 times to obtain an epoxidation product; taking 1 part by weight of an epoxidation product, adding 2 parts by weight of 8% sodium hydroxide aqueous solution, and stirring at 90 ℃ for 0.5h to obtain an intermediate product IV;
the infrared data are as follows: 3509cm -1 : -OH is present; 1161cm -1 : -c=s present; 740cm -1 : the C-Cl disappeared.
(5) 1mol of II is added into 30mol of DMSO containing 1mol of IV in a dropwise manner, nitrogen is introduced, the mixture is heated to 170 ℃ and stirred for 6 hours, cooled, stood and concentrated in vacuum; slowly adding 90 ℃ deionized water, stirring for 10min, standing for layering, drying an organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain an intermediate product V;
the infrared data are as follows: 3501cm -1 : -OH is present; 1561cm -1 、1250cm -1 、761cm -1 : the benzene ring exists; 1723cm -1 : -c=o present; 988cm -1 : -C-S-present; 1187cm -1 : -C-F is present; 1162cm -1 : -c=s is present.
(6) 1mol of V and 1.3mol of triethylamine are added into 50mol of DMSO, the solution is stirred in an ice water bath, 1.3mol of acryloyl chloride is slowly added into the solution in a dropwise manner, and the solution is stirred for 10 hours; washing with 1M dilute hydrochloric acid solution, deionized water, saturated sodium bicarbonate solution and saturated saline respectively, separating, drying the organic phase with anhydrous sodium sulfate, filtering, and vacuum drying to obtain the photopolymerisable single-component thioxanthone photoinitiator, namely the target product VI.
The infrared data are as follows: 3501cm -1 : -OH vanishes;1561cm -1 、1250cm -1 、761cm -1 : the benzene ring exists; 1723cm -1 : -c=o present; 988cm -1 : -C-S-present; 1187cm -1 : -C-F is present; 1161cm -1 : -c=s present; 1610cm -1 、810cm -1 : -c=c-present.
The nuclear magnetic hydrogen spectrum data are as follows: 1 h NMR (400 mhz, dmso, delta ppm): 7.2-8.5 (14H, benzene ring); 4.02 (2H, -CH) 2 -)；4.23(2H，-CH 2 -)；3.64(6H，-CH 2 -)；4.41(2H，-CH-)；3.05(2H，-CH 2 -)；5.96(1H，-CH＝)；5.61/6.30(2H，CH 2 ＝)。
Example 3
A method for preparing a photopolymerizable single-component thioxanthone photoinitiator, comprising the following steps:
(1) Adding 1mol of hydroxythioxanthone, 1.1mol of bromoethanol and 1.1mol of potassium carbonate into 50mol of DMF, heating to 120 ℃ and stirring strongly for 2 hours, cooling, standing, and concentrating the solution in vacuum to enrich the residual components; slowly adding 60mol of water, stirring for 30min, adding 50mol of DMSO, stirring for 30min, standing for layering, drying the organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain an intermediate product I;
the infrared data are as follows: 3508cm -1 : -OH is present; 1555cm -1 、1248cm -1 、760cm -1 : the benzene ring exists; 1723cm -1 : -c=o present; 987cm -1 : -C-S-present; 582cm -1 : -C-Br is absent.
(2) Adding 1mol of I, 1.1mol of perfluoro glutaric anhydride and 3wt% of palygorskite solid acid into 50mol of DMSO, introducing nitrogen, heating to 90 ℃ and stirring for 8 hours, cooling, and standing for later use to obtain an intermediate product II;
the dosage of the palygorskite solid acid serving as the catalyst is the percentage of the total mass of the perfluoro glutaric anhydride;
the infrared data are as follows: 3483cm -1 : -OH is present; 1556cm -1 、1250cm -1 、760cm -1 : the benzene ring exists; 1723cm -1 : -c=o present; 988cm -1 ：-C-S-present; 1187cm -1 : -C-F is present.
(3) 1mol of 4-hydroxymethyl-1, 3-dioxo-2-thione was added to a solution containing 1wt% BF 3 Heating 1.1mol of ethyl ether in 1.1mol of epichlorohydrin to 70 ℃ for 4 hours of reaction; standing, and distilling under reduced pressure at 40 ℃ to obtain an intermediate product III;
the BF 3 The consumption of the diethyl ether is 1 weight percent of the mass of the epichlorohydrin;
the infrared data are as follows: 3512cm -1 : -OH is present; 1162cm -1 : -c=s present; 910cm -1 : the epoxy group is absent; 741cm -1 : -C-Cl is present.
(4) Adding 1mol of sodium hydroxide into 1mol of III, stirring for 2 hours at 70 ℃, and washing with deionized water for 3 times to obtain an epoxidation product; taking 1 part by weight of an epoxidation product, adding 1 part by weight of 10% sodium hydroxide aqueous solution, and stirring for 10 hours at 30 ℃ to obtain an intermediate product IV;
the infrared data are as follows: 3512cm -1 : -OH is present; 1162cm -1 : -c=s present; 741cm -1 : the C-Cl disappeared.
(5) 1.1mol of II is added into 30mol of DMSO containing 1mol of IV in a dropwise manner, nitrogen is introduced, the mixture is heated to 190 ℃ and stirred for 2 hours, cooled, stood and concentrated in vacuum; slowly adding 90 ℃ deionized water, stirring for 10min, standing for layering, drying an organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain an intermediate product V;
the infrared data are as follows: 3501cm -1 : -OH is present; 1562cm -1 、1250cm -1 、762cm -1 : the benzene ring exists; 1723cm -1 : -c=o present; 988cm -1 : -C-S-present; 1187cm -1 : -C-F is present; 1162cm -1 : -c=s is present.
(6) 1mol of V and 1.1mol of triethylamine are added into 50mol of DMSO, the solution is stirred in an ice water bath, 1.1mol of acryloyl chloride is slowly added into the solution in a dropwise manner, and the solution is stirred for 12 hours; washing with 1M dilute hydrochloric acid solution, deionized water, saturated sodium bicarbonate solution and saturated saline respectively, separating, drying the organic phase with anhydrous sodium sulfate, filtering, and vacuum drying to obtain the photopolymerisable single-component thioxanthone photoinitiator, namely the target product VI.
The infrared data are as follows: 3501cm -1 : -OH vanishes; 1562cm -1 、1250cm -1 、762cm -1 : the benzene ring exists; 1723cm -1 : -c=o present; 988cm -1 : -C-S-present; 1187cm -1 : -C-F is present; 1162cm -1 : -c=s present; 1611cm -1 、810cm -1 : -c=c-present.
The nuclear magnetic hydrogen spectrum data are as follows: 1 h NMR (400 mhz, dmso, delta ppm): 7.2-8.5 (14H, benzene ring); 4.02 (2H, -CH) 2 -)；4.23(2H，-CH 2 -)；3.64(6H，-CH 2 -)；4.41(2H，-CH-)；3.05(2H，-CH 2 -)；5.96(1H，-CH＝)；5.61/6.30(2H，CH 2 ＝)。
Example 4
A method for preparing a photopolymerizable single-component thioxanthone photoinitiator, comprising the following steps:
(1) Adding 1mol of hydroxythioxanthone, 1.2mol of bromoethanol and 1.2mol of potassium carbonate into 50mol of DMF, heating to 120 ℃ and stirring strongly for 2 hours, cooling, standing, and concentrating the solution in vacuum to enrich residual components; slowly adding 60mol of water, stirring for 30min, adding 50mol of DMSO, stirring for 30min, standing for layering, drying the organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain an intermediate product I;
the infrared data are as follows: 3512cm -1 : -OH is present; 1562cm -1 、1250cm -1 、762cm -1 : the benzene ring exists; 1723cm -1 : -c=o present; 988cm -1 : -C-S-present; 582cm -1 : -C-Br is absent.
(2) Adding 1mol of I, 1.3mol of perfluoro-glutaric anhydride and 4wt% of sodium aluminate into 50mol of DMSO, introducing nitrogen, heating to 100 ℃, stirring for 15h, cooling, and standing for later use to obtain an intermediate product II;
the dosage of the catalyst sodium aluminate is the percentage of the total mass of I and perfluoro glutaric anhydride;
the infrared data are as follows: 3483cm -1 : -OH is present; 1562cm -1 、1250cm -1 、762cm -1 : the benzene ring exists; 1723cm -1 : -c=o present; 988cm -1 : -C-S-present; 1187cm -1 : -C-F is present.
(3) 1mol of 4-hydroxymethyl-1, 3-dioxo-2-thione was added to a solution containing 2wt% BF 3 Heating 1.1mol of ethyl ether in 1.1mol of epichlorohydrin to 50 ℃ for reaction for 6 hours; standing, and distilling under reduced pressure at 40 ℃ to obtain an intermediate product III;
the BF 3 The consumption of the diethyl ether is 2 weight percent of the mass of the epichlorohydrin;
the infrared data are as follows: 3512cm -1 : -OH is present; 1160cm -1 : -c=s present; 910cm -1 : the epoxy group is absent; 741cm -1 : -C-Cl is present.
(4) Adding 1.2mol of sodium hydroxide into 1mol of III, stirring for 5 hours at 40 ℃, and washing with deionized water for 3 times to obtain an epoxidation product; taking 1 part by weight of an epoxidation product, adding 5 parts by weight of 0.5% sodium hydroxide aqueous solution, and stirring for 5 hours at 50 ℃ to obtain an intermediate product IV;
the infrared data are as follows: 3512cm -1 : -OH is present; 1160cm -1 : -c=s present; 741cm -1 : the C-Cl disappeared.
(5) Dropwise adding 1.1mol of II into 30mol of DMSO containing 1mol of IV, introducing nitrogen, heating to 180 ℃, stirring for 3 hours, cooling, standing, and concentrating in vacuum; slowly adding 90 ℃ deionized water, stirring for 10min, standing for layering, drying an organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain an intermediate product V;
the infrared data are as follows: 3501cm -1 : -OH is present; 1562cm -1 、1250cm -1 、762cm -1 : the benzene ring exists; 1723cm -1 : -c=o present; 988cm -1 : -C-S-present; 1187cm -1 : -C-F is present; 1161cm -1 : -c=s is present.
(6) 1mol of V and 1.5mol of triethylamine are added into 50mol of DMSO, the solution is stirred in an ice water bath, 1.5mol of acryloyl chloride is slowly added into the solution in a dropwise manner, and the solution is stirred for 6 hours; washing with 1M dilute hydrochloric acid solution, deionized water, saturated sodium bicarbonate solution and saturated saline respectively, separating, drying the organic phase with anhydrous sodium sulfate, filtering, and vacuum drying to obtain the photopolymerisable single-component thioxanthone photoinitiator, namely the target product VI.
The infrared data are as follows: 3501cm -1 : -OH vanishes; 1562cm -1 、1250cm -1 、762cm -1 : the benzene ring exists; 1723cm -1 : -c=o present; 988cm -1 : -C-S-present; 1187cm -1 : -C-F is present; 1161cm -1 : -c=s present; 1611cm -1 、810cm -1 : -c=c-present.
The nuclear magnetic hydrogen spectrum data are as follows: 1 h NMR (400 mhz, dmso, delta ppm): 7.2-8.5 (14H, benzene ring); 4.02 (2H, -CH) 2 -)；4.23(2H，-CH 2 -)；3.64(6H，-CH 2 -)；4.41(2H，-CH-)；3.05(2H，-CH 2 -)；5.96(1H，-CH＝)；5.61/6.30(2H，CH 2 ＝)。
Example 5
A method for preparing a photopolymerizable single-component thioxanthone photoinitiator, comprising the following steps:
(1) Adding 1mol of hydroxythioxanthone, 1.1mol of bromoethanol and 1.1mol of potassium carbonate into 50mol of DMF, heating to 130 ℃, stirring strongly for 1h, cooling, standing, and concentrating the solution in vacuum to enrich the residual components; slowly adding 60mol of water, stirring for 30min, adding 50mol of DMSO, stirring for 30min, standing for layering, drying the organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain an intermediate product I;
the infrared data are as follows: 3512cm -1 : -OH is present; 1560cm -1 、1249cm -1 、761cm -1 : the benzene ring exists; 1723cm -1 : -c=o present; 988cm -1 : -C-S-present; 582cm -1 : -C-Br is absent.
(2) Adding 1mol of I, 1.2mol of tetrafluorosuccinic anhydride and 1wt% of tetrabutyl titanate into 50mol of DMSO, introducing nitrogen, heating to 80 ℃, stirring for 10 hours, cooling, and standing for later use to obtain an intermediate product II;
the dosage of the catalyst tetrabutyl titanate is the percentage of the total mass of I and tetrafluorosuccinic anhydride;
the infrared data are as follows: 3483cm -1 : -OH is present; 1560cm -1 、1249cm -1 、761cm -1 : the benzene ring exists; 1723cm -1 : -c=o present; 988cm -1 : -C-S-present; 1187cm -1 : -C-F is present.
(3) 1mol of 4-hydroxymethyl-1, 3-dioxo-2-thione was added to a solution containing 1.5wt% BF 3 Heating 1.2mol of ethyl ether in 1.2mol of epichlorohydrin to 60 ℃ for 4 hours of reaction; standing, and distilling under reduced pressure at 40 ℃ to obtain an intermediate product III;
the BF 3 The consumption of the diethyl ether is 1.5 weight percent of the mass of the epichlorohydrin;
the infrared data are as follows: 3512cm -1 : -OH is present; 1162cm -1 : -c=s present; 910cm -1 : the epoxy group is absent; 741cm -1 : -C-Cl is present.
(4) Adding 1.1mol of sodium hydroxide into 1mol of III, stirring for 4 hours at 50 ℃, and washing with deionized water for 3 times to obtain an epoxidation product; taking 1 part by weight of an epoxidation product, adding 5 parts by weight of a 3% sodium hydroxide aqueous solution, and stirring at 80 ℃ for 2 hours to obtain an intermediate product IV;
the infrared data are as follows: 3512cm -1 : -OH is present; 1162cm -1 : -c=s present; 741cm -1 : the C-Cl disappeared.
(5) 1mol of II is added into 30mol of DMSO containing 1mol of IV in a dropwise manner, nitrogen is introduced, the mixture is heated to 190 ℃ and stirred for 3 hours, cooled, stood and concentrated in vacuum; slowly adding 90 ℃ deionized water, stirring for 10min, standing for layering, drying an organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain an intermediate product V;
the infrared data are as follows: 3501cm -1 : -OH is present; 1560cm -1 、1249cm -1 、761cm -1 : the benzene ring exists; 1723cm -1 : -c=o present; 988cm -1 : -C-S-present; 1187cm -1 : -C-F is present; 1162cm -1 : -c=s is present.
(6) 1mol of V and 1.2mol of triethylamine are added into 50mol of DMSO, the solution is stirred in an ice water bath, 1.2mol of acryloyl chloride is slowly added into the solution in a dropwise manner, and the solution is stirred for 10 hours; washing with 1M dilute hydrochloric acid solution, deionized water, saturated sodium bicarbonate solution and saturated saline respectively, separating, drying the organic phase with anhydrous sodium sulfate, filtering, and vacuum drying to obtain the photopolymerisable single-component thioxanthone photoinitiator, namely the target product VI.
The infrared data are as follows: 3501cm -1 : -OH vanishes; 1560cm -1 、1249cm -1 、761cm -1 : the benzene ring exists; 1723cm -1 : -c=o present; 988cm -1 : -C-S-present; 1187cm -1 : -C-F is present; 1162cm -1 : -c=s present; 1611cm -1 、810cm -1 : -c=c-present.
The nuclear magnetic hydrogen spectrum data are as follows: 1 h NMR (400 mhz, dmso, delta ppm): 7.2-8.5 (14H, benzene ring); 4.02 (2H, -CH) 2 -)；4.23(2H，-CH 2 -)；3.64(6H，-CH 2 -)；4.41(2H，-CH-)；3.05(2H，-CH 2 -)；5.96(1H，-CH＝)；5.61/6.30(2H，CH 2 ＝)。
The photoinitiator obtained in the specific example 1 was used as a base material in application examples and applied to a photocurable coating.
Application example 1
The photo-curing coating comprises the following raw materials in parts by weight: acrylate resin SM6202 67, TMPTA 10, TPGDA 8, butyl acrylate 12 and target product VI 3.
The preparation method comprises the following steps: the raw materials were mixed in parts by weight, coated on a PET containing a primer, and irradiated under UV light for 60 seconds to obtain a coating film 2 μm thick in dry film.
Application example 2
The photo-curing coating comprises the following raw materials in parts by weight: acrylate resin SM6202 65, TMPTA 10, TPGDA 8, butyl acrylate 12 and target product VI 5.
The preparation method comprises the following steps: the raw materials were mixed in parts by weight, coated on a PET containing a primer, and irradiated under UV light for 30 seconds to obtain a coating film having a dry film thickness of 2. Mu.m.
Application example 3
A photo-curing coating is prepared from the following raw materials in parts by weight: acrylate resin SM6202 69, TMPTA 10, TPGDA 8, butyl acrylate 12 and target product VI 1.
Preferably, the preparation method of the photo-curing coating comprises the following steps: the raw materials were mixed in parts by weight, coated on a PET containing a primer, and irradiated under UV light for 180 seconds to obtain a coating film 2 μm thick in dry film.
Application example 4
The photo-curing coating comprises the following raw materials in parts by weight: acrylate resin SM6202 67, TMPTA 10, TPGDA 8, butyl acrylate 12 and target product VI 3.
The preparation method comprises the following steps: the raw materials were mixed in parts by weight, coated on a PET containing a primer, and irradiated under UV light for 120 seconds to obtain a coating film 2 μm thick in dry film.
Comparative examples 1-3 were applied to apply example 1 as a control.
Application example 1
The photo-curing coating comprises the following raw materials in parts by weight: acrylate resin SM6202 67, TMPTA 10, TPGDA 8, butyl acrylate 12 and ITX 3.
The preparation method comprises the following steps: the raw materials were mixed in parts by weight, coated on a PET containing a primer, and irradiated under UV light for 60 seconds to obtain a coating film 2 μm thick in dry film.
Application example 2
The photo-curing coating comprises the following raw materials in parts by weight: acrylate resin SM6202 67 parts, TMPTA 10 parts, TPGDA 8 parts, butyl acrylate 12 parts, ITX 3 parts and EDAB 3 parts.
The preparation method comprises the following steps: the raw materials were mixed in parts by weight, coated on a PET containing a primer, and irradiated under UV light for 60 seconds to obtain a coating film 2 μm thick in dry film.
Physical properties of the macrophotoinitiators of the present invention, including migration, yellowing, and initiation efficiency, prepared in application examples 1 to 4 and application examples 1 to 3, respectively, were measured, and the results are shown in Table 1.
Table 1 physical test performance of various examples
First, as can be seen from table 1, the photopolymerizable single-component thioxanthone photoinitiator of the present invention is compared with the currently commonly used small molecule photoinitiator ITX and the two-component itx+edab; the product of the invention can self-initiate self-crosslinking, has no migration problem, and has no smell; meanwhile, the thioketone ring structure is used as an intramolecular hydrogen donor, so that the problem of yellowing of tertiary amine is avoided, and the initiation efficiency is higher. Therefore, the product of the invention has the advantages of no smell, no yellowing, difficult migration, more environmental protection and the like;
secondly, compared with the existing common small molecular photoinitiator, the polyurethane photoinitiator has larger water contact angle and certain water repellency;
in combination, compared with the existing photoinitiator, the photopolymerizable single-component thioxanthone photoinitiator not only overcomes the defects of low initiation efficiency, need of auxiliary initiator, easy migration and precipitation and yellowing of the traditional double-component micromolecular photoinitiator, but also has high initiation efficiency and certain water-repellent capacity.
The test method comprises the following steps:
(1) Smell: the evaluation was performed by direct fan method, the lower the odor, the lower the migration.
(2) Mobility: and (3) placing the sample to be tested in acetonitrile in an oven at 40 ℃ for soaking for 24 hours, preparing the same concentration, and testing the molar absorption coefficient of the sample under the corresponding photoinitiator by using an ultraviolet-visible spectrometer. Migration expression method: 5 is optimal and 1 is worst.
(3) Yellowing: visual inspection of the film gave an assessment of the darker film color, indicating more severe yellowing. The yellowing expression method comprises the following steps: 5 is colorless, most preferably, 1 is dark and worst.
(4) And (3) testing the initiation efficiency of oxygen polymerization inhibition and double bonds:
the testing method comprises the following steps: the polymerization kinetics of the photocurable resin was monitored by a series of real-time infrared spectra. Will containThe sample with photoinitiator is coated on KBr salt sheet, then is put into RTIR, is irradiated by an ultraviolet point light source for 120s for solidification, the light intensity is measured by Sup>A UV-A ultraviolet irradiation meter, and the light intensity is set to 80mW/cm 2 . By monitoring the near infrared region C=C-H at 776-828cm -1 The change in the absorption peak area of (2) intuitively reflects the extent to which polymerization proceeds. The double bond conversion (DC) of the polymerization system can be calculated by combining OMNIC 8.2 infrared software and Excel data processing software with a formula, and each sample test is repeated 3 times to obtain an average value.
Wherein DC represents the conversion rate of carbon-carbon double bonds when the illumination time is t, A 0 Represents the initial area of the absorption peak of double bonds before illumination, A t Represents the area of the double bond absorption peak at the time of illumination t.
(5)t(R p(max) ) S: the time required for reaching the maximum polymerization rate is obtained by monitoring the polymerization kinetics process of the photo-curing resin by using a series of real-time infrared spectra and deriving the time-conversion curve p A curve.
(6) Contact angle: testing was performed as described in ASTM D7334-2008 (2013). The higher the water contact angle value, the lower the surface tension, and the better the stain resistance.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (6)
1. A photopolymerizable single-component thioxanthone photoinitiator, which is characterized by the following structural formula:
wherein, -R-is-CF 2 -or-C 2 F 4 -。
2. A process for the preparation of a photopolymerizable single-component thioxanthone photoinitiator according to claim 1, characterized by: comprises the following steps:
(1) Adding 1mol of hydroxythioxanthone, 1-1.2mol of bromoethanol and 1-1.2mol of potassium carbonate into 50mol of DMF, heating to 110-130 ℃ and stirring strongly for 1-3h, cooling, standing, and concentrating the solution in vacuum to enrich residual components; slowly adding 60mol of water, stirring for 30min, adding 50mol of DMSO, stirring for 30min, standing for layering, drying the organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain an intermediate product I;
(2) Adding 1mol of I, 1.1-1.4mol of fluorine-containing anhydride and 0.5-4wt% of catalyst into 50mol of DMSO, introducing nitrogen, heating to 80-110 ℃ and stirring for 3-15h, cooling, and standing for later use to obtain an intermediate product II;
the using percentage of the catalyst is based on the total mass of I and fluorine-containing anhydride;
(3) 1mol of 4-hydroxymethyl-1, 3-dioxo-2-thione is added to a solution containing 0.5-3wt% BF 3 Heating 1-1.2mol of ethyl ether in epichlorohydrin to 40-80 ℃ for 2-8h; standing, and distilling under reduced pressure at 40 ℃ to obtain an intermediate product III;
the BF 3 The consumption of the diethyl ether is 0.5-3wt% of the mass of the epichlorohydrin;
(4) Adding 1-1.2mol of sodium hydroxide into 1mol of III, stirring for 0.5-5h at 40-80 ℃, and washing with deionized water for 3 times to obtain an epoxidation product; 1 weight part of epoxidation product is taken, 1 to 5 weight parts of 0.5 to 10 percent aqueous solution of sodium hydroxide is added, and the mixture is stirred for 0.5 to 10 hours at the temperature of 30 to 90 ℃ to obtain an intermediate product IV;
(5) Dropwise adding 1-1.1mol of II into 30mol of DMSO containing 1mol of IV, introducing nitrogen, heating to 170-200 ℃, stirring for 1-6h, cooling, standing, and concentrating in vacuum; slowly adding 90 ℃ deionized water, stirring for 10min, standing for layering, drying an organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain an intermediate product V;
(6) Adding 1mol of V and 1.1-1.5mol of triethylamine into 50mol of DMSO, carrying out ice water bath, stirring, slowly dripping 1.1-1.5mol of acryloyl chloride into the solution, and stirring for 6-12h; washing with 1M dilute hydrochloric acid solution, deionized water, saturated sodium bicarbonate solution and saturated saline respectively, separating, drying the organic phase with anhydrous sodium sulfate, filtering, and vacuum drying to obtain the photopolymerisable single-component thioxanthone photoinitiator, namely the target product VI.
3. The method for preparing the photopolymerizable single-component thioxanthone photoinitiator according to claim 2, wherein the method comprises the following steps: the fluorine-containing anhydride is tetrafluorosuccinic anhydride and perfluoro glutaric anhydride.
4. The method for preparing the photopolymerizable single-component thioxanthone photoinitiator according to claim 2, wherein the method comprises the following steps: the catalyst is tetrabutyl titanate, p-toluenesulfonic acid, palygorskite solid acid or sodium aluminate.
5. A photo-curing coating is prepared from the following raw materials in parts by weight: 65-69 parts of acrylate resin, 10 parts of TMPTA, 8 parts of TPGDA, 12 parts of butyl acrylate and 1-5 parts of the photopolymerizable single-component thioxanthone photoinitiator according to claim 1.
6. A photocurable coating according to claim 5, prepared by: mixing the raw materials in parts by weight, coating on PET containing the base coat, and irradiating for 30-180s under UV light to obtain a coating with a dry film thickness of 2 μm.
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