CN116675798A - Single-component macromolecular thioxanthone photoinitiator and preparation method thereof - Google Patents
Single-component macromolecular thioxanthone photoinitiator and preparation method thereof Download PDFInfo
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- CN116675798A CN116675798A CN202310661246.2A CN202310661246A CN116675798A CN 116675798 A CN116675798 A CN 116675798A CN 202310661246 A CN202310661246 A CN 202310661246A CN 116675798 A CN116675798 A CN 116675798A
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- thioxanthone
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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 22
- 238000002360 preparation method Methods 0.000 title claims description 8
- -1 amino (methyl) acrylic ester Chemical class 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- 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
- 239000003999 initiator Substances 0.000 claims description 29
- 239000000047 product Substances 0.000 claims description 23
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 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 6
- 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
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- 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
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-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 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000008096 xylene 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
- 239000004342 Benzoyl peroxide Substances 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
- 229910001870 ammonium persulfate Inorganic materials 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
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 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
- 230000005012 migration Effects 0.000 abstract description 5
- 238000013508 migration Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000010146 3D printing Methods 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 125000003277 amino group Chemical group 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 231100000053 low toxicity Toxicity 0.000 abstract 1
- 238000004377 microelectronic Methods 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 239000000178 monomer Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000002211 ultraviolet spectrum Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000000852 hydrogen donor Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- 238000004383 yellowing Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 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
- 238000004061 bleaching Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/32—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
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a single-component macromolecular thioxanthone photoinitiator, which is prepared by taking 2-vinyl thioxanthone and amino (methyl) acrylic ester as comonomers through copolymerization reaction, wherein the single-component macromolecular thioxanthone photoinitiator contains both thioxanthone and amine groups, the photoinitiation activity can be obviously improved, the molecular weight of the macromolecular photoinitiator is high, the migration stability is high, the product has low toxicity and high safety, the synthesis process of the product is simple, the product is suitable for industrial production, the light matching degree with LEDs is high, and the single-component macromolecular thioxanthone photoinitiator can be used in the fields of coating, adhesives, packaging, microelectronics, 3D printing and the like.
Description
Technical Field
The invention relates to the technical field of synthesis of photoinitiators, in particular to a single-component 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 is irradiated by an incident light source, absorbs radiation energy to generate active fragments such as free radicals, cations or anions, and the like, and initiates a photosensitive material (unsaturated acrylate monomer and cyclic monomer) to perform polymerization reaction, so that the monomer is converted into a polymer. Thus, the photoinitiator is used in small amounts in the photopolymerization system, but is a key component of the system. As a hydrogen abstraction type photoinitiator with very wide application, thioxanthone has strong ultraviolet absorption and high initiation efficiency, but the thioxanthone needs to be matched with a hydrogen donor in the use process, so that residual small molecular initiator and the hydrogen donor are very easy to migrate after photopolymerization reaction occurs, thereby generating the problems of odor, toxicity, yellowing and the like.
Disclosure of Invention
First, the technical problem to be solved
In order to overcome the defects of the prior art, a single-component macromolecular thioxanthone photoinitiator and a preparation method thereof are provided, wherein the initiator has a large molecular weight and contains an ammonia hydrogen donor, and is difficult to migrate after light polymerization is initiated by illumination, so that the migration stability of the photoinitiator is improved, the toxicity and yellowing are reduced, and the odor is reduced.
(II) technical scheme
The invention is realized by the following technical scheme: the invention provides a single-component macromolecular thioxanthone photoinitiator, which has the following structural formula:
wherein R is 1 Hydrogen and methyl; r is R 2 Straight or branched chain alkane substituents containing from 1 to 4 carbon atoms including methylene, dimethylene, trimethylene, 1, 2-propylene, tetramethylene, 1, 2-butylene, 2-methyl-1, 2-propylene; r is R 3 、R 4 Methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, independently of one another,One of the isobutyl groups.
A single-component macromolecular thioxanthone photoinitiator and a preparation method thereof comprise the following steps:
step one: dissolving 2-vinyl thioxanthone and amino (methyl) acrylic ester in an organic solvent, stirring until the 2-vinyl thioxanthone and the amino (methyl) acrylic ester are completely dissolved, adding an initiator to react for a period of time, cooling by using an ice water bath, precipitating and filtering to obtain a crude product, and washing with the organic solvent for multiple times to obtain a target product;
step two: and detecting the target product in the first step.
Further, the structural general formula of the amino (methyl) acrylic ester is as follows
Further, the preparation route is as follows:
wherein R is 1 Hydrogen and methyl; r is R 2 Straight or branched chain alkane substituents containing from 1 to 4 carbon atoms including methylene, dimethylene, trimethylene, 1, 2-propylene, tetramethylene, 1, 2-butylene, 2-methyl-1, 2-propylene; r is R 3 、R 4 Is one of methyl, ethyl, propyl, isopropyl, butyl, sec-butyl and isobutyl which are independent of each other.
Further, the initiator is one of benzoyl peroxide, tert-butyl peroxybenzoate, azodiisobutyronitrile, azodiisoheptonitrile, dimethyl azodiisobutyrate, potassium persulfate and ammonium persulfate.
Further, the organic solvent is one of dichloromethane, dichloroethane, chloroform, carbon tetrachloride, dimethyl sulfoxide, benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene, acetonitrile, ethylbenzene, anisole, petroleum ether, hexane, dioxane, tetrahydrofuran, N-dimethylformamide, acetone, butanone, methanol, ethanol and propanol.
(III) beneficial effects
Compared with the prior art, the invention has the following beneficial effects:
the single-component macromolecular thioxanthone photoinitiator and the preparation method thereof have the advantages that the single-component macromolecular thioxanthone photoinitiator has high molecular weight and contains an ammonia hydrogen donor, and is difficult to migrate after light polymerization is conducted by illumination, so that the migration stability of the photoinitiator is improved, the toxicity and yellowing are reduced, and the odor is reduced; different photoinitiation groups are introduced into the same polymer chain, and the photoinitiation performance is improved by utilizing the synergistic effect; the macromolecular photoinitiator with good compatibility is designed according to the resin performance in the formula, so that the problems of migration and yellowing of the initiator in the product are avoided, and the toxicity of the product is reduced; the macromolecular skeleton also overcomes the influence of the shielding effect on the initiator to a certain extent. The polymer chain can help to reduce the probability of the coupling termination between active species, maintain higher density of active species in the reaction process, and enable the reaction to continuously and stably proceed.
Drawings
FIG. 1 is a graph showing the ultraviolet absorption spectrum of the product of example 1 of the present invention.
FIG. 2 shows the real-time conversion of double bonds for the polymerization of the product-initiated monomer PEGDA in example 2 of this invention. A drawing.
FIG. 3 is a schematic chemical structure of a one-component macromolecular thioxanthone photoinitiator.
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
2-vinyl thioxanthone (0.1 mol,29.6 g) and dimethylaminoethyl methacrylate (0.1 mol, 15.7) were dissolved in ethyl acetate (100 mL) and stirred until completely dissolved, and azobisisobutyronitrile (0.01 mol,1.64 g) as an initiator was added and stirred, reacted at 60℃for 6 hours, cooled with an ice water bath, precipitated and filtered to give a crude product, and washed with petroleum ether several times to give the objective product.
The performance of the initiator prepared in this example was tested as follows:
dissolving the synthesized product in acetonitrile solvent with molar concentration of 3-10 -5 mol·L -1 And performing ultraviolet spectrum test to obtain the ultraviolet spectrum.
And (3) dissolving the synthesized product in a monomer, carrying out real-time infrared test on double-salt tablets, and setting different mass concentration gradients (1%, 0.5%,0.25%,0.1%,0.02% and 0.01%) to obtain the double-bond real-time conversion rate of different initiator concentrations.
Experimental results: the maximum absorption wavelength of the single-component macromolecular thioxanthone photoinitiator prepared in the embodiment reaches 390nm, the initiator content is only 0.01wt% under the condition of no auxiliary initiator, and the double bond conversion rate of the monomer PEGDA in 300s is 80%.
The structural formula of the target product is as follows:
example 2
2-vinyl thioxanthone (0.1 mol,29.6 g) and diethylaminoethyl methacrylate (0.1 mol, 18.5) were dissolved in ethyl acetate (150 mL) and stirred until complete, and azobisisobutyronitrile (0.015 mol,2.46 g) as an initiator was added thereto, stirred, reacted at 65℃for 5 hours, cooled with an ice water bath, and precipitated and filtered to give a crude product, which was washed with cyclohexane several times to give the objective product.
The performance of the initiator prepared in this example was tested as follows:
dissolving the synthesized product in acetonitrile solvent with molar concentration of 3-10 -5 mol·L -1 And performing ultraviolet spectrum test to obtain the ultraviolet spectrum.
And (3) dissolving the synthesized product in a monomer, carrying out real-time infrared test on double-salt tablets, and setting different mass concentration gradients (1%, 0.5%,0.25%,0.1%,0.02% and 0.01%) to obtain the double-bond real-time conversion rate of different initiator concentrations.
Experimental results: the maximum absorption wavelength of the long-wavelength macromolecular photoinitiator prepared in the embodiment reaches 403nm, the initiator content is only 0.01wt% under the condition of no auxiliary initiator, and the double bond conversion rate of the monomer PEGDA in 300s is 92%.
The structure of the target product is as follows:
example 3
2-vinyl thioxanthone (0.1 mol,29.6 g) and diethylaminoethyl acrylate (0.1 mol,17.1 g) were dissolved in xylene (120 mL) and stirred until complete, and dibenzoyl peroxide (0.01 mol,2.42 g) as an initiator was added thereto, stirred, reacted at 90℃for 4.5 hours, cooled in an ice water bath, precipitated and filtered to obtain a crude product, and washed with n-hexane several times to obtain the objective product.
The performance of the initiator prepared in this example was tested as follows:
dissolving the synthesized product in acetonitrile solvent with molar concentration of 3-10 -5 mol·L -1 And performing ultraviolet spectrum test to obtain the ultraviolet spectrum.
And (3) dissolving the synthesized product in a monomer, carrying out real-time infrared test on double-salt tablets, and setting different mass concentration gradients (1%, 0.5%,0.25%,0.1%,0.02% and 0.01%) to obtain the double-bond real-time conversion rate of different initiator concentrations.
Experimental results: the maximum absorption wavelength of the long-wavelength macromolecular photoinitiator prepared in the embodiment reaches 405nm, the initiator content is only 0.01wt% under the condition of no auxiliary initiator, the double bond conversion rate of the monomer PEGDA in 300s is 89%, and the photobleaching effect is achieved.
The structure of the target product is as follows:
example 4
2-vinyl thioxanthone (0.1 mol,29.6 g) and N- (propylene oxyethyl) phthalimide (0.1 mol, 25.4) were dissolved in toluene (130 mL) and stirred until completely dissolved, dibenzoyl peroxide (0.01 mol,2.42 g) as an initiator was added and stirred, the mixture was reacted at 95℃for 5 hours, and the crude product was obtained by precipitation filtration after cooling with an ice water bath and washing with N-heptane a plurality of times.
The performance of the initiator prepared in this example was tested as follows:
dissolving the synthesized product in acetonitrile solvent with molar concentration of 3-10 -5 mol·L -1 And performing ultraviolet spectrum test to obtain the ultraviolet spectrum.
And (3) dissolving the synthesized product in a monomer, carrying out real-time infrared test on double-salt tablets, and setting different mass concentration gradients (1%, 0.5%,0.25%,0.1%,0.02% and 0.01%) to obtain the double-bond real-time conversion rate of different initiator concentrations.
Experimental results: the maximum absorption wavelength of the long-wavelength polymerizable photoinitiator prepared in the embodiment reaches 408nm, the initiator content is only 0.01wt% under the condition of no addition of a co-initiator, and the double bond conversion rate of the monomer PEGDA is 90% within 600s, so that the photo-bleaching effect is achieved.
The structure is as follows
The synthetic products obtained in examples 1 to 4 were added to PEGDA monomers respectively at a mass fraction of 0.01%, numbered 1,2,3,4 respectively, and after curing under an LED lamp source of 365nm, the cured bulk polymer was immersed in acetonitrile for 24 hours and sonicated for 2 hours. The leaching solution is taken to measure ultraviolet spectrum.
Experimental results: as shown in the following table, the leaching solution has no ultraviolet absorption in the 250nm-450nm band, i.e., the initiator has no small molecule migration in the initiating system.
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 one-component macromolecular thioxanthone photoinitiator, characterized by: the structural formula is as follows:
wherein R is 1 Hydrogen and methyl; r is R 2 Straight or branched chain alkane substituents containing from 1 to 4 carbon atoms including methylene, dimethylene, trimethylene, 1, 2-propylene, tetramethylene, 1, 2-butylene, 2-methyl-1, 2-propylene; r is R 3 、R 4 Is one of methyl, ethyl, propyl, isopropyl, butyl, sec-butyl and isobutyl which are independent of each other.
2. The method for preparing the single-component macromolecular thioxanthone photoinitiator according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
step one: dissolving 2-vinyl thioxanthone and amino (methyl) acrylic ester in an organic solvent, stirring until the 2-vinyl thioxanthone and the amino (methyl) acrylic ester are completely dissolved, adding an initiator to react for a period of time, cooling by using an ice water bath, precipitating and filtering to obtain a crude product, and washing with the organic solvent for multiple times to obtain a target product;
step two: and detecting the target product in the first step.
3. The method for preparing the single-component macromolecular thioxanthone photoinitiator according to claim 2, wherein the method comprises the following steps: the structural general formula of the amino (methyl) acrylic ester is
4. The method for preparing the single-component macromolecular thioxanthone photoinitiator according to claim 2, wherein the method comprises the following steps: the preparation route is as follows:
wherein R is 1 Hydrogen and methyl; r is R 2 Straight or branched chain alkane substituents containing from 1 to 4 carbon atoms including methylene, dimethylene, trimethylene, 1, 2-propylene, tetramethylene, 1, 2-butylene, 2-methyl-1, 2-propylene; r is R 3 、R 4 Is one of methyl, ethyl, propyl, isopropyl, butyl, sec-butyl and isobutyl which are independent of each other.
5. The method for preparing the single-component macromolecular thioxanthone photoinitiator according to claim 2, wherein the method comprises the following steps: the initiator is one of benzoyl peroxide, tert-butyl peroxybenzoate, azodiisobutyronitrile, azodiisoheptonitrile, dimethyl azodiisobutyrate, potassium persulfate and ammonium persulfate.
6. The method for preparing the single-component macromolecular thioxanthone photoinitiator according to claim 2, wherein the method comprises the following steps: the organic solvent is one of dichloromethane, dichloroethane, chloroform, carbon tetrachloride, dimethyl sulfoxide, benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene, acetonitrile, ethylbenzene, anisole, petroleum ether, hexane, dioxane, tetrahydrofuran, N-dimethylformamide, acetone, butanone, methanol, ethanol and propanol.
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