CN112939779B - Terephthaloyl formate type photoinitiator suitable for UV-LED deep photopolymerization and preparation method thereof - Google Patents
Terephthaloyl formate type photoinitiator suitable for UV-LED deep photopolymerization and preparation method thereof Download PDFInfo
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- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 17
- -1 aliphatic hydrocarbon radicals Chemical class 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000012043 crude product Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 11
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 10
- 239000004925 Acrylic resin Substances 0.000 claims description 10
- 229920000178 Acrylic resin Polymers 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000004440 column chromatography Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 150000003254 radicals Chemical class 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000012024 dehydrating agents Substances 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical group O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 6
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical group C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 5
- 239000013067 intermediate product Substances 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- SKBBQSLSGRSQAJ-UHFFFAOYSA-N 1-(4-acetylphenyl)ethanone Chemical compound CC(=O)C1=CC=C(C(C)=O)C=C1 SKBBQSLSGRSQAJ-UHFFFAOYSA-N 0.000 claims description 4
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 4
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 239000002274 desiccant Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 claims description 2
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- BGRWYRAHAFMIBJ-UHFFFAOYSA-N diisopropylcarbodiimide Natural products CC(C)NC(=O)NC(C)C BGRWYRAHAFMIBJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 19
- 238000010521 absorption reaction Methods 0.000 abstract description 10
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000000977 initiatory effect Effects 0.000 abstract description 4
- 150000005840 aryl radicals Chemical class 0.000 abstract description 2
- 150000002170 ethers Chemical class 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 11
- 229910052753 mercury Inorganic materials 0.000 description 11
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 239000003999 initiator Substances 0.000 description 8
- 239000011342 resin composition Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000003776 cleavage reaction Methods 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000007017 scission Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000005254 oxyacyl group Chemical group 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
- C07C69/738—Esters of keto-carboxylic acids or aldehydo-carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- 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
- C08F122/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F122/10—Esters
- C08F122/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
-
- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a terephthaloyl formate type photoinitiator suitable for ultraviolet light-emitting diode (UV-LED) deep photopolymerization, which relates to the field of photosensitive polymers, and is based on the problems that the existing photoinitiator has poor initiation performance under the irradiation of a UV-LED light source and is limited in application in the deep polymerization field, wherein the chemical structural general formula of the photoinitiator is as follows:wherein R is 1 Selected from the group consisting of C1-C16 aliphatic hydrocarbon radicals, aralkyl radicals, ethers, and aryl radicals; the invention also provides a preparation method of the photoinitiator and application of the photoinitiator in a photopolymerization system; the invention has the beneficial effects that: the photoinitiator prepared by the method has proper absorption capacity in a visible light region, ensures higher photopolymerization efficiency under the action of a UV-LED light source, can be applied to the deep polymerization field, and is beneficial to the development of the UV-LED photopolymerization industry.
Description
Technical Field
The invention belongs to the field of photosensitive high polymer materials, and particularly relates to a terephthaloyl formate type photoinitiator suitable for ultraviolet light-emitting diode (UV-LED) deep photopolymerization and application thereof in the field of photopolymerization.
Background
Photopolymerization refers to the technique of converting a liquid monomer or oligomer into a solid material under irradiation of light (ultraviolet light, visible light, or infrared light). Compared with the traditional thermal polymerization, the photopolymerization is a green technology and has the advantages of low VOC, high curing speed, energy conservation, environmental protection, low curing temperature and the like. In addition, photopolymerization technology is widely used in various fields such as functional coating, ink, adhesive, photoresist, medical and 3D printing due to its "5E" property, high Efficiency (Enabling), economy (Econometric), energy Saving (Energy Saving), and environmental friendliness (Environmental Friendly).
The UV-LED photo-curing technology first appears in 2008, even if it is a hot spot in the field of photopolymerization, the advantages of the LED light source are as follows: (1) Long service life, concentrated output energy and high energy conversion efficiency; the service life of the LED light source is generally more than 10000h, and compared with the service life of a mercury lamp, the service life of the LED light source is only about 1000 h. The main peak of the emitted light of the LED light source is narrow and single, and more than 90% of light output is concentrated in the range of 10nm of the main peak. (2) low operating temperature; the temperature of the lamp body of the LED light source is below 100 ℃, the temperature of the lamp surface is about 60 ℃, the temperature of the lamp body surface of the mercury lamp can reach 600 ℃, and the temperature of the working surface can also reach about 80 ℃. (3) instant light emission; the LED light source can be used immediately after being started without preheating, and the service life of the LED light source is not affected by the switching times. The mercury lamp needs to be preheated for 3-5 min, and after the lamp is turned off, the lamp can be restarted after being cooled for 5-10 min, and the service life is influenced by the switching times. (4) low output voltage and adjustable power; the LED light source is superior to mercury lamps in luminous intensity, uniformity and stability. And the output power of the LED light source can be adjusted through current, but the mercury lamp cannot be adjusted. (5) no mercury pollution and no ozone generation; mercury is a harmful heavy metal, seriously affects ecological environment and human health, and is inevitably polluted by mercury by using a mercury lamp. The LED light source does not use mercury, so that the environmental protection effect is self-evident, and no ozone is generated, and the LED light source is used for replacing a mercury lamp light source, so that the LED light source is a necessary path in the photopolymerization field.
The radiation wavelength of the LED light source is generally above 385nm, and common wavelengths are 395nm, 405nm, 455nm and the like. The traditional ultraviolet initiator cannot be well matched with an LED light source because the absorption wavelength of the traditional ultraviolet initiator is difficult to reach the visible light region, and the popularization and the application of the UV-LED photopolymerization technology are limited. In addition, along with the red shift of the wavelength of the light source, the absorption wavelength of the photoinitiator tends to be red shift, so that the commonly used UV-LED photopolymerization photoinitiator has good absorption capacity in the visible light region, and has color; in deep polymerization, as the UV-LED photoinitiator has strong absorption capacity in the visible light region, light irradiated by a light source can be almost absorbed by the photoinitiator at the surface layer of the photopolymerization system, so that the photoinitiator at the inner part of the polymerization system cannot effectively absorb light energy, the deep polymerization is influenced, and the application range of the photoinitiator is limited.
Disclosure of Invention
The invention provides a terephthaloyl formate photoinitiator suitable for ultraviolet light-emitting diode (UV-LED) deep photopolymerization. The photoinitiator can be well matched with a common UV-LED light source (the emission wavelength is 385nm,395nm and 405 nm), has good initiation capability, and meanwhile, compared with a commercial UV-LED photoinitiator, the photoinitiator provided by the invention has weaker absorption capability in a visible light region, so that the capability of being applied to the deep polymerization field is provided. The photoinitiator has simple synthesis process and great advantages in preparation.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
1. a terephthaloyl formate photoinitiator suitable for UV-LED deep photopolymerization, characterized in that: the chemical structural general formula of the photoinitiator is shown as follows:
wherein R is 1 Selected from the group consisting of C1-C16 aliphatic hydrocarbon radicals, aralkyl radicals, ethers and aryl radicals.
2. The terephthaloyl formate photoinitiator suitable for deep photopolymerization of UV-LED according to item 1, wherein: r is R 1 Selected from methyl, ethyl and phenyl.
3. A process for preparing a terephthaloyl formate photoinitiator suitable for deep photopolymerization of UV-LED according to item 1 or 2, characterized in that: the general synthesis process is as follows:
4. the method according to item 3, wherein: the preparation method of the photoinitiator comprises the following steps:
(1) In the step a, adding 1, 4-diacetyl benzene and an oxidant into a reaction vessel, adding a proper amount of pyridine as a solvent, refluxing and stirring for 1h at a reaction temperature of 120 ℃, cooling to 90 ℃ and reacting for 4h, wherein the reaction is carried out in a nitrogen atmosphere; after the reaction is finished, cooling the reaction liquid to room temperature, pouring the reaction liquid into water, filtering to remove black selenium powder, adding a proper amount of dilute hydrochloric acid to a pH value of about 3, extracting a water layer with a proper amount of ethyl acetate for three times, merging organic phases, drying the organic phases with a drying agent, distilling under reduced pressure to remove the ethyl acetate to obtain a crude product, and purifying the crude product with column chromatography to obtain an intermediate product A;
(2) In the step b, adding alcohol or phenol, a dehydrating agent and alkali into a reaction container, adding a proper amount of ethyl acetate as a solvent, dissolving an intermediate product A by using ethyl acetate, slowly dropwise adding the intermediate product A into the reaction container, and stirring at 25 ℃ until the dropwise addition is finished; after the addition, the white precipitate is removed by filtration, the solvent is removed by distillation under reduced pressure to obtain a crude product, and then the crude product is purified by column chromatography to obtain a final product.
5. The method according to item 4, wherein: in the step a, the oxidant is selected from selenium dioxide, potassium permanganate, potassium dichromate and hydrogen peroxide; the molar ratio of the oxidant to the 1, 4-diacetyl benzene is 1:3; the concentration of the dilute hydrochloric acid is 1mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the The drying agent is selected from anhydrous sodium sulfate and anhydrous magnesium sulfate.
6. The method according to claim 4, wherein: in the step b, the alcohol is selected from C1-C16 fatty alkyl alcohol, aralkyl alcohol and hydroxy ether; the phenol is phenol; the dehydrating agent is selected from dicyclohexylcarbodiimide, diisopropylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide; the base is selected from pyridine, 3-methylpyridine, 2-methylpyridine, 4-dimethylaminopyridine, triethylamine and diethylamine; the molar ratio of the intermediate A, the alcohol or the phenol, the dehydrating agent and the alkali is 1:3:3:0.05.
7. A free radical photopolymerizable composition comprising a terephthaloyl formate type photoinitiator according to item 1 or 2 suitable for UV-LED deep photopolymerization; the composition comprises 1% -5% of the terephthaloyl formate type photoinitiator and 95% -99% of a photocurable resin or monomer, based on the total weight of the composition.
8. The composition of item 7, wherein the photocurable resin is selected from one or more of epoxy (meth) acrylic resins, polyurethane (meth) acrylic resins, polyester (meth) acrylic resins, polyether (meth) acrylic resins, acrylated poly (meth) acrylic resins; the monomer is one or more of monofunctional, difunctional or polyfunctional (methyl) acrylic ester.
9. Use of the terephthaloyl formate photoinitiator according to item 1 or 2 for deep photopolymerization of UV-LEDs in deep photopolymerization.
In the following description of the present invention, numerical values in this application are considered to be modified by the word "about" unless explicitly stated otherwise. However, the inventors have reported the numerical values set forth in the examples as precisely as possible, even though they inevitably include certain errors.
The invention has the beneficial effects that: compared with the traditional photoinitiator, the photoinitiator prepared by the method can be applied to the field of UV-LED photopolymerization, overcomes the limitation that the common UV-LED photoinitiator is difficult to apply to the field of deep polymerization, and is beneficial to development of the photopolymerization industry.
Drawings
FIG. 1 is a photo-initiation mechanism diagram of a photoinitiator provided by the present invention;
FIGS. 2 and 3 are ultraviolet absorption spectra of terephthaloyl formate type photoinitiators prepared in Synthesis example 1, example 2, and example 3;
FIGS. 4 and 5 are respectively real-time infrared spectra of polymerization of trimethylolpropane triacrylate and tripropylene glycol diacrylate as monomers initiated by terephthaloyl formate photoinitiator prepared in Synthesis example 1;
FIG. 6 is a comparative graph of the deep polymerization of monomeric tripropylene glycol diacrylate initiated by terephthaloyl formate photoinitiator prepared in synthetic example 1 with commercial photoinitiator 819.
Detailed Description
In order that the technical scheme and advantages of the present invention may become more apparent, the present invention will be further described in detail by way of the following examples, which are not intended to limit the scope of the present invention.
The photoinitiator can be subjected to photolysis under the irradiation of a common UV-LED light source (emission wavelengths are 385nm, 390 nm and 405 nm) so as to initiate polymerization, and the mechanism is shown in the accompanying figure 1: under illumination, the photoinitiator is firstly subjected to first-step cleavage to generate a molecule of terephthaloyl free radical and two molecules of oxyacyl free radicals, then the oxyacyl radicals are subjected to second-step cleavage to remove a molecule of carbon dioxide to generate a molecule of free radical, and the terephthaloyl free radical generated by the first-step cleavage and the free radical can initiate a monomer to undergo polymerization reaction.
Example 1:
the structural formula of the photoinitiator DM-BD-F is as follows:
(a) 1, 4-diacetone (0.649 g,0.004 mol), selenium dioxide (1.553 g,0.012 mol) and 5mL pyridine are added into a 250mL single-neck flask, and the mixture is heated to 120 ℃ under the protection of nitrogen, stirred at constant temperature for 1h, cooled to 90 ℃ and stirred at constant temperature for 4h. After the reaction is finished, after the reaction solution is cooled to room temperature, black precipitates are removed by filtration, and then the reaction solution is combined with 50mL of deionized water, and 20mL of dilute hydrochloric acid (1 mol/L) is added until Ph=3; subsequently, the aqueous layer was extracted three times with ethyl acetate (30 ml×3), the organic layers were combined and dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and then the crude product was purified by column chromatography to give intermediate BDFA.
(b) Methanol (0.192 g, 0.006mol), dicyclohexylcarbodiimide (1.236 g, 0.006mol) and 4-dimethylaminopyridine (12.2 mg,0.1 mmol) were added to a 100mL single neck flask, and 30mL ethyl acetate was added as solvent; BDFA (0.444 g, 0.002mol) was dissolved in 30mL ethyl acetate and added dropwise to a 250mL single neck flask at a temperature of 25℃at a rate of 1 drop per second with stirring. After the reaction, the white precipitate is removed by filtration, the solvent is removed by distillation under reduced pressure to obtain a crude product, and then the crude product is purified by column chromatography to obtain a final product DM-BD-F, and structural identification is carried out by nuclear magnetic resonance spectroscopy.
The hydrogen spectrum data of the photoinitiator DM-BD-F are: 1 H NMR(400MHz,CDCl 3 ,ppm):δ8.11(s,4H),3.94(s,6H).
the carbon spectrum data of the photoinitiator DM-BD-F are as follows: 13 C NMR(100MHz,CDCl 3 ,ppm):δ190.31,167.79,141.80,135.54,58.43.
example 2:
the photoinitiator DE-BD-F is synthesized, and the structural formula of the DE-BD-F is as follows:
ethanol (0.276 g, 0.006mol), dicyclohexylcarbodiimide (1.236 g, 0.006mol) and 4-dimethylaminopyridine (12.2 mg,0.1 mmol) were added to a 100mL single neck flask, and 30mL ethyl acetate was added as solvent; the intermediate BDFA synthesized in example 1 (0.444 g, 0.002mol) was dissolved in 30mL ethyl acetate and added dropwise to a 100mL single neck flask at a temperature of 25℃at a rate of 1 drop per second with stirring. After the reaction, the white precipitate is removed by filtration, the solvent is removed by distillation under reduced pressure to obtain a crude product, and then the crude product is purified by column chromatography to obtain a final product DE-BD-F, and structural identification is carried out by nuclear magnetic resonance spectroscopy.
The hydrogen spectrum data of the photoinitiator DE-BD-F are: 1 H NMR(400MHz,CDCl 3 ,ppm):δ8.10(s,4H),4.35(dd,J＝8.0,8.0Hz,4H),1.39(t,J＝7.6,6H).
the carbon spectrum data of the photoinitiator DE-BD-F are: 13 C NMR(100MHz,CDCl 3 ,ppm):δ185.63,164.15,138.82,130.56,60.85,13.84.
example 3:
the light initiator DP-BD-F is synthesized, and the structural formula of the DP-BD-F is as follows:
phenol (0.564 g, 0.006mol), dicyclohexylcarbodiimide (1.236 g, 0.006mol) and 4-dimethylaminopyridine (12.2 mg,0.1 mmol) were added to a 100mL single neck flask, and 30mL ethyl acetate was added as a solvent; the intermediate BDFA synthesized in example 1 (0.444 g, 0.002mol) was dissolved in 30mL ethyl acetate and added dropwise to a 100mL single neck flask at a temperature of 25℃at a rate of 1 drop per second with stirring. After the reaction, the white precipitate is removed by filtration, the solvent is removed by distillation under reduced pressure to obtain a crude product, and then the crude product is purified by column chromatography to obtain a final product DP-BD-F, and structural identification is carried out by nuclear magnetic resonance spectroscopy.
The hydrogen spectrum data of the photoinitiator DP-BD-F are: 1 H NMR(400MHz,CDCl 3 ,ppm):δ8.14(s,4H),7.44(t,J＝7.9Hz,4H),7.33(m,6H).
the carbon spectrum data of the photoinitiator DP-BD-F are as follows: 13 C NMR(100MHz,CDCl 3 ,ppm):δ185.63,157.35,151.38,138.82,130.44,129.12,125.56,121.69.
example 4:
example 4 is intended to illustrate the absorption of terephthaloyl formate photoinitiators prepared in examples 1-3 at the emission wavelength of the LED.
50mL of anhydrous acetonitrile solutions of photoinitiators synthesized in example 1, example 2 and example 3 were prepared, respectively, at a concentration of 1X 10 -5 mol L -1 . Three different solutions were tested at wavelengths of 220-500nm using ultraviolet spectrophotometry, respectivelyAbsorption curves in the range, i.e. the ultraviolet visible absorption spectrum.
The UV-visible absorption spectra of the three photoinitiators are shown in FIG. 2 and FIG. 3; it can be seen from fig. 2 and 3 that the three photoinitiators all have a maximum absorption wavelength below 300nm, but they all have a certain absorption capacity at about 400nm, i.e. at the emission wavelength of the LED, and that this weak absorption capacity not only gives the initiator the ability to initiate at the emission wavelength of the LED, but also facilitates deep curing.
Examples 5 to 6:
examples 5-6 are intended to illustrate that the terephthaloyl formate photoinitiator prepared in example 1 is effective to initiate polymerization of monomers under irradiation of a UV-LED light source.
1. Photosensitive resin composition is disposed
Two kinds of acrylate monomers and the terephthaloyl formate type photoinitiator prepared in example 1 were respectively selected, and two kinds of photosensitive resin compositions were prepared according to the following ratio:
example 5: trimethylolpropane triacrylate (99 parts by mass), photoinitiator (1 part by mass)
Example 6: tripropylene glycol diacrylate (99 parts by mass), photoinitiator (1 part by mass)
2. Polymerization Performance test
Uniformly stirring the above composition in the absence of light, uniformly coating on a potassium bromide sheet with capillary tube to form a coating film of about 30 μm, covering with another potassium bromide sheet, placing in a real-time infrared instrument (model Nicolet 5700 of Feishan technology Co., U.S. Pat.), and using UV-LED light source (model UVEC-4II of Ricke technology Co., shenzhen, lanceolate) to obtain a coating film with a light intensity of 100mW/cm 2 ) The coating film was exposed to light at a wavelength of 405nm for 200 seconds.
The test results of the photosensitive resin composition formulated in example 5 and the photosensitive resin composition formulated in example 6 are shown in fig. 4 and fig. 5, respectively. The photoinitiator prepared by the invention can smoothly initiate the photopolymerization reaction of the acrylic ester monomer under the irradiation of a UV-LED light source with the emission wavelength of 405nm, which shows that the photoinitiator has better applicability under a UV-LED photopolymerization system.
Examples 7 to 8:
the effect of the UV-LED photoinitiator 819, which is currently commercially available, on initiating deep photopolymerization under UV-LED light irradiation with the terephthaloyl formate photoinitiator prepared in example 1 was determined:
1. two photosensitive resin compositions were prepared in the following proportions:
example 7: tripropylene glycol diacrylate (99 parts by mass), photoinitiator 819 (1 part by mass)
Example 8: tripropylene glycol diacrylate (99 parts by mass), photoinitiator DM-BD-F (1 part by mass)
2. Polymerization depth test
Two kinds of photosensitive resins were injected into a glass tube having a depth of 7.5cm and a diameter of 0.7cm, and irradiated with a UV-LED light source of 405nm at a distance of 4cm from the bottom of the glass tube. After 30 seconds the glass tube was inverted and the depth of the polymerized polytrimethylene glycol diacrylate in the test tube was measured. The test results are shown in FIG. 6. Under the same conditions, the photo-initiator photosensitive resin composition prepared by the invention has a polymerization depth of 6.6cm under the irradiation of a UV-LED light source of 405nm, can successfully initiate the deep polymerization of monomers, and the polymerization depth of a commercial photo-initiator 819 is only 0.8cm and is far lower than that of a photo-initiator DM-BD-F, which shows that the photo-initiator has excellent capability of initiating the deep polymerization under a UV-LED photo-polymerization system.
The above is only a preferred embodiment of the present invention, and the scope of the present invention is not limited to the above examples, but various process schemes without substantial differences from the concept of the present invention are within the scope of the present invention.
Claims (8)
1. A terephthaloyl formate photoinitiator suitable for UV-LED deep photopolymerization, characterized in that: the chemical structural general formula of the photoinitiator is shown as follows:
wherein R is 1 Is phenyl.
2. A method for preparing a terephthaloyl formate photoinitiator suitable for UV-LED deep photopolymerization, the photoinitiator having the chemical structural formula:
wherein R is 1 Is phenyl;
the method is characterized in that: the general synthesis process is as follows:
(a)
(b)
wherein in the step b, the phenol is phenol.
3. The method according to claim 2, characterized in that: the preparation method of the photoinitiator comprises the following steps:
(1) In the step a, 1, 4-diacetyl benzene and an oxidant are added into a reaction vessel, a proper amount of pyridine is added as a solvent, the mixture is refluxed and stirred for 1h at the reaction temperature of 120 ℃, then the mixture is cooled to 90 ℃ for reaction for 4h, and the reaction is carried out in a nitrogen atmosphere; after the reaction is finished, cooling the reaction liquid to room temperature, pouring the reaction liquid into water, filtering to remove black selenium powder, adding a proper amount of dilute hydrochloric acid to a pH value of 3, extracting a water layer with a proper amount of ethyl acetate three times, merging organic phases, drying the organic phases with a drying agent, distilling under reduced pressure to remove the ethyl acetate to obtain a crude product, and purifying the crude product with column chromatography to obtain an intermediate product A;
(2) In the step b, phenol, a dehydrating agent and alkali are added into a reaction container, a proper amount of ethyl acetate is added as a solvent, an intermediate product A is dissolved by ethyl acetate, and is slowly dripped into the reaction container, and stirring is carried out at 25 ℃ until dripping is finished; after the addition, the white precipitate is removed by filtration, the solvent is removed by distillation under reduced pressure to obtain a crude product, and then the crude product is purified by column chromatography to obtain a final product.
4. A method according to claim 3, characterized in that: in the step a, the oxidant is selected from selenium dioxide, potassium permanganate, potassium dichromate and hydrogen peroxide; the molar ratio of the oxidant to the 1, 4-diacetyl benzene is 1:3; the concentration of the dilute hydrochloric acid is 1mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the The drying agent is selected from anhydrous sodium sulfate and anhydrous magnesium sulfate.
5. A method according to claim 3, characterized in that: in said step b, said dehydrating agent is selected from dicyclohexylcarbodiimide, diisopropylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide; the base is selected from pyridine, 3-methylpyridine, 2-methylpyridine, 4-dimethylaminopyridine, triethylamine and diethylamine; the molar ratio of the intermediate A to the phenol to the dehydrating agent to the base is 1:3:3:0.05.
6. A free radical photopolymerizable composition comprising a terephthaloyl formate type photoinitiator according to claim 1 suitable for UV-LED deep photopolymerization; the composition comprises 1% -5% of the terephthaloyl formate type photoinitiator and 95% -99% of a photocurable resin or monomer, based on the total weight of the composition.
7. The composition of claim 6, wherein the photocurable resin is selected from one or more of epoxy (meth) acrylic resin, polyurethane (meth) acrylic resin, polyester (meth) acrylic resin, polyether (meth) acrylic resin, acrylated poly (meth) acrylic resin; the monomer is one or more of monofunctional, difunctional or polyfunctional (methyl) acrylic ester.
8. The application of terephthaloyl formate photoinitiator suitable for UV-LED deep photopolymerization in deep photopolymerization is characterized in that: the chemical structural general formula of the photoinitiator is shown as follows:
wherein R is 1 Selected from methyl, ethyl and phenyl.
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