CN114315575A - Preparation method and application of photoinitiator intermediate - Google Patents
Preparation method and application of photoinitiator intermediate Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 106
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 37
- 238000002156 mixing Methods 0.000 claims abstract description 16
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 66
- 239000000243 solution Substances 0.000 claims description 56
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 150000001875 compounds Chemical class 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000010521 absorption reaction Methods 0.000 claims description 28
- 239000012074 organic phase Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 21
- 239000005457 ice water Substances 0.000 claims description 20
- 239000012071 phase Substances 0.000 claims description 20
- 238000006460 hydrolysis reaction Methods 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 230000007062 hydrolysis Effects 0.000 claims description 13
- WHFKYDMBUMLWDA-UHFFFAOYSA-N 2-phenoxyethyl acetate Chemical compound CC(=O)OCCOC1=CC=CC=C1 WHFKYDMBUMLWDA-UHFFFAOYSA-N 0.000 claims description 11
- 239000002250 absorbent Substances 0.000 claims description 11
- 230000002745 absorbent Effects 0.000 claims description 11
- 238000004321 preservation Methods 0.000 claims description 11
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- DGMOBVGABMBZSB-UHFFFAOYSA-N 2-methylpropanoyl chloride Chemical compound CC(C)C(Cl)=O DGMOBVGABMBZSB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 13
- 239000012752 auxiliary agent Substances 0.000 abstract description 8
- 238000005893 bromination reaction Methods 0.000 abstract description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 5
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- 230000031709 bromination Effects 0.000 abstract description 3
- 239000013067 intermediate product Substances 0.000 abstract description 2
- 125000006239 protecting group Chemical group 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 15
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- -1 2-hydroxyethoxy Chemical group 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Abstract
The invention relates to a preparation method and application of a photoinitiator intermediate, which comprises the following steps: mixing ethyl 2- (4-isobutyrylphenoxy) acetate and sulfuric acid with the concentration of 30-85%, introducing chlorine gas, and carrying out chlorination reaction to generate the photoinitiator intermediate; the sulfuric acid with the specific concentration is added as an auxiliary agent, so that the electronic state on a benzene ring in the ethyl 2- (4-isobutyrylphenoxy) acetate can be changed, the occurrence of chlorination reaction on the benzene ring and a methyl group of an acetyl group of a protecting group is further inhibited, the rate of alpha-chlorination reaction of a ketone carbonyl group is increased, the chlorination selectivity is improved, the methyl chlorination of the acetyl group is avoided, and the yield of alpha-chlorinated products is improved; compared with the traditional bromination process, the chlorination process has the advantages of low process cost and simple recovery operation, and compared with the traditional chlorination process, the chlorination process has higher selectivity on alpha-chlorination reaction and higher yield of target intermediate products.
Description
Technical Field
The invention belongs to the field of photoinitiator preparation, and relates to a preparation method and application of a photoinitiator intermediate.
Background
Photoinitiator 2959, chinese name: 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone, which is a high-efficiency non-yellowing ultraviolet initiator and is used for initiating the UV polymerization reaction of unsaturated prepolymer and monomer.
CN101811951A discloses a preparation method of 2-hydroxy-1- {4- (2-hydroxyethoxy) phenyl } -2-methyl-1-acetone, which comprises the steps of taking 2-phenoxyethyl acetate as a raw material, and carrying out Friedel-crafts reaction on isobutyryl chloride with the molar ratio of 1-1.2 times equivalent under the catalysis of Lewis acid; then carrying out bromination reaction under the catalysis of N, N-dimethylformamide or iodine; catalyzing and hydrolyzing the brominated product at room temperature by using a phase transfer catalyst; finally, purifying and crystallizing to obtain the product, wherein the preparation method adopts a bromination process, so that the bromine cost is high, and the recovery operation is complex; the traditional chlorination process has the problems of poor alpha-chlorination selectivity and low product yield.
Therefore, the development of a preparation method of the photoinitiator chloro intermediate with low cost, high activity and high chloro selectivity is still of great significance.
Disclosure of Invention
The invention aims to provide a preparation method and application of a photoinitiator intermediate, which comprises the following steps: mixing ethyl 2- (4-isobutyrylphenoxy) acetate and sulfuric acid with the concentration of 30-85%, introducing chlorine gas, and carrying out chlorination reaction to generate the photoinitiator intermediate; the sulfuric acid with the specific concentration is added as an auxiliary agent, so that the electronic state on a benzene ring in the ethyl 2- (4-isobutyrylphenoxy) acetate can be changed, the occurrence of chlorination reaction on the benzene ring and a methyl group of an acetyl group of a protecting group is further inhibited, the rate of alpha-chlorination reaction of a ketone carbonyl group is increased, the chlorination selectivity is improved, the methyl chlorination of the acetyl group is avoided, and the yield of alpha-chlorinated products is improved; compared with the traditional bromination process, the chlorination process has the advantages of low process cost and simple recovery operation, and compared with the traditional chlorination process, the chlorination process has higher selectivity on alpha-chlorination reaction and higher yield of target intermediate products.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of a photoinitiator intermediate, wherein the molecular formula of the photoinitiator intermediate is shown as a formula a;
the preparation method comprises the following steps: mixing the compound solution of the formula b with sulfuric acid with the concentration of 30-85% (exemplary including 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75% or 80%), to obtain a mixed solution, and introducing chlorine gas to perform chlorination reaction, to obtain the photoinitiator intermediate solution; the molecular formula of the compound of the formula b is shown as follows;
the traditional preparation process of the photoinitiator 2959 generally comprises the steps of taking phenoxyethanol as a raw material, and obtaining the photoinitiator through acetic acid protection, Friedel-crafts acylation reaction, bromination reaction and alkaline hydrolysis reaction; wherein, the bromination reaction process has the problems of high bromine cost and complex recovery operation; the traditional chlorination process is easy to generate chlorine substitution reaction on a benzene ring, so that the problems of poor selectivity and low product yield of the alpha-chlorination reaction are caused; in order to solve the problems, the invention develops a preparation method of a photoinitiator intermediate which has low cost, high alpha chlorination selectivity and recyclable auxiliary agent.
The traditional chlorination process has the problems of poor selectivity of alpha-chlorination reaction and low product yield, and researches show that the reason for poor selectivity of the traditional chlorination process is mainly that ethoxy groups exist on benzene rings of reaction substrates, and the ethoxy groups are electron-donating groups, so that substitution reaction on the benzene rings is easy to occur in the chlorination reaction process, and benzene ring chlorine substitution byproducts are produced, thereby causing low product yield; in order to overcome the problems and improve the selectivity of the chlorination reaction, experimental research shows that sulfuric acid with the concentration of 30-85% is added as an auxiliary agent in the chlorination reaction process, and the auxiliary agent can change the electronic state on a benzene ring in ethyl 2- (4-isobutyrylphenoxy) acetate, so that the chlorination reaction on the benzene ring is inhibited, the rate of the ketocarbonyl alpha-chlorination reaction is increased, the chlorination selectivity is improved, and the yield of a target product (a compound in a formula a) is improved.
Experimental research shows that the alpha-chloro selectivity can reach over 90 percent by adopting the chlorination process, the production of the benzene ring chloro by-product is effectively reduced, and the yield of the target product is improved.
By adopting the chlorination process, the sulfuric acid is convenient to recover and recycle, and the process cost is low.
The reaction equation of the preparation method of the photoinitiator intermediate is shown as follows:
preferably, the temperature is controlled between-5 ℃ and 5 ℃, for example, -4 ℃, -3 ℃, -2 ℃, -1 ℃, 0 ℃,1 ℃,2 ℃, 3 ℃ or 4 ℃ during the mixing of the solution of the compound of formula b and sulfuric acid with a concentration of 30% to 85%.
Preferably, the temperature of the mixed solution is raised to 25 to 50 ℃ before the chlorine gas is introduced, for example, 30 ℃, 35 ℃, 40 ℃ or 45 ℃.
The reaction temperature is preferably in the temperature range, when the temperature is higher than 50 ℃, the selectivity of the chlorination reaction in the ketocarbonyl alpha-chlorination reaction can be reduced, and when the temperature is lower than 25 ℃, the reaction rate is lower, the production period is not shortened, and the efficiency is improved.
Preferably, the solvent of the compound solution of formula b is selected from any one or a combination of at least two of chlorobenzene, dichloroethane, dichloromethane, cyclohexane, n-hexane or methylcyclohexane.
When higher concentrations of sulfuric acid are used, preferably any one or a combination of at least two of chlorobenzene, dichloroethane, or dichloromethane; when a lower concentration of sulfuric acid is used, any one or a combination of at least two of chlorobenzene, n-hexane, cyclohexane or methylcyclohexane is preferred.
Preferably, the compound of formula b is reacted with H in sulfuric acid2SO4The mass ratio of (a) to (b) is 1.2 to 1.8:1, for example, 1.3:1, 1.4:1, 1.5:1, 1.6:1 or 1.7: 1.
The invention adopts the proportion, which is convenient for improving the selectivity of alpha-chlorination reaction and reducing the generation of byproducts; when the addition amount of sulfuric acid is low, the effect of the auxiliary agent is not obvious, a sulfuric acid phase cannot be separated directly after the reaction is finished, a large amount of water needs to be added for separating liquid, the obtained diluted sulfuric acid cannot be recycled, the generation of waste acid water cannot be effectively reduced, the environmental pressure is high, and when the addition amount of the sulfuric acid is too high, more products can be dissolved, so that the yield is low.
Preferably, stirring is accompanied during the chlorination reaction.
Preferably, the chlorination reaction is finished by adding water into the reaction liquid, mixing and separating to obtain an organic phase and a sulfuric acid phase.
In the present invention, the water is added after the chlorination reaction is completed in order to dilute the sulfuric acid, thereby facilitating the separation of the sulfuric acid phase from the organic phase. The amount of water added needs to be regulated and controlled according to the concentration and the addition amount of the initial sulfuric acid, and H in the sulfuric acid phase obtained by liquid separation is controlled2SO4Is 30-70%, which facilitates the subsequent two-phase stratification, and if the initial sulfuric acid concentration is within the above range (i.e., 30-70%), no water is added for dilution.
Preferably, the method further comprises washing the organic phase with water after the liquid separation is finished.
Preferably, the amount of water added is such that H is in the sulphuric acid phase2SO4The concentration of (b) is 30% to 70%, for example, 35%, 40%, 45%, 50%, 55%, 60%, 65%, etc.
The concentration of the obtained sulfuric acid phase is 30-70% by controlling the addition of water, which is not only beneficial to the layering of the sulfuric acid phase and the organic phase, but also convenient for the recycling of the sulfuric acid phase.
Preferably, the chlorination reaction is carried out in a reaction device which is connected with a tail gas absorption device; preferably, the absorption liquid adopted by the tail gas absorption device is a sodium hydroxide aqueous solution.
The sodium hydroxide water solution is used as the absorption liquid, which can absorb HCl and a small amount of excessive chlorine generated by chlorination reaction, thereby avoiding environmental pollution.
Preferably, the compound of formula b is prepared by a process comprising the steps of:
(a) adding a catalyst into the 2-phenoxyethyl acetate solution;
(b) and (b) dropwise adding isobutyryl chloride into the solution in the step (a), carrying out heat preservation reaction, then carrying out hydrolysis, and carrying out liquid separation to obtain a compound solution in the formula b.
Preferably, the catalyst in step (a) is selected from anhydrous aluminum trichloride and/or ferric trichloride.
In the preparation method of the invention, the reaction equation of the compound in the formula b is shown as follows;
preferably, the molar ratio of catalyst to 2-phenoxyethyl acetate in step (a) is 2-2.2: 1, such as 2.1:1, etc.
The amount of the catalyst added in the present invention is within the above range, which is advantageous for the reaction to proceed sufficiently.
Preferably, the solvent of the 2-phenoxyethyl acetate solution in the step (a) is selected from any one or a combination of at least two of chlorobenzene, dichloroethane, dichloromethane, cyclohexane, n-hexane or methylcyclohexane.
Preferably, the temperature at which step (a) is operated is from-5 ℃ to 0 ℃, such as-4 ℃, -3 ℃, -2 ℃ or-1 ℃ and the like.
Preferably, the operation in step (a) is accompanied by stirring.
Preferably, the temperature at which the reaction is maintained in step (b) is from 0 ℃ to 5 ℃, e.g., 1 ℃,2 ℃, 3 ℃ or 4 ℃, etc.
In the present invention, the incubation reaction is carried out at the above temperature, which can prevent side reactions from occurring, and the isomerization reaction is likely to occur at a temperature higher than this temperature.
Preferably, after the heat preservation reaction in step (b) is finished, the temperature is reduced to-5 ℃ to 0 ℃, such as-4 ℃, 3 ℃,2 ℃ or-1 ℃ before the hydrolysis.
In the invention, after the heat preservation reaction is finished and before the hydrolysis reaction, the temperature of the reaction liquid is reduced to the range, because the hydrolysis reaction is an exothermic reaction, the side reaction caused by overhigh local temperature in the hydrolysis process can be effectively avoided by adopting the operation.
Preferably, the hydrolysis in step (b) comprises adding the reaction solution into ice water containing HCl for hydrolysis, then separating the solution, and washing the organic phase with water to obtain the compound solution of formula b.
Preferably, the preparation process of the compound of formula b is carried out in a reaction device connected to a tail gas absorption device, preferably, the absorbent of the tail gas absorption device is water, preferably ice water.
In the invention, ice water is used as an absorbent, which is beneficial to inhibiting the volatilization of HCl, and on the other hand, the ice water can be directly used for hydrolysis reaction.
Preferably, the ice water comprising HCl in step (b) is selected from ice water in a tail gas absorption unit.
According to the invention, the absorbent in the tail gas absorption device adopts ice water, and the byproduct hydrogen chloride enters the tail gas absorption device in the reaction process and is absorbed by the absorbent ice water to obtain the ice water containing HCl, and the ice water is used as a reagent for hydrolysis reaction, so that the comprehensive utilization of resources is facilitated.
In a second aspect, the present invention provides a method for preparing a photoinitiator, wherein the formula of the photoinitiator is represented by formula c below;
the preparation method comprises the following steps:
(1) preparing a photoinitiator intermediate solution according to the method of the first aspect;
(2) and (2) mixing the photoinitiator intermediate solution in the step (1) with alkali liquor, and heating for reaction to obtain the photoinitiator.
In the preparation method of the invention, the equation of the reaction in the step (2) is shown as follows;
preferably, the alkali solution in step (2) is selected from sodium hydroxide solution, preferably sodium hydroxide solution with concentration of 10% to 50% (exemplary including 15%, 20%, 25%, 30%, 35%, 40% or 45%, etc.).
Preferably, the molar ratio of the photoinitiator intermediate in step (2) to the base in the alkali solution is 1:2 to 2.4, such as 1:2.1, 1:2.2 or 1: 2.3.
Preferably, the temperature of the heating reaction in step (2) is selected from 60 ℃ to 90 ℃, such as 65 ℃, 70 ℃, 75 ℃, 80 ℃ or 85 ℃ and the like.
In the preparation method, the alkaline hydrolysis reaction is carried out at the temperature, so that the reaction rate can be improved, the side reaction can be controlled, and when the temperature is lower than 60 ℃, the reaction time is relatively long, which is not beneficial to shortening the production period; when the temperature is higher than 90 ℃, the a-chlorine is easy to generate elimination reaction, side reaction is increased, and the yield is reduced.
Preferably, the heating in step (2) is accompanied by stirring.
Preferably, after the heating reaction in step (2) is finished, the method further comprises cooling, liquid separation, organic phase washing, desolventizing, recrystallizing and drying to obtain the photoinitiator.
Preferably, the desolventizing mode is evaporation desolventizing.
Preferably, the solvent for recrystallization is selected from any one of methanol, ethanol, propanol or isopropanol or a combination of at least two thereof.
As a preferred technical scheme of the invention, the preparation method of the photoinitiator comprises the following steps:
adding 2-phenoxyethyl acetate and an organic solvent into a reaction device, wherein the reaction device is communicated with a tail gas absorption device, and an absorbent of the tail gas absorption device is ice water; adding anhydrous aluminum trichloride into a reaction device at the temperature of-5-0 ℃, and stirring to obtain a mixed solution;
(II) dropwise adding isobutyryl chloride into the mixed solution obtained in the step (I) at the temperature of 0-5 ℃, and then carrying out heat preservation reaction;
(III) after the reaction in the step (II) is finished, cooling to-5-0 ℃, adding the reaction liquid into ice water of a tail gas absorption device for hydrolysis, stirring, standing for layering, separating liquid, and washing an organic phase to obtain a compound solution in a formula b;
(IV) mixing the solution of the compound b in the step (III) with sulfuric acid with the concentration of 30-85% in a reaction device at the temperature of-5 ℃, wherein the reaction device is communicated with a tail gas absorption device, an absorbent in the tail gas absorption device is selected from sodium hydroxide aqueous solution, then heating to the temperature of 25-50 ℃, and introducing chlorine into the reaction device with stirring to perform chlorination;
(V) after the reaction in the step (IV) is finished, adding water into the reaction device, stirring, standing for layering, and separating to obtain an organic phase and a sulfuric acid phase, wherein the concentration of the sulfuric acid phase is selected from 30-70%; washing the organic phase with water to obtain a compound solution of the formula a;
and (VI) mixing the compound solution of the formula a obtained in the step (V) with a sodium hydroxide solution, stirring, heating to 60-90 ℃ for heat preservation reaction, cooling after the reaction is completed, standing for layering, separating liquid, washing an organic phase with water, desolventizing, recrystallizing, filtering, and drying to obtain the photoinitiator.
Compared with the prior art, the invention has the following beneficial effects:
(1) in the preparation method, the chlorination reaction adopts 30-85% sulfuric acid as an auxiliary agent, which can change the electronic state on a benzene ring in the compound shown in the formula b, so that the chlorination reaction on the benzene ring is inhibited, the rate of the alpha-chlorination reaction of the ketocarbonyl group is increased, the chlorination selectivity is improved, and the yield of the alpha-chlorination process is further improved;
(2) in the preparation method, the sulfuric acid used as the auxiliary agent can be recycled, so that the process cost is reduced.
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 2959, which specifically comprises the following steps:
(1) friedel-crafts reaction:
dissolving 36g (0.2mol) of 2-phenoxyethyl acetate in 70g of chlorobenzene to obtain a 2-phenoxyethyl acetate solution, connecting a tail gas absorption device (an absorbent is ice water), adding 56g (0.42mol) of anhydrous aluminum trichloride into the solution at the temperature of minus 3 ℃, and stirring for 0.5 h; then heating to 3 ℃, adding 21.3g (0.2mol) of isobutyryl chloride dropwise with stirring, keeping the temperature for 6 hours after the dropwise addition is finished, cooling the reaction liquid to-3 ℃, adding the reaction liquid into ice water of a tail gas absorption device for hydrolysis, stirring for 0.5 hour, standing for layering, separating out an organic phase, and washing with water to obtain a compound solution of the formula b;
(2) chlorination reaction:
uniformly mixing a compound solution of a formula b obtained by a Friedel-crafts reaction with 70g of 50% sulfuric acid at 0 ℃, heating to 30 ℃, connecting a tail gas absorption device (an absorbent is an aqueous solution of sodium hydroxide), introducing chlorine into a reaction solution along with stirring, controlling the introduction rate of the chlorine to be slow at the final stage of the reaction, detecting by thin-layer chromatography until the reaction is complete, standing for layering, separating liquid to obtain an organic phase and a sulfuric acid phase, and washing the organic phase with water for the next reaction; the concentration of the sulfuric acid phase is 50%;
the results of H-NMR analysis of the product obtained in step (2) are shown below;
1H-NMR(400MHz,CDCl3):7.83(d,2H),6.85(d,2H),4.52(t,2H),4.21(t,2H),2.05(s,3H),1.84(s,6H)。
the purity of the compound of formula a is 95.1% by HPLC detection of the product obtained in step (2).
(3) Hydrolysis and deprotection reactions:
mixing the organic phase obtained in the step (2) with 53.3g (0.4mol) of 30% NaOH solution, raising the temperature to 75 ℃, fully stirring and carrying out heat preservation reaction, detecting by thin-layer chromatography until the reaction is complete, cooling to room temperature, standing for layering, separating liquid to obtain an organic phase and a water phase, washing the organic phase with water, evaporating out an organic solvent, carrying out recrystallization purification by using methanol, filtering and drying to obtain 40.6g of a white solid of a photoinitiator 2959, wherein the melting point is 87-90 ℃, the purity is 99.2% and the yield is 90.5%;
the results of H-NMR analysis of the product obtained in step (3) are shown below; 1H-NMR (400MHz, CDCl3) 7.80(d,2H),6.80(d,2H),4.17(t,2H),4.01(t,2H),2.56(s,1H),2.15(s,1H), 1.49(s, 6H).
Example 2
This example differs from example 1 only in that the sulfuric acid phase obtained in step (2) is used in step (1) as a set, and the other parameters and conditions are exactly the same as in example 1.
The photoinitiator 2959 product obtained in this example was a white solid with a purity of 99.0% and a yield of 89.5%.
Example 3
This example differs from example 1 only in that 70g of 50% sulfuric acid in step (2) was replaced with 54g of 65% sulfuric acid, and the other parameters and conditions were exactly the same as in example 1.
The photoinitiator 2959 product obtained in this example was a white solid with a purity of 99.0% and a yield of 89.8%.
Example 4
This example differs from example 1 only in that 70g of 50% sulfuric acid in step (2) was replaced by 44g of 80% sulfuric acid solution and 26g of water was added after the chlorination reaction was completed, and the other parameters and conditions were exactly the same as in example 1.
The photoinitiator 2959 product obtained in this example was a white solid with a purity of 99.0% and a yield of 87.9%.
Example 5
This example differs from example 1 only in that 70g of 50% sulfuric acid was replaced by 44g of 80% sulfuric acid solution in step (2), no water was added after the chlorination reaction was completed, and other parameters and conditions were exactly the same as in example 1.
In this example, since the concentration of the initially used sulfuric acid is greater than 70%, after the chlorination reaction is completed, the sulfuric acid is not diluted with water, and more products are dissolved in the separated sulfuric acid phase, thereby decreasing the yield of the final product.
Comparative example 1
This comparative example differs from example 1 only in that no sulfuric acid was added in step (2) and the other parameters and conditions were exactly the same as in example 1.
The reaction solution obtained in step (2) was tested by HPLC, and the purity of the compound of formula a was 45.0%.
Comparative example 2
This comparative example differs from example 1 only in that 70g of 50% sulfuric acid in step (2) was replaced with 100g of 20% sulfuric acid, and the other parameters and conditions were exactly the same as in example 1.
The reaction solution obtained in step (2) was tested by HPLC and the purity of the compound of formula a was 77.0%. 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 are within the scope and disclosure of the present invention.
Claims (10)
1. The preparation method of the photoinitiator intermediate is characterized in that the molecular formula of the photoinitiator intermediate is shown as a formula a;
the preparation method comprises the following steps: mixing the compound solution of the formula b with sulfuric acid with the concentration of 30-85% to obtain a mixed solution, and then introducing chlorine gas to perform chlorination reaction to obtain the photoinitiator intermediate solution; the molecular formula of the compound of the formula b is shown as follows;
2. the preparation method according to claim 1, wherein the temperature is controlled at-5 ℃ to 5 ℃ during the mixing of the compound solution of the formula b and the sulfuric acid with the concentration of 30% to 85%;
preferably, the temperature of the mixed solution is raised to 25 to 50 ℃ before the chlorine gas is introduced.
3. The preparation method according to claim 1 or 2, wherein the solvent of the compound solution of formula b is selected from any one or a combination of at least two of chlorobenzene, dichloroethane, dichloromethane, cyclohexane, n-hexane or methylcyclohexane;
preferably, the compound of formula b is reacted with H in sulfuric acid2SO4The mass ratio of (A) to (B) is 1.2-1.8: 1;
preferably, stirring is accompanied during the chlorination reaction.
4. The preparation method according to any one of claims 1 to 3, further comprising adding water to the reaction solution after the chlorination reaction is completed, mixing, and separating to obtain an organic phase and a sulfuric acid phase;
preferably, the method further comprises the step of washing the organic phase with water after the liquid separation is finished;
preferably, the amount of water added is such that H is in the sulphuric acid phase2SO4The concentration of (A) is 30-70%;
preferably, the chlorination reaction is carried out in a reaction device which is connected with a tail gas absorption device; preferably, the absorption liquid adopted by the tail gas absorption device is a sodium hydroxide aqueous solution.
5. The process according to any one of claims 1 to 4, wherein the compound of formula b is prepared by a process comprising the steps of:
(a) adding a catalyst into the 2-phenoxyethyl acetate solution;
(b) and (b) dropwise adding isobutyryl chloride into the solution in the step (a), carrying out heat preservation reaction, then carrying out hydrolysis, and carrying out liquid separation to obtain a compound solution in the formula b.
6. The process according to claim 5, wherein the catalyst in the step (a) is selected from the group consisting of anhydrous aluminum trichloride and/or iron trichloride;
preferably, the molar weight ratio of the catalyst to the 2-phenoxyethyl acetate in the step (a) is 2-2.2: 1;
preferably, the solvent of the 2-phenoxyethyl acetate solution in the step (a) is selected from any one or a combination of at least two of chlorobenzene, dichloroethane, dichloromethane, cyclohexane, n-hexane or methylcyclohexane;
preferably, the temperature operated in step (a) is between-5 ℃ and 0 ℃;
preferably, the operation in step (a) is accompanied by stirring;
preferably, the temperature for the heat preservation reaction in the step (b) is 0 ℃ to 5 ℃;
preferably, after the heat preservation reaction in the step (b) is finished, the temperature is reduced to-5-0 ℃ before hydrolysis;
preferably, the hydrolysis in step (b) comprises adding the reaction solution into ice water containing HCl for hydrolysis, then separating the solution, and washing the organic phase with water to obtain a compound solution of formula b;
preferably, the preparation process of the compound of formula b is performed in a reaction device, the reaction device is connected with a tail gas absorption device, and preferably, the absorbent of the tail gas absorption device is water, preferably ice water;
preferably, the ice water comprising HCl in step (b) is selected from ice water in a tail gas absorption unit.
7. The preparation method of the photoinitiator is characterized in that the molecular formula of the photoinitiator is shown as the following formula c;
the preparation method comprises the following steps:
(1) preparing a photoinitiator intermediate solution according to the method of any one of claims 1-6;
(2) and (2) mixing the photoinitiator intermediate solution in the step (1) with alkali liquor, and heating for reaction to obtain the photoinitiator.
8. The method according to claim 7, wherein the alkali solution in step (2) is selected from sodium hydroxide solution, preferably 10-50% sodium hydroxide solution;
preferably, the molar weight ratio of the photoinitiator intermediate in the step (2) to the alkali in the alkali liquor is 1: 2-2.4.
9. The method according to claim 7 or 8, wherein the temperature of the heating reaction in the step (2) is selected from 60 ℃ to 90 ℃;
preferably, stirring is carried out during the heating reaction in the step (2);
preferably, after the heating reaction in the step (2) is finished, cooling, separating, washing with water of an organic phase, desolventizing, recrystallizing and drying are further included to obtain the photoinitiator;
preferably, the solvent for recrystallization is selected from any one of methanol, ethanol, propanol or isopropanol or a combination of at least two thereof.
10. The method of any one of claims 7 to 9, comprising the steps of:
adding 2-phenoxyethyl acetate and an organic solvent into a reaction device, wherein the reaction device is communicated with a tail gas absorption device, and an absorbent of the tail gas absorption device is ice water; adding anhydrous aluminum trichloride into a reaction device at the temperature of-5-0 ℃, and stirring to obtain a mixed solution;
(II) dropwise adding isobutyryl chloride into the mixed solution obtained in the step (I) at the temperature of 0-5 ℃, and then carrying out heat preservation reaction;
(III) after the reaction in the step (II) is finished, cooling to-5-0 ℃, adding the reaction liquid into ice water of a tail gas absorption device for hydrolysis, stirring, standing for layering, separating liquid, and washing an organic phase to obtain a compound solution in a formula b;
(IV) mixing the solution of the compound b in the step (III) with sulfuric acid with the concentration of 30-85% in a reaction device at the temperature of-5 ℃, wherein the reaction device is communicated with a tail gas absorption device, an absorbent in the tail gas absorption device is selected from sodium hydroxide aqueous solution, then heating to the temperature of 25-50 ℃, and introducing chlorine into the reaction device with stirring to perform chlorination;
(V) after the reaction in the step (IV) is finished, adding water into the reaction device, stirring, standing for layering, and separating to obtain an organic phase and a sulfuric acid phase, wherein the concentration of the sulfuric acid phase is selected from 30-70%; washing the organic phase with water to obtain a compound solution of the formula a;
and (VI) mixing the compound solution of the formula a obtained in the step (V) with a sodium hydroxide solution, stirring, heating to 60-90 ℃ for heat preservation reaction, cooling after the reaction is completed, standing for layering, separating liquid, washing an organic phase with water, desolventizing, recrystallizing, filtering, and drying to obtain the photoinitiator.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811951A (en) * | 2010-05-07 | 2010-08-25 | 甘肃金盾化工有限责任公司 | Preparation method of 2-hydroxyl-1-{4-(2-hydroxyethyl) phenyl}-2-methyl-1-acetone |
| CN109651134A (en) * | 2019-02-13 | 2019-04-19 | 天津城建大学 | A kind of preparation method of photoinitiator 2- methyl -2- hydroxyl -1- phenylacetone |
| CN111138260A (en) * | 2019-12-31 | 2020-05-12 | 天津久日新材料股份有限公司 | Preparation method of α -hydroxyketone bifunctional photoinitiator |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811951A (en) * | 2010-05-07 | 2010-08-25 | 甘肃金盾化工有限责任公司 | Preparation method of 2-hydroxyl-1-{4-(2-hydroxyethyl) phenyl}-2-methyl-1-acetone |
| CN109651134A (en) * | 2019-02-13 | 2019-04-19 | 天津城建大学 | A kind of preparation method of photoinitiator 2- methyl -2- hydroxyl -1- phenylacetone |
| CN111138260A (en) * | 2019-12-31 | 2020-05-12 | 天津久日新材料股份有限公司 | Preparation method of α -hydroxyketone bifunctional photoinitiator |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115304556A (en) * | 2022-09-05 | 2022-11-08 | 天津久日新材料股份有限公司 | Solid photoinitiator and preparation method and application thereof |
| CN115304556B (en) * | 2022-09-05 | 2024-03-29 | 天津久日新材料股份有限公司 | Solid photoinitiator and preparation method and application thereof |
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