CN116515019A - Macromolecular thioxanthone photoinitiator and preparation method thereof - Google Patents
Macromolecular thioxanthone photoinitiator and preparation method thereof Download PDFInfo
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- CN116515019A CN116515019A CN202310573195.8A CN202310573195A CN116515019A CN 116515019 A CN116515019 A CN 116515019A CN 202310573195 A CN202310573195 A CN 202310573195A CN 116515019 A CN116515019 A CN 116515019A
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- macromolecular
- thioxanthone
- photoinitiator
- thioxanthone photoinitiator
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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 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- KHDGCKOTVWKNMB-UHFFFAOYSA-N 2-ethenylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C=C)=CC=C3SC2=C1 KHDGCKOTVWKNMB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 28
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 150000001924 cycloalkanes Chemical class 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000178 monomer Substances 0.000 abstract description 9
- 231100000419 toxicity Toxicity 0.000 abstract description 5
- 230000001988 toxicity Effects 0.000 abstract description 5
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 3
- 239000012634 fragment Substances 0.000 abstract description 2
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- 238000004383 yellowing Methods 0.000 abstract description 2
- 238000006303 photolysis reaction Methods 0.000 abstract 1
- 230000015843 photosynthesis, light reaction Effects 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 12
- -1 acrylic ester Chemical class 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000003211 polymerization photoinitiator Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000012952 cationic photoinitiator Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- 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
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses a macromolecular thioxanthone photoinitiator and a preparation method thereof, which are based on the problems of toxicity, yellowing and unpleasant smell caused by the fact that traditional thioxanthone micromolecular photoinitiators and photolysis fragments thereof are easy to migrate and volatilize, 2-vinyl thioxanthone is taken as a monomer, and the thioxanthone macromolecule photoinitiator is obtained through solution free radical polymerization.
Description
Technical Field
The invention relates to the technical field of photo-curing materials, in particular to a macromolecular thioxanthone photoinitiator and a preparation method thereof.
Background
Photopolymerization refers to a reaction that utilizes light energy to initiate polymerization of monomers. The photoinitiator can absorb radiation energy to generate active fragments such as free radicals, cations or anions after being irradiated by a proper light source, and initiate unsaturated acrylate monomers or cyclic monomers to polymerize, so that the liquid monomers are converted into polymers. Photoinitiators can be classified into radical polymerization photoinitiators and cationic photoinitiators according to the initiation mechanism, and radical polymerization photoinitiators are most widely used.
Some commonly used photoinitiators, such as ITX, TPO, irgacure2959, BP, etc., are widely used in the photopolymerization field. However, these conventional small molecule photoinitiators have disadvantages of odor, toxicity, and easy migration, which makes their use very limited. Macromolecular photoinitiators are effective ways to solve the above series of problems and are an important direction in the field of photoinitiator research. However, the synthesis strategy of the macromolecular photoinitiator is complex, the cost is high, and the loss caused by the defects of high efficiency and low mobility is difficult to balance, so that the strategy for developing a novel simple and convenient macromolecular photoinitiator still has great significance.
Disclosure of Invention
First, the technical problem to be solved
In order to overcome the defects of the prior art, a macromolecular thioxanthone photoinitiator and a preparation method thereof are provided, the preparation method is simple, the reaction condition is mild, the purification is easy, and the problems of migration and toxicity of the photoinitiator can be solved.
(II) technical scheme
The invention is realized by the following technical scheme: the invention provides a macromolecular thioxanthone photoinitiator, which has the following structural general formula:
definition R 1 And R is 2 Is H, halogen atom, R 0 、OR 0 、NHR0、N(R 0 ) 2 、SH；R 0 Is a branched or straight chain or cyclic alkane containing from 1 to 24 carbon atoms.
A preparation method of a macromolecular thioxanthone photoinitiator comprises the following steps:
step 1: adding an initiator, 2-vinyl thioxanthone and an organic solvent into a flask, stirring until the initiator is completely dissolved, slowly heating to 50-150 ℃ and reacting for 3-7h;
step 2: after the reaction is finished, cooling by using ice water bath, spin-drying the solvent, washing for a plurality of times by using an organic solvent,
the product is obtained.
Further, the reaction equation is as follows:
further, the structural general formula of the 2-vinyl thioxanthone is as follows:
definition R 1 And R is 2 Is H, halogen atom, R 0 、OR 0 、NHR0、N(R 0 ) 2 、SH；R 0 Is a branched or straight chain or cyclic alkane containing from 1 to 24 carbon atoms.
Further, the initiator is selected from one or any combination of benzoyl peroxide, tert-butyl peroxybenzoate, azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate.
Further, the organic solvent is selected from one or any combination of dimethyl sulfoxide, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, benzene, toluene, xylene, acetonitrile, chlorobenzene, dichlorobenzene, anisole, petroleum ether, dioxane, tetrahydrofuran, pyridine, N-dimethylformamide, N-methylpyrrolidone, methyl tertiary butyl ether, ethylene glycol dimethyl ether, acetone, butanone, methanol, ethanol and propanol.
The macromolecular thioxanthone photoinitiator is prepared by the method, and the chemical structural formula of the macromolecular thioxanthone photoinitiator is shown in figure 3.
(III) beneficial effects
Compared with the prior art, the invention has the following beneficial effects:
according to the macromolecular thioxanthone photoinitiator and the preparation method thereof, 2-vinyl thioxanthone is selected for bulk polymerization to prepare the macromolecular thioxanthone photoinitiator, one-step synthesis of the thioxanthone macromolecular photoinitiator can be realized, the preparation method is simple, the reaction condition is mild, the purification is easy, and the problems of migration and toxicity of the photoinitiator are solved; the synthetic route does not involve toxic substances such as halogen and the like and high-boiling point solvents, is environment-friendly, and is suitable for industrial production; the prepared macromolecular thioxanthone photoinitiator and the auxiliary agent trigger acrylic ester monomers, the double bond polymerization speed is high, the conversion rate is high, the double bond conversion rate within 300s can reach about 90%, and the macromolecular thioxanthone photoinitiator has low toxicity and low mobility; the macromolecular thioxanthone photoinitiator has good solubility, can be dissolved in chlorine-containing solvents, ethanol and low-molecular fatty acid, and can be mixed with various resins.
Drawings
FIG. 1 is a graph showing the ultraviolet absorption spectrum of poly (2-vinylthioxanthone) as a product in example 1 of the present invention.
FIG. 2 is a graph showing the double bond conversion of poly (2-vinyl-5, 7-diethylthioxanthone) product of example 3 of the present invention to initiate polymerization of PEGDA.
FIG. 3 is a structural formula of a thioxanthone photoinitiator according to the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
Step 1: in a three-necked flask equipped with a stirrer, a condenser, a thermometer and toluene (100 ml) as a solvent, dibenzoyl peroxide (0.238 g, 9.8X10 g) as an initiator was charged -4 mol) and 2-vinyl thioxanthone (23.8 g,0.1 mol) as reaction monomers, stirring until the mixture is completely dissolved, controlling the reaction temperature in an oil bath at 80-95 ℃ and stirring for 3h;
step 2: after the reaction is completed, cooling by using ice water bath, spin-drying toluene, and washing for many times by petroleum ether to obtain the product, wherein the structural formula is as follows:
and (3) detection: the photoinitiators poly 2-vinylthioxanthone and the co-initiator ethyl 4-dimethylaminobenzoate prepared in example 1 were each used in a molar fraction of 1X 10 -5 mol·L -1 Added to acetonitrile and its UV absorbance was measured.
Experimental results: as shown in FIG. 1, the effective wavelength absorption range is 325nm-425nm, and the maximum absorption peak is 390nm; the optimal concentration is 0.01% wt, and the highest conversion rate can reach 90%.
Example 2
Step 1: in a three-necked flask equipped with a stirrer, a condenser, a thermometer and solvent xylene (100 ml), was charged the initiator benzoyl peroxide (0.504 g, 2.08X10) -3 mol) and 2-vinyl-6-methyl thioxanthone (25.2 g,0.1 mol) as reaction monomers, stirring until the mixture is completely dissolved, controlling the reaction temperature in an oil bath at 80-90 ℃ and stirring for 4 hours;
step 2: after the reaction is completed, the xylene is cooled by ice water bath and dried by spin, and the product is obtained after washing for many times by cyclohexane.
The structural formula is as follows:
and (3) detection: the product of example 2, poly 2-vinyl-6-methylthioxanthone and the co-initiator ethyl 4-dimethylaminobenzoate were each used in a molar fraction of 1X 10 -5 mol·L -1 Added to acetonitrile and tested for uv absorption.
Experimental results: the effective wavelength absorption range is 330nm-425nm, and the maximum absorption peak is 395nm.
Example 3
Step 1: in a three port equipped with stirrer, condenser, thermometer and solvent ethyl acetate (150 ml)The flask was charged with the initiator azobisisobutyronitrile (0.504 g, 5.37X10) -3 mol) and 2-vinyl-5, 7-diethyl thioxanthone (29.4 g,0.1 mol), stirring to dissolve completely, controlling the reaction temperature in an oil bath at 60-68 ℃, stirring for 5h;
step 2: after the reaction is completed, the ethyl acetate is cooled by ice water bath and dried by spin, and the product is obtained after washing for many times by n-hexane.
The structural formula is as follows:
and (3) detection: the photoinitiator poly 2-vinyl-5, 7-diethylthioxanthone prepared in example 3 and the co-initiator ethyl 4-dimethylaminobenzoate were each used in a mole fraction of 1X 10 -5 mol·L -1 Added to acetonitrile and tested for uv absorption.
Experimental results: the wavelength absorption range is 330nm-428nm, and the maximum absorption peak is 396nm;
as shown in FIG. 2, the optimal concentration is 0.01% wt, and the highest conversion rate can reach 90%;
example 4
Step 1: in a three-necked flask equipped with a stirrer, a condenser, a thermometer and a solvent of butyl acetate (200 ml), azobisisobutyronitrile (1.41 g, 8.56X10) -1 mol) and 2-vinyl-6, 7-dimethyl thioxanthone (26.6 g,0.1 mol), stirring to dissolve completely, controlling the reaction temperature in an oil bath at 60-68 ℃, stirring for 5h;
step 2: after the reaction is completed, the butyl acetate is cooled by ice water bath and dried by spin, and the product is obtained after the butyl acetate is washed by n-heptane for a plurality of times.
The structure is as follows
And (3) detection: the product of example 4, poly 2-vinyl-6, 7-dimethylthioxanthone and the co-initiator, ethyl 4-dimethylaminobenzoate, were each used in a molar fraction of 1X 10 -5 mol·L -1 Added to acetonitrile and tested for uv absorption.
Experimental results: the wavelength absorption range is 330nm-426nm, and the maximum absorption peak is 396nm.
Example 5
Step 1: in a three-necked flask equipped with a stirrer, a condenser, a thermometer and solvent ethanol (200 ml), azobisisoheptonitrile (1.41 g, 8.56X10) -1 mol) and 2-vinyl-6-methoxythioxanthone (26.1 g,0.1 mol), stirring until completely dissolved, controlling the reaction temperature in an oil bath at 55-65 ℃, and stirring for 4h;
step 2: after the reaction is completed, cooling by using an ice water bath, spin-drying ethanol, and washing for multiple times by using cyclohexane to obtain a product.
The structure is as follows
And respectively adding the thioxanthone photoinitiator and the co-initiator 4-dimethylaminobenzoic acid ethyl ester into the PEGDA monomer according to the mass fraction of 0.01 percent, and uniformly mixing to obtain the resin prepolymer.
1. Double bond conversion test
The prepared formula is respectively injected into a silica gel mold with the thickness of 30mm and 1mm, then 365nm LEDs and the like are used for irradiation for 10min, and simultaneously infrared is utilized to detect double bond absorption peaks, and double bond conversion rate is calculated after the reaction is completed. The test results are shown in Table 1 for double bond conversion.
2. Mobility test
Pouring the prepared resin prepolymer into a cylindrical mold (height 1cm, diameter 1 cm), irradiating with 365nm LED lamp source, curing for 15 min on both sides, immersing the cured round piece into dichloromethane, placing in an ultrasonic box, and monitoring the solution at intervals of one hour.
The table shows that the macromolecule thioxanthone photoinitiator synthesized under the same condition has no obvious reduction in initiation efficiency and obvious reduction in mobility, and the photoinitiator has high initiation activity and very low mobility, so that the problems of toxicity, yellowing and the like caused by the photoinitiator can be effectively solved.
The above examples are merely illustrative of the preferred embodiments of the present invention and are not intended to limit the spirit and scope of the present invention. Various modifications and improvements of the technical scheme of the present invention will fall within the protection scope of the present invention without departing from the design concept of the present invention, and the technical content of the present invention is fully described in the claims.
Claims (6)
1. A preparation method of a macromolecular thioxanthone photoinitiator is characterized by comprising the following steps: the method comprises the following steps:
step 1: adding an initiator, 2-vinyl thioxanthone and an organic solvent into a flask, stirring until the initiator is completely dissolved, slowly heating to 50-150 ℃ and reacting for 3-7h;
step 2: after the reaction is finished, cooling by using an ice water bath, spin-drying the solvent, and washing for multiple times by using an organic solvent to obtain a product, wherein the thioxanthone photoinitiator has the structural formula:
definition R 1 And R is 2 Is H, halogen atom, R 0 、OR 0 、NHR0、N(R 0 ) 2 、SH；R 0 Is a branched or straight chain or cyclic alkane containing from 1 to 24 carbon atoms.
2. The method for preparing the macromolecular thioxanthone photoinitiator according to claim 1, wherein the method comprises the following steps: the reaction equation is as follows:
3. the method for preparing the macromolecular thioxanthone photoinitiator according to claim 1, wherein the method comprises the following steps: the structural general formula of the 2-vinyl thioxanthone is as follows:
definition R 1 And R is 2 Is H, halogen atom, R 0 、OR 0 、NHR0、N(R 0 ) 2 、SH；R 0 Is a branched or straight chain or cyclic alkane containing from 1 to 24 carbon atoms.
4. The method for preparing the macromolecular thioxanthone photoinitiator according to claim 1, wherein the method comprises the following steps: the initiator is selected from one or any combination of benzoyl peroxide, tert-butyl peroxybenzoate, azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate.
5. The method for preparing the macromolecular thioxanthone photoinitiator according to claim 1, wherein the method comprises the following steps: the organic solvent is selected from one or any combination of dimethyl sulfoxide, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, benzene, toluene, xylene, acetonitrile, chlorobenzene, dichlorobenzene, anisole, petroleum ether, dioxane, tetrahydrofuran, pyridine, N-dimethylformamide, N-methylpyrrolidone, methyl tertiary butyl ether, ethylene glycol dimethyl ether, acetone, butanone, methanol, ethanol and propanol.
6. A macromolecular thioxanthone photoinitiator, characterized by: the macromolecular thioxanthone photoinitiator is prepared according to any one of claims 1-5.
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| WO2007092935A1 (en) * | 2006-02-08 | 2007-08-16 | Albemarle Corporation | Hydroxyalkylaminoalkylthioxanthones |
| CN106995430A (en) * | 2017-03-15 | 2017-08-01 | 同济大学 | New thioxanthone compound and its application |
| CN111087494A (en) * | 2019-12-31 | 2020-05-01 | 阜阳欣奕华材料科技有限公司 | Polymerizable photoinitiator and preparation method and application thereof |
| US20210147585A1 (en) * | 2018-05-11 | 2021-05-20 | Insight High Technology Co., Ltd | Polyacrylate macromolecular photoinitiator, synthesis method therefor and use thereof |
| CN113831428A (en) * | 2021-09-22 | 2021-12-24 | 贵州师范学院 | Thioxanthone-chalcone photoinitiator and preparation method and application thereof |
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| WO2007092935A1 (en) * | 2006-02-08 | 2007-08-16 | Albemarle Corporation | Hydroxyalkylaminoalkylthioxanthones |
| CN106995430A (en) * | 2017-03-15 | 2017-08-01 | 同济大学 | New thioxanthone compound and its application |
| US20210147585A1 (en) * | 2018-05-11 | 2021-05-20 | Insight High Technology Co., Ltd | Polyacrylate macromolecular photoinitiator, synthesis method therefor and use thereof |
| CN111087494A (en) * | 2019-12-31 | 2020-05-01 | 阜阳欣奕华材料科技有限公司 | Polymerizable photoinitiator and preparation method and application thereof |
| CN113831428A (en) * | 2021-09-22 | 2021-12-24 | 贵州师范学院 | Thioxanthone-chalcone photoinitiator and preparation method and application thereof |
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