CN115785023A - Preparation method of photoinitiator, product and application thereof - Google Patents
Preparation method of photoinitiator, product and application thereof Download PDFInfo
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- CN115785023A CN115785023A CN202211555054.5A CN202211555054A CN115785023A CN 115785023 A CN115785023 A CN 115785023A CN 202211555054 A CN202211555054 A CN 202211555054A CN 115785023 A CN115785023 A CN 115785023A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000047 product Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000012074 organic phase Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000003495 polar organic solvent Substances 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Chemical group 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 14
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000005580 one pot reaction Methods 0.000 abstract description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 238000000746 purification Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 4-methylthiophenyl Chemical group 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical group [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- DGMOBVGABMBZSB-UHFFFAOYSA-N 2-methylpropanoyl chloride Chemical compound CC(C)C(Cl)=O DGMOBVGABMBZSB-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 206010074268 Reproductive toxicity Diseases 0.000 description 1
- PVQATPQSBYNMGE-UHFFFAOYSA-N [benzhydryloxy(phenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)OC(C=1C=CC=CC=1)C1=CC=CC=C1 PVQATPQSBYNMGE-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000007696 reproductive toxicity Effects 0.000 description 1
- 231100000372 reproductive toxicity Toxicity 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
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- 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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of a photoinitiator, a product and application thereof, wherein the preparation method takes 2-methyl-1- [ 4-halogenated phenyl ] -2- (4-morpholinyl) -1-acetone and thiourea as raw materials, the photoinitiator is obtained through one-step reaction, the raw materials are simple in composition, the reaction process is short, the energy consumption and the cost are low, side reactions are few, the yield of the target product is high, the color of the obtained photoinitiator is white, and the product purity is high.
Description
Technical Field
The invention belongs to the field of photocuring, and relates to a preparation method of a photoinitiator, a product and application thereof.
Background
2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone (photoinitiator 907) is widely applied by virtue of high initiating efficiency, low price advantage and deep curing capability suitable for a colored system; however, reproductive toxicity is becoming more and more of a concern to the industry; especially after appearing in the 22 nd batch hazardous substance control list of the European Union, the search for a new substitute of the photoinitiator 907 becomes a problem which needs to be solved at present.
As an alternative to the photoinitiator 907, a compound having two groups capable of photoinitiation; thereby having higher photoinitiator activity;
CN103664827A discloses a preparation method of a photoinitiator of the above formula, which comprises the following steps: (1) Dissolving diphenyl sulfide and isobutyryl chloride in a first solvent, and carrying out Friedel-crafts reaction under the catalytic action of aluminum trichloride; (2) Performing halogenation reaction on the product obtained in the step (1) and halogen; (3) Mixing the halogenated product in the step (2) with sodium methoxide in a second solvent, and carrying out epoxidation reaction under the action of a catalyst; (4) Carrying out ring-opening reaction on the product obtained in the step (3) and morpholine to obtain a photoinitiator shown as the formula; in the preparation process of the method, the diphenylmethyl ether is used as a raw material, so that the process cost is high, and the synthesis difficulty of the diepoxide is high.
Therefore, it is still of great importance to develop a method for preparing the photoinitiator with low cost and high product quality.
Disclosure of Invention
The invention aims to provide a preparation method of a photoinitiator, a product and application thereof, wherein the preparation method takes 2-methyl-1- [ 4-halogenated phenyl ] -2- (4-morpholinyl) -1-acetone and thiourea as raw materials, the photoinitiator is obtained through one-step reaction, the raw materials are simple in composition, the reaction flow is short, the energy consumption and the cost are low, the side reaction is less, the yield of the target product is high, the color of the obtained photoinitiator is white, and the product purity is high.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method of preparing a photoinitiator, the method comprising: under the protection of inert atmosphere, mixing a compound shown in a formula a, a sulfur source and a solvent, and reacting to obtain a photoinitiator shown in a formula b; the sulfur source is selected from thiourea;
wherein X is selected from chlorine or bromine, preferably chlorine.
The preparation method of the photoinitiator takes a compound shown in a formula a and thiourea as raw materials, and the compound and the thiourea undergo a substitution reaction in a polar organic solvent to obtain the photoinitiator shown in a formula b, wherein the reaction equation is shown as follows:
the solid photoinitiator prepared by the method has the advantages of simple raw material composition, short one-step reaction flow, low cost and energy consumption and high yield of target products, the yield of the target photoinitiator can reach more than 83 percent based on the addition of the compound of the formula a, the obtained photoinitiator is a white solid, the product purity is high, the impurity content is low, the purification is easy, and the preparation of the photoinitiator product with high quality, low energy consumption and low cost is realized.
The purity of the white solid photoinitiator obtained by the preparation method can reach more than 98 percent, thereby being beneficial to improving the application effect of the white solid photoinitiator.
The preparation method takes the thiourea as the sulfur source, and has simple process and easy operation.
Preferably, the solvent is selected from polar solvents, preferably N, N-dimethylformamide.
In the preparation method, the reaction solvent is preferably a polar solvent, and more preferably N, N-dimethylformamide, so that compared with a non-polar organic solvent, the reaction rate is higher, and the target photoinitiator with high purity and high yield can be obtained more favorably.
Preferably, the molar ratio of the compound of formula a to the sulfur source is 1.5 to 3, such as 1.
Preferably, the ratio of the molar amount of the compound of formula a to the volume of the solvent is 1.5mol/L to 2.0mol/L, such as 1.6mol/L, 1.7mol/L, 1.8mol/L, or 1.9mol/L, and the like. Here, the concentration of the compound of formula a is in the above range, and the concentration of the reactant is high, resulting in shortening of the reaction time.
Preferably, the inert atmosphere is selected from any one of nitrogen, argon or helium atmosphere or a combination of at least two thereof.
Preferably, the reaction is carried out at a temperature of 95 ℃ to 105 ℃, for example 98 ℃, 100 ℃, or 103 ℃.
In the preparation method, the reaction temperature is in the range, the reaction system is cleaner, the impurities are less, the reaction is slow when the temperature is too low, and the reaction system becomes impure when the temperature is too high.
Preferably, the reaction also comprises post-treatment after the reaction is finished.
After the reaction is completed in the preparation method, the main components in the reaction liquid comprise target products, urea, sodium hydroxide, inorganic salt and the like, and after the post-treatment operation is carried out on the reaction liquid, impurities can be effectively removed, the purity of the photoinitiator is improved, the appearance of the photoinitiator is improved, the loss of the photoinitiator in the post-treatment process is less, and the yield of the target photoinitiator is high.
Preferably, the post-treatment method comprises the steps of cooling the reaction solution, adding a non-polar organic solvent and water for extraction and liquid separation to obtain an organic phase, and then washing and concentrating the organic phase to obtain a crude photoinitiator product.
The preparation method can achieve the purpose of primary purification through the specific steps of extraction, water washing and concentration, and obtain a crude product of the photoinitiator; the crude photoinitiator was a pale yellow solid.
Preferably, the end point of the temperature reduction is to room temperature.
Preferably, the non-polar organic solvent is selected from toluene.
Preferably, the volume ratio of the non-polar organic solvent to water is 1.8 to 2.2, such as 1:2, and the like.
The preparation method adopts the specific mixed solvent for extraction, urea, inorganic salt and the like enter a water phase in the extraction process, a target product enters an organic phase, and then the organic phase is obtained through liquid separation.
Preferably, the concentration further comprises alcohol washing.
The alcohol washing can realize the purification effect, and then the pure product of the photoinitiator is obtained through filtering and drying, and the purity of the pure product can reach more than 98 percent.
Preferably, the alcohol-washed solvent is selected from low molecular alcohols, preferably methanol and/or ethanol.
Preferably, the alcohol washing method comprises the steps of mixing the crude photoinitiator product with an alcohol washing solvent, refluxing and stirring, cooling, performing suction filtration, and drying to obtain a pure photoinitiator product.
The preparation method can realize the collection and purification of the target photoinitiator through the post-treatment steps, and the yield of the target photoinitiator can reach more than 83 percent and the purity can reach more than 98 percent by taking the addition amount of the compound of the formula a as a raw material as a basis; the obtained solid photoinitiator is white and has good appearance, thereby being beneficial to improving the application performance of the solid photoinitiator.
As a preferable technical scheme of the invention, the preparation method of the white solid photoinitiator comprises the following steps:
(1) Under the protection of inert atmosphere, adding a compound shown in the formula a, thiourea and N, N-dimethylformamide into a reactor, and heating to 95-105 ℃ for reaction;
(2) After the reaction in the step (1) is completed, cooling the reaction liquid to room temperature, adding toluene and water for extraction and liquid separation to obtain an organic phase, washing the organic phase with water, and concentrating and desolventizing to obtain a crude product of the photoinitiator;
(3) And (3) mixing the crude photoinitiator in the step (2) with methanol, refluxing and stirring, naturally cooling to room temperature, carrying out suction filtration, and naturally drying a filter cake to obtain a white solid photoinitiator.
In a second aspect, the present invention provides a white solid photoinitiator, the white solid photoinitiator being prepared by the method of the first aspect, the white solid photoinitiator having a formula as follows:
the photoinitiator has a white solid appearance and a good appearance, is favorable for optimizing subsequent use performance and avoids interference of colors and impurities.
In a third aspect, the present invention provides a photocurable composition comprising the white solid photoinitiator according to the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation method of the photoinitiator takes the compound shown in the formula a and thiourea as raw materials, and obtains the target photoinitiator through one-step reaction in a polar organic solvent, the raw materials of the preparation method are simple in composition, the reaction process is short, the cost and the energy consumption are low, side reactions are few, the yield of the target photoinitiator is high, and the yield can reach more than 83%;
(2) The photoinitiator prepared by the preparation method of the photoinitiator has a simple purification process, a white solid photoinitiator can be obtained by subsequent alcohol washing, the appearance of a target product is good, the product purity is high, and the purity can reach more than 98%.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of a photoinitiator, which comprises the following steps:
(1) Opening mechanical stirring, adding the compound (0.0373 mol), thiourea (0.0747 mol) and NMP (20 mL) into a 100mL reaction flask under the protection of nitrogen atmosphere, heating to 100 ℃, carrying out temperature-controlled reaction for 10h, and detecting the completion of the raw material reaction by TLC;
(2) After the reaction in the step (1) is finished, cooling the reaction liquid to room temperature, adding toluene (40 mL) and water (80 mL), extracting and separating liquid to obtain an organic phase, washing the organic phase with water for three times, and using 80mL of water each time, and then concentrating the organic phase until the organic phase does not run off, so as to obtain a crude photoinitiator product which is a light yellow solid;
(3) And (3) adding methanol (15 mL) into the light yellow solid obtained in the step (2), refluxing and stirring for 1h, naturally cooling to room temperature, carrying out suction filtration, and naturally drying the filter cake to obtain a white solid photoinitiator.
In this example, the yield of the target product was calculated to be 85% and the purity 98.3%.
The white solid photoinitiator obtained in this example was analyzed by mass spectrometry and H-NMR, and the analysis results are shown below;
the mass spectrometry method and test results are as follows:
MS:m/z＝[M+1] + ＝497.24(MW＝496.67)；
the H-NMR test method and results are shown below:
1 H-NMR(400MHz,CDCl 3 ):δ7.77～7.74(m,4H),7.45～7.42(m,4H),3.66～3.64(t,8H),2.50～2.48(t,8H),1.55(s,12H)。
example 2
This example differs from example 1 only in that the amount of thiourea added was changed from 0.0747mol to 0.05603mol, and the other parameters and conditions were exactly the same as in example 1.
The molar ratio of the amount of thiourea added to the amount of compound of formula c added in this example was 1.5, which corresponds to a yield of 81% for the target photoinitiator and a purity of 98.1%.
Example 3
This example differs from example 1 in that the amount of thiourea added was changed from 0.0747mol to 0.09338mol, and the other parameters and conditions were exactly the same as in example 1.
The molar ratio of the amount of thiourea added to the amount of compound of formula c added in this example was 2.5, which corresponds to a yield of 84.8% for the target photoinitiator and a purity of 98.4%.
Example 4
This example differs from example 1 in that the amount of thiourea added was changed from 0.0747mol to 0.0373mol, and the other parameters and conditions were exactly the same as in example 1.
In this example, the addition amount of thiourea was small, the raw material consumption was incomplete during the reaction, and the yield of the corresponding target photoinitiator was only 66.1%.
Example 5
This example differs from example 1 in that the solvent was replaced with toluene in equal volume from DMF (N, N-dimethylformamide) and the other parameters and conditions were exactly the same as in example 1.
In this embodiment, the solvent used in the temperature-raising reaction is a nonpolar organic solvent, i.e., toluene, and a large amount of raw materials are left and hardly react.
Example 6
This example differs from example 1 only in that the reaction temperature was adjusted from 100 ℃ to 125 ℃ and the other parameters and conditions were exactly the same as in example 1.
The yield of the target photoinitiator in this example was 84.4% with a purity of 97.4%.
Comparative example 1
This comparative example is different from example 1 in that an equimolar amount of thiourea was replaced with sodium sulfide, and other parameters and conditions were exactly the same as those in example 1.
In the comparative example, sodium sulfide is used as a sulfur source, a large amount of raw materials are left, and only a small amount of target products are obtained.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention disclosed herein fall within the scope and disclosure of the present invention.
Claims (10)
1. A method of preparing a photoinitiator, the method comprising: under the protection of inert atmosphere, mixing a compound shown in a formula a, a sulfur source and a solvent, and reacting to obtain a photoinitiator shown in a formula b; the sulfur source is selected from thiourea;
wherein X is selected from chlorine or bromine.
2. The method of claim 1, wherein the solvent is selected from the group consisting of polar solvents;
the molar weight ratio of the compound of formula a to the sulfur source is 1.5 to 3;
the ratio of the molar weight of the compound of the formula a to the volume of the solvent is 1.5 mol/L-2.0 mol/L;
the inert atmosphere is selected from any one of nitrogen, argon or helium atmosphere or the combination of at least two of the nitrogen, argon or helium atmosphere.
3. The method of claim 2, wherein the polar solvent is selected from the group consisting of N, N-dimethylformamide.
4. The method according to claim 1, wherein the reaction is carried out at a temperature of 95 to 105 ℃.
5. The preparation method according to claim 1, further comprising a post-treatment after the reaction;
the post-treatment method comprises the steps of cooling the reaction solution, adding a non-polar organic solvent and water for extraction and liquid separation to obtain an organic phase, and then washing and concentrating the organic phase to obtain a crude product of the photoinitiator.
6. The method of claim 5, wherein the non-polar organic solvent is selected from the group consisting of toluene;
the volume ratio of the nonpolar organic solvent to the water is 1.8-2.2.
7. The method according to claim 5, wherein the concentration further comprises an alcohol wash;
the solvent for alcohol washing is selected from methanol and/or ethanol;
the alcohol washing method comprises the steps of mixing the crude photoinitiator product with an alcohol washing solvent, refluxing and stirring, cooling, carrying out suction filtration, and drying to obtain a pure photoinitiator product.
8. The method of claim 1, comprising the steps of:
(1) Under the protection of inert atmosphere, adding a compound shown in the formula a, thiourea and N, N-dimethylformamide into a reactor, and heating to 95-105 ℃ for reaction;
(2) After the reaction in the step (1) is completed, cooling the reaction liquid to room temperature, adding toluene and water for extraction and liquid separation to obtain an organic phase, washing the organic phase with water, and concentrating and desolventizing to obtain a crude product of the photoinitiator;
(3) And (3) mixing the crude photoinitiator in the step (2) with methanol, refluxing and stirring, naturally cooling to room temperature, carrying out suction filtration, and naturally drying a filter cake to obtain a white solid photoinitiator.
9. A white solid photoinitiator, prepared by a process according to any one of claims 1 to 8, and having the formula:
10. a photocurable composition comprising the white solid photoinitiator according to claim 9.
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| CN105218418A (en) * | 2015-10-01 | 2016-01-06 | 宜春学院 | A kind of preparation method of thioether |
| CN111559976A (en) * | 2020-05-29 | 2020-08-21 | 扬州大学 | Synthetic method of heteroaryl thioether |
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- 2022-12-06 CN CN202211555054.5A patent/CN115785023A/en active Pending
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