CN115448948A - Bisacylphosphine oxide photoinitiator as well as preparation method and application thereof - Google Patents
Bisacylphosphine oxide photoinitiator as well as preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000000016 photochemical curing Methods 0.000 claims abstract description 11
- 238000001723 curing Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 53
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 45
- 239000002904 solvent Substances 0.000 claims description 41
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- 238000004809 thin layer chromatography Methods 0.000 claims description 20
- 238000012544 monitoring process Methods 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 239000012074 organic phase Substances 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- -1 2,4, 6-trimethyl benzoyl phenyl ethyl Chemical group 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 6
- YMCOIFVFCYKISC-UHFFFAOYSA-N ethoxy-[2-(2,4,6-trimethylbenzoyl)phenyl]phosphinic acid Chemical compound CCOP(O)(=O)c1ccccc1C(=O)c1c(C)cc(C)cc1C YMCOIFVFCYKISC-UHFFFAOYSA-N 0.000 claims description 6
- 150000007529 inorganic bases Chemical class 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000012071 phase Substances 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 230000000171 quenching effect Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 235000009518 sodium iodide Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 238000013508 migration Methods 0.000 abstract description 11
- 238000000576 coating method Methods 0.000 abstract description 10
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- 239000005548 dental material Substances 0.000 abstract description 7
- 238000013461 design Methods 0.000 abstract description 4
- 238000007639 printing Methods 0.000 abstract description 4
- 238000010146 3D printing Methods 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 39
- 238000001228 spectrum Methods 0.000 description 12
- 230000000977 initiatory effect Effects 0.000 description 11
- 239000003999 initiator Substances 0.000 description 10
- 239000000178 monomer Substances 0.000 description 9
- 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 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000012360 testing method Methods 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 235000019504 cigarettes Nutrition 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012949 free radical photoinitiator Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- 241000022852 Letis Species 0.000 description 1
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- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000012682 free radical photopolymerization Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3247—Esters of acids containing the structure -C(=X)-P(=X)(R)(XH) or NC-P(=X)(R)(XH), (X = O, S, Se)
- C07F9/3252—Esters of acids containing the structure -C(=X)-P(=X)(R)(XH) or NC-P(=X)(R)(XH), (X = O, S, Se) containing the structure -C(=X)-P(=X)(R)(XR), (X = O, S, Se)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3264—Esters with hydroxyalkyl compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- Health & Medical Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
The invention discloses a bisacylphosphine oxide photoinitiator and a preparation method and application thereof; the structural formula of the bisacylphosphine oxide photoinitiator is as follows:
wherein n =1,2,3,4,5,6,7,8,9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19,20. The bisacylphosphine oxide photoinitiator disclosed by the invention has zero migration and high photoinitiation efficiency, can be used as a photoinitiator initiated by a UV-LED and a visible light purple light source, is used for photocuring coatings, printing ink, adhesives, plane art design, 3D printing, dental materials and the like, can realize deep curing, and has wide market application prospects.
Description
Technical Field
The invention belongs to the technical field of photoinitiators, and particularly relates to a bisacylphosphine oxide photoinitiator and a preparation method and application thereof.
Technical Field
The acylphosphine oxide photoinitiator is a type I cracking type free radical photoinitiator, the ultraviolet-visible effective absorption spectrum of the acylphosphine oxide photoinitiator is mainly between 350 and 400nm, the acylphosphine oxide photoinitiator can initiate free radical photopolymerization under the irradiation of a light source in the wavelength range, and the acylphosphine oxide photoinitiator has the characteristics of high initiation efficiency and excellent deep curing.
Currently, TPO-L (2, 4, 6-trimethyl benzoyl phenyl ethyl phosphonate) is an I-type cracking free radical photoinitiator widely applied in industrialization, has high initiation efficiency, high solubility in photocuring oligomers and functional monomers and excellent deep curing performance, and is mainly applied to the fields of ultraviolet curing wood coatings, printing ink, 3D printing and the like. With the continuous development of the photo-curing technology, in addition to high initiation efficiency, the reduction of the mobility of the photo-initiator also becomes the main trend of the development of the photo-initiator. The low-migration photoinitiator is mainly applied to human body contactable coatings, such as home decoration woodware coatings, food packaging ink, cigarette packet ink and dental materials. TPO-L belongs to micromolecule photoinitiators, the problem of high mobility of an applied photocuring system is solved, the application of the TPO-L in a plurality of low-mobility fields is limited, and the development of the acyl phosphine oxide photoinitiator with low mobility and high initiation efficiency becomes the technical development trend.
The acylphosphine oxide photoinitiator TPO-L (2,4,6-trimethyl benzoyl phenyl ethyl phosphonate) prepared by the patent CN107226824A has the characteristics of high initiation efficiency and good solubility, has potential harm to human bodies and environment due to high mobility, and is less applied to the fields of low-mobility food packaging, cigarette packets, dental materials and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to reduce the problem of high mobility of the photoinitiator in the coating, provides a bisacylphosphine oxide photoinitiator with no migration, high initiation efficiency and high solubility and a preparation method thereof, is applied to UV-LED and visible light purple light photocuring coatings, and has the characteristics of no migration and high initiation rate; the application range of the acylphosphine oxide photoinitiator in the fields of food outer packaging, cigarette case printing ink and dental materials is increased, and the application of the photocuring technology in environment-friendly coating and printing ink is expanded. Meanwhile, the method has higher initiation efficiency in a visible light and purple light wave band of non-ultraviolet light, and has wide application prospect in the medical field of dental materials and the like.
The purpose of the invention is realized by the following technical scheme:
a bisacylphosphine oxide photoinitiator has the following structural formula:
wherein n =1,2,3,4,5,6,7,8,9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19,20.
The preparation method of the bisacylphosphine oxide photoinitiator comprises the following steps:
(1) Dissolving an inorganic base and 2,4, 6-trimethyl benzoyl phenyl ethyl phosphonate in a solvent 1, and monitoring the reaction to be complete by TLC; purifying to obtain a product 1; the yield is more than or equal to 85 percent;
(2) Adding the product 1 into a sulfuric acid aqueous solution, monitoring by TLC (thin layer chromatography) until the reaction is complete, and purifying to obtain a product 2; the yield is more than or equal to 95 percent;
(3) Dissolving the product 2 in a solvent 3, adding a catalyst and a chlorine-containing raw material, stirring, monitoring by TLC (thin layer chromatography) until the reaction is complete, and purifying to obtain a product 3;
(4) Adding the product 3 into a solvent 4, adding an acid-binding agent and a diol derivative, monitoring by TLC (thin layer chromatography) until the reaction is complete, and purifying to obtain a photoinitiator; the yield is more than or equal to 50 percent;
the structural formula of the product 1 is as follows:
the structural formula of the product 2 is as follows:
the structural formula of the product 3 is as follows:
preferably, in the step (1), the inorganic base is one or more of sodium iodide, sodium hydroxide, sodium carbonate and sodium bicarbonate;
preferably, in the step (1), the solvent 1 is one or two of acetone and 2-butanone.
Preferably, in the step (1), the molar ratio of the ethyl 2,4, 6-trimethylbenzoylphenylphosphonate to the inorganic base is 1: 1.0-3.0;
preferably, in the step (1), the mass ratio of the ethyl 2,4, 6-trimethylbenzoylphenylphosphonate to the solvent 1 is 1: 15-30;
preferably, in the step (1), the temperature of the reaction is 40 ℃ to 80 ℃; the reaction time is 10-48 hours.
Preferably, the purification in step (1) is performed by washing with solvent 1 for 3-5 times and removing the solvent under reduced pressure.
Preferably, in the step (2), the concentration of the aqueous sulfuric acid solution is 0.5-lmmol/L.
Preferably, in the step (2), the addition amount of the aqueous sulfuric acid solution is adjusted to a pH value of 0-1.
Preferably, in the step (2), the temperature of the reaction is 15 ℃ to 40 ℃; the reaction time is 1-10 hours.
Preferably, the purification in step (2) is ethyl acetate extraction 3-5 times, organic phases are combined, and the organic phases are washed 3-5 times with saturated sodium chloride solution, dried over anhydrous sodium sulfate, filtered, and the solvent is removed under reduced pressure.
Preferably, the anhydrous sodium sulfate is dried by adding the anhydrous sodium sulfate into the organic phase containing the product, uniformly mixing and stirring, observing that the sodium sulfate is a flowing powder, and standing for 30 minutes to 2 hours until no obvious moisture exists in the system.
Preferably, in the step (3), the solvent 3 is one or two of toluene and dichloromethane.
Preferably, in step (3), the catalyst is N, N-dimethylformamide.
Preferably, in the step (3), the chlorine-containing raw material is one or two of thionyl chloride and formyl chloride.
Preferably, in the step (3), the mass ratio of the product 2 to the solvent 3 is 1: 10-40.
Preferably, in the step (3), the mass ratio of the product 2 to the catalyst is 1: 0.05-0.2;
preferably, in the step (3), the mass ratio of the product 2 to the chlorine-containing raw materials is 1: 1.5-10;
preferably, in the step (3), the temperature of the reaction is 15 ℃ to 110 ℃; the reaction time is 3-24 hours.
Preferably, the purification in step (3) is to remove the solvent and the chlorine-containing raw material under reduced pressure.
Preferably, in the step (4), the solvent 4 is dichloromethane.
Preferably, in the step (4), the acid-binding agent is triethylamine.
Preferably, in step (4), the diol derivative is
Wherein n =1,2,3,4,5,6,7,8,9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19,20.
Preferably, in the step (4), the mass ratio of the product 3 to the solvent 4 is 1: 10-30;
preferably, in the step (4), the mass ratio of the product 3 to the acid binding agent is 1: 0.2-1;
preferably, in the step (4), the mass ratio of the product 3 to the diol derivative is 1: 0.2-0.5;
preferably, in the step (4), the temperature of the reaction is 15 ℃ to 50 ℃; the reaction time is 2-24 hours.
Preferably, the purification in the step (4) is quenching the reaction with deionized water; extracting with ethyl acetate for 3-5 times, mixing organic phases, drying with anhydrous sodium sulfate, filtering, removing solvent under reduced pressure, performing column chromatography with petroleum ether and ethyl acetate mixed solvent as mobile phase, and drying.
Preferably, the anhydrous sodium sulfate is dried by adding the anhydrous sodium sulfate into the organic phase containing the product, uniformly mixing and stirring, observing that the sodium sulfate is a flowing powder, and standing for 30 minutes to 2 hours until no obvious moisture exists in the system.
More preferably, the volume ratio of the mixed solvent of the petroleum ether and the ethyl acetate is 1 to (1-10).
Further preferably, the drying is vacuum blotting.
The application of the bisacylphosphine oxide photoinitiator in photocuring.
Preferably, the light wavelength of the light curing is 350-420nm.
Further preferably, the light curing has an irradiation wavelength of 405 to 420nm.
Compared with the prior art, the invention has the advantages and beneficial effects that:
(1) In order to solve the problem of high migration of residual photoinitiators after UV-LED photoinitiators are subjected to photocuring, the invention provides a bisacylphosphine oxide photoinitiator which has the characteristics of high initiation efficiency, zero migration, high solubility and deep curing, is applied to UV-LED and visible light purple light photocuring coatings, ink coatings, adhesives, planar art designs, 3D printing, dental materials and the like, and can realize zero migration of photoinitiators. The photoinitiator has the characteristic of no migration, and can be applied to the field of low-migration photocuring.
(2) The bisacylphosphine oxide photoinitiator is a photoinitiator with zero migration, high initiation efficiency, excellent solubility and deep curing.
(3) The bisacylphosphine oxide photoinitiator disclosed by the invention has high initiation efficiency in visible light (405-420 nm violet light), is high in safety and less harmful to a human body compared with traditional ultraviolet light, and has obvious advantages in the fields of dental materials and the like which are in contact with the human body.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of the acylphosphino derivatives prepared in example 1.
FIG. 2 is a nuclear magnetic carbon spectrum of the acylphosphino derivatives prepared in example 1.
FIG. 3 is a nuclear magnetic phosphorus spectrum of the acylphosphino derivative prepared in example 1.
FIG. 4 is a nuclear magnetic hydrogen spectrum of the acylphosphine oxide derivative prepared in example 2.
FIG. 5 is a nuclear magnetic carbon spectrum of the acylphosphino derivatives prepared in example 2.
FIG. 6 is a nuclear magnetic phosphorus spectrum of the acylphosphino derivative prepared in example 2.
FIG. 7 is a nuclear magnetic hydrogen spectrum of the acylphosphine oxide derivative prepared in example 3.
FIG. 8 is a nuclear magnetic carbon spectrum of the acylphosphino derivative prepared in example 3.
FIG. 9 is a nuclear magnetic phosphorus spectrum of the acylphosphino derivative prepared in example 3.
FIG. 10 is a UV-Vis spectrum of acylphosphinoxy derivatives prepared in examples 1-3 and TPO-L.
FIG. 11 is a C = C conversion curve at LED @365nm for the acylphosphinoxy derivatives prepared in examples 1-3 and TPO-L initiator.
FIG. 12 is a plot of C = C conversion at LED @385nm for the acylphosphinoxy derivatives prepared in examples 1-3 and the TPO-L initiator.
FIG. 13 is a C = C conversion curve at LED @420nm for acylphosphino derivatives and TPO-L initiators prepared in examples 1-3.
Detailed Description
The present invention will be described in further detail with reference to the following examples and drawings, but the embodiments and the scope of the present invention are not limited thereto.
Example 1
(1) Dissolving sodium iodide (1.4 mol) and ethyl 2,4, 6-trimethylbenzoylphenylphosphonate (1 mol) in 2-butanone (30 mol) at room temperature, adjusting the temperature to 80 ℃, reacting for a period of time (10 h), and monitoring the reaction to be complete by TLC; washing with 2-butanone for 3-5 times, and removing solvent under reduced pressure to obtain product 1 with yield of 88%.
(2) At room temperature, adding the product 1 into sulfuric acid aqueous solution (0.5 mmol/L), adjusting the pH value to 1, adjusting the temperature to 40 ℃, reacting for a period of time (1 h), monitoring the reaction to be complete by TLC, extracting with ethyl acetate for 3-5 times, combining organic phases, washing with saturated sodium chloride solution for 3 times, drying with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure to obtain the product 2 with the yield of 97%.
(3) Dissolving the product 2 (1 mol) in toluene (27 mol), adding N, N-dimethylformamide (0.05 mol) and thionyl chloride (10 mol), adjusting the temperature to 110 ℃, reacting for a period of time (24 h), monitoring the reaction by TLC to be complete, and removing the solvent and thionyl chloride under reduced pressure to obtain the product 3.
(4) Adding the product 3 (1 mol) into dichloromethane (10 mol), adding triethylamine (0.2 mol) and triethylene glycol (0.5 mol), adjusting the temperature to 15 ℃, reacting for a period of time (24 h), monitoring the reaction by TLC (thin layer chromatography) until the reaction is complete, quenching the reaction by deionized water, extracting for 3-5 times by ethyl acetate, combining organic phases, drying by anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, using a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of 1: 2 as a mobile phase, performing column chromatography, and drying to obtain the photoinitiator, wherein the yield is 51%.
The nuclear magnetic hydrogen spectra of the photoinitiator obtained in this example are shown in fig. 1,2, and 3. The target product prepared in the present application is illustrated.
Example 2
(1) Dissolving sodium hydroxide (1.0 mol) and ethyl 2,4, 6-trimethylbenzoylphenylphosphonate (1 mol) in 2-butanone (15 mol), adjusting the temperature to 65 ℃, reacting for a period of time (24 h), and monitoring the reaction to be complete by TLC; washing with 2-butanone 3-5 times, and removing solvent under reduced pressure to obtain product 1 with yield of 89%.
(2) Adding the product 1 (1 mol) into sulfuric acid aqueous solution (1 mmol/L), adjusting the pH value to 1, monitoring the reaction by TLC until the reaction is complete, adjusting the temperature to 15 ℃, reacting for a period of time (10 h), extracting with ethyl acetate for 3-5 times, combining organic phases, washing with saturated sodium chloride solution for 3 times, drying with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure to obtain a product 2, wherein the yield is more than or equal to 95%.
(3) Dissolving the product 2 (1 mol) in dichloromethane (40 mol), adding N, N-dimethylformamide (0.2 mol) and formyl chloride (1.5 mol), adjusting the temperature to 25 ℃, reacting for a period of time (12 h), monitoring the reaction by TLC to be complete, and removing the solvent and chlorine-containing raw materials under reduced pressure to obtain a product 3.
(4) Adding the product 3 (1 mol) into dichloromethane (20 mol), adding triethylamine (1 mol) and tetraethyleneglycol (0.35 mol), adjusting the temperature to 40 ℃, reacting for a period of time (12 h), monitoring the reaction by TLC (thin layer chromatography) until the reaction is complete, quenching the reaction by using deionized water, extracting for 3-5 times by using ethyl acetate, combining organic phases, drying by using anhydrous sodium sulfate, filtering, removing a solvent under reduced pressure, using a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of 1: 3 as a mobile phase, performing column chromatography, and drying to obtain a photoinitiator; the yield was 55%.
The nuclear magnetic hydrogen spectra of the photoinitiator obtained in this example are shown in fig. 4,5, and 6. The target product prepared in the present application is illustrated.
Example 3
(1) Sodium bicarbonate (3.0 mol)) and ethyl 2,4, 6-trimethylbenzoylphenylphosphonate (1 mol) were dissolved in acetone (25 mol), the temperature was adjusted to 40 ℃, the reaction was carried out for a period of time (48 h), and the reaction was monitored by TLC to completion; washing with solvent 1 for 3-5 times, and removing solvent under reduced pressure to obtain product 1; the yield is more than or equal to 85 percent.
(2) Adding the product 1 (1 mol) into a sulfuric acid aqueous solution (0.8 mmol/L), monitoring the reaction to be complete by using a TLC (thin layer chromatography), adjusting the temperature to 25 ℃, reacting for a period of time (6 h), extracting for 3-5 times by using ethyl acetate, combining organic phases, washing for 3 times by using a saturated sodium chloride solution, drying by using anhydrous sodium sulfate, filtering, and removing the solvent under reduced pressure to obtain a product 2; the yield was 96%.
(3) Dissolving the product 2 (1 mol) in dichloromethane (27 mol), adding N, N-dimethylformamide (0.1) and formyl chloride (7 mol), adjusting the temperature to 25 ℃, reacting for a period of time (6 h), monitoring the reaction by TLC to be complete at 15-110 ℃ for 3-24h, and removing the solvent and chlorine-containing raw materials under reduced pressure to obtain a product 3.
(4) Adding the product 3 (1 mol) into dichloromethane (30 mol), adding triethylamine (0.4) and heptaglycol (0.2), monitoring the reaction to be complete by TLC (thin layer chromatography), cooling the reaction to 50 ℃ by 15 ℃ for 2-24h, and quenching the reaction by deionized water; extracting with ethyl acetate for 3-5 times, mixing organic phases, drying with anhydrous sodium sulfate, filtering, removing solvent under reduced pressure, performing column chromatography with petroleum ether and ethyl acetate mixed solvent at volume ratio of 1: 5 as mobile phase, and drying to obtain photoinitiator; the yield was 53%.
The nuclear magnetic hydrogen spectra of the photoinitiators obtained in this example are shown in fig. 7,8, and 9. The target product prepared in the application is illustrated.
Performance testing
TPO-L has the following structural formula:
(1) Solubility test
Photoinitiators (photoinitiator prepared in examples 1-3 and TPO-L) were mixed with three monomers, hydroxypropyl methacrylate (HPMA), 1, 6-hexanediol diacrylate (HDDA), trimethylolpropane triacrylate (TMPTA), respectively, at room temperature, and sonicated for 1min, with increasing photoinitiator until the photoinitiator just completely dissolved. The solubility of the initiator in the monomer was tested. Recording the mass of the photoinitiator as m light, the mass of the monomer as m single, and the solubility S of the photoinitiator in the monomer according to the following formula:
TABLE 1 solubility of photoinitiators in different monomers
| Monomer | Example 1 | Example 2 | Example 3 | TPO-L |
| HPMA | ＞50％ | ＞50％ | ＞50％ | ＞50％ |
| HDDA | ＞50％ | ＞50％ | ＞50％ | ＞50％ |
| TMPTA | ＞50％ | ＞50％ | ＞50％ | ＞50％ |
As can be seen from Table 1, the solubility of the photoinitiators of the examples in all three monomers and TPO-L is greater than 50%, and the solubility is good. In industrial application, the initiator has high solubility, so that the formula generation cost can be reduced, the energy consumption generated by dissolving the initiator is reduced, the production efficiency is improved, and the solubility of the photoinitiator restricts the breadth and the depth of industrial application. The initiator has excellent solubility in HPMA, HDDA and TMPTA, and reaches the design target.
(2) Migration test
The TMPTA mixture containing 2wt% of photoinitiator (photoinitiator prepared in examples 1-3 and TPO-L) was spread uniformly in a 250mL flat bottom flask, the flask was purged with nitrogen three times and then lit with a 365nm LED point source (100 mW/cm) 2 ) Irradiation for 5min ensured complete curing. The solidified film was removed and ground into a powder. The solidified membrane powder (500 mg-1000 mg) was weighed into 5mL of acetonitrile, stirred for 48 hours, filtered, and the filtrate was made to volume of 10mL. The absorbance of the solution was tested and the mobility was calculated according to lambert-beer law as follows:
a is the absorbance at the maximum absorption wavelength of the photoinitiator, mr is the relative molecular mass of the photoinitiator,. Epsilon.is the molar extinction coefficient at the maximum absorption wavelength,. Epsilon.is the length of the absorption cell (1 cm), m is the length of the absorption cell 0 Is the mass of the cured film powder.
TABLE 2 mobility of the photoinitiators
As can be seen from Table 2, the photoinitiator used in the examples of the present invention has zero mobility, and the competitive product TPO-L is 0.98%;
(3) Double bond conversion rate: 1wt% of initiator is added into monomer trimethylolpropane triacrylate (TMPTA) to be evenly stirred; a drop of the mixture was spread evenly on a polypropylene film, the upper layer was air-insulated with a layer of polypropylene film, and the thickness of the coating was controlled to about 40 microns. And irradiating by using LED point light sources with the wavelengths of 365nm, 385nm and 420nm, and testing the double bond conversion rate by using a Fourier transform real-time infrared spectrometer Nico letIS 50.
TABLE 3 conversion of the photoinitiator double bonds
From Table 3, it can be seen that the double bond conversion rate of example 1 is higher than that of TPO-L under 365nm light source irradiation; under the light source of 420nm, the double bond conversion rate of example 1 is close to that of TPO-L, and the conversion rate of examples 2 and 3 is higher than that of TPO-L. The conclusion is that the conversion of the double bonds at 420nm for the example photoinitiators is close to or higher than that of the commercially available TPO-L. Because the conversion rate of TPO-L double bonds is higher, the conversion rate of the double bonds of the photoinitiator is higher, and the design goal is completed.
The UV-Vis spectra of the acylphosphine oxide derivatives prepared in examples 1-3 and TPO-L are shown in FIG. 10. As can be seen from FIG. 10, the UV absorption spectrum peak pattern of the photoinitiator prepared in the example is close to that of the commercially available TPO-L, and the absorption wavelength is close, the molar extinction coefficient of the photoinitiator of the example is more than 2 times that of the commercially available TPO-L under the same wavelength, and the light absorption capability of the photoinitiator of the example is stronger under the same light source.
The C = C conversion curves at LED @365nm for the photoinitiators prepared in examples 1-3 and TPO-L are shown in FIG. 11. The C = C conversion curves at led @385nm for the photoinitiators prepared in examples 1-3 and TPO-L are shown in fig. 12. The C = C conversion curves of the photoinitiators and TPO-L prepared in examples 1-3 at led @420nm are shown in fig. 13.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A bisacylphosphine oxide photoinitiator is characterized by having a structural formula as follows:
wherein n =1,2,3,4,5,6,7,8,9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19,20.
2. A process for preparing the bisacylphosphine oxide photoinitiator according to claim 1, comprising the steps of:
(1) Dissolving an inorganic base and 2,4, 6-trimethyl benzoyl phenyl ethyl phosphonate in a solvent 1, and monitoring the reaction to be complete by TLC; purifying to obtain a product 1;
(2) Adding the product 1 into a sulfuric acid aqueous solution, monitoring by TLC (thin layer chromatography) until the reaction is completed, and purifying to obtain a product 2;
(3) Dissolving the product 2 in a solvent 3, adding a catalyst and a chlorine-containing raw material, stirring, monitoring by TLC (thin layer chromatography) until the reaction is complete, and purifying to obtain a product 3;
(4) Adding the product 3 into a solvent 4, adding an acid-binding agent and a diol derivative, monitoring by TLC (thin layer chromatography) until the reaction is complete, and purifying to obtain a photoinitiator;
the structural formula of the product 1 is as follows:
the structural formula of the product 2 is as follows:
the structural formula of the product 3 is as follows:
3. the preparation method according to claim 2, wherein in the step (1), the inorganic base is one or more of sodium iodide, sodium hydroxide, sodium carbonate and sodium bicarbonate;
the solvent 1 is one or two of acetone and 2-butanone;
the molar ratio of the 2,4, 6-trimethylbenzoyl phenyl ethyl phosphonate to the inorganic base is 1: 1.0-3.0;
the mass ratio of the 2,4, 6-trimethylbenzoyl phenyl phosphonic acid ethyl ester to the solvent 1 is 1: 15-30;
the temperature of the reaction is 40 ℃ to 80 ℃; the reaction time is 10-48 hours;
the purification is carried out by washing 3-5 times with a solvent 1 and removing the solvent under reduced pressure.
4. The method according to claim 2, wherein in the step (2), the concentration of the aqueous sulfuric acid solution is 0.5 to 1mmol/L;
the addition amount of the sulfuric acid aqueous solution is to adjust the pH value to 0-1;
the temperature of the reaction is 15 ℃ to 40 ℃; the reaction time is 1-10 hours;
the purification is extracting with ethyl acetate for 3-5 times, combining organic phases, washing with saturated sodium chloride solution for 3-5 times, drying with anhydrous sodium sulfate, filtering, and removing solvent under reduced pressure.
5. The production method according to claim 2, wherein in the step (3), the solvent 3 is one or both of toluene and dichloromethane;
the catalyst is N, N-dimethylformamide;
the chlorine-containing raw material is one or two of thionyl chloride and formyl chloride;
the mass ratio of the product 2 to the solvent 3 is 1: 10-40;
the mass ratio of the product 2 to the catalyst is 1: 0.05-0.2;
the mass ratio of the product 2 to the chlorine-containing raw material is 1: 1.5-10;
the temperature of the reaction is 15 ℃ to 110 ℃; the reaction time is 3 to 24 hours.
6. The method according to claim 2, wherein the purification in step (3) is to remove the solvent and the chlorine-containing raw material under reduced pressure.
7. The method according to claim 2, wherein in the step (4), the solvent 4 is dichloromethane;
the acid-binding agent is triethylamine;
the diol derivative is
Wherein n =1,2,3,4,5,6,7,8,9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19,20;
the mass ratio of the product 3 to the solvent 4 is 1: 10-30;
the mass ratio of the product 3 to the acid-binding agent is 1: 0.2-1;
the mass ratio of the product 3 to the diol derivative is 1: 0.2-0.5;
the temperature of the reaction is 15 ℃ to 50 ℃; the reaction time is 2-24 hours.
8. The method of claim 2, wherein the purification of step (4) is quenching the reaction with deionized water; extracting with ethyl acetate for 3-5 times, mixing organic phases, drying with anhydrous sodium sulfate, filtering, removing solvent under reduced pressure, performing column chromatography with petroleum ether and ethyl acetate mixed solvent as mobile phase, and drying.
9. Use of the bisacylphosphine oxide photoinitiator according to claim 1 in photocuring.
10. Use according to claim 9, wherein the light curing is at a wavelength of 405-420nm.
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| CN107001400A (en) * | 2014-05-30 | 2017-08-01 | 意大利艾坚蒙树脂有限公司 | Multifunctional acylphosphine oxide light trigger |
| CN109071979A (en) * | 2016-05-04 | 2018-12-21 | 爱克发有限公司 | Acylphosphine oxide photoinitiator |
| CN110144020A (en) * | 2019-06-11 | 2019-08-20 | 长沙新宇高分子科技有限公司 | A kind of Beta-cyclodextrin-based photoinitiator, preparation method and application |
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| CN107001400A (en) * | 2014-05-30 | 2017-08-01 | 意大利艾坚蒙树脂有限公司 | Multifunctional acylphosphine oxide light trigger |
| CN109071979A (en) * | 2016-05-04 | 2018-12-21 | 爱克发有限公司 | Acylphosphine oxide photoinitiator |
| CN110144020A (en) * | 2019-06-11 | 2019-08-20 | 长沙新宇高分子科技有限公司 | A kind of Beta-cyclodextrin-based photoinitiator, preparation method and application |
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