CN114835564B - Method for producing photoinitiator UV-1173 by condensation method - Google Patents
Method for producing photoinitiator UV-1173 by condensation method Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000009833 condensation Methods 0.000 title claims abstract description 8
- 230000005494 condensation Effects 0.000 title claims abstract description 8
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000003054 catalyst Substances 0.000 claims abstract description 69
- BSMGLVDZZMBWQB-UHFFFAOYSA-N 2-methyl-1-phenylpropan-1-one Chemical compound CC(C)C(=O)C1=CC=CC=C1 BSMGLVDZZMBWQB-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000002994 raw material Substances 0.000 claims abstract description 60
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000006482 condensation reaction Methods 0.000 claims abstract description 33
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 28
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 28
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 21
- 238000005904 alkaline hydrolysis reaction Methods 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000011259 mixed solution Substances 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 20
- 230000004913 activation Effects 0.000 claims description 14
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 claims description 11
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 10
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 abstract description 28
- 239000002910 solid waste Substances 0.000 abstract description 9
- 238000002474 experimental method Methods 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000013067 intermediate product Substances 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 238000010924 continuous production Methods 0.000 abstract description 2
- 230000009849 deactivation Effects 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000011572 manganese Substances 0.000 description 19
- 239000007789 gas Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 10
- QMZIDZZDMPWRHM-UHFFFAOYSA-L manganese(2+);dibenzoate Chemical compound [Mn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 QMZIDZZDMPWRHM-UHFFFAOYSA-L 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- UYSVXJZQVNOLNB-UHFFFAOYSA-N 1-(4-tert-butylphenyl)-2-methylpropan-1-one Chemical compound CC(C)C(=O)C1=CC=C(C(C)(C)C)C=C1 UYSVXJZQVNOLNB-UHFFFAOYSA-N 0.000 description 5
- ZDFKSZDMHJHQHS-UHFFFAOYSA-N 2-tert-butylbenzoic acid Chemical compound CC(C)(C)C1=CC=CC=C1C(O)=O ZDFKSZDMHJHQHS-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- VZFUCHSFHOYXIS-UHFFFAOYSA-N cycloheptane carboxylic acid Natural products OC(=O)C1CCCCCC1 VZFUCHSFHOYXIS-UHFFFAOYSA-N 0.000 description 5
- 230000003213 activating effect Effects 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- -1 2-hydroxy-2-methyl phenyl Chemical group 0.000 description 3
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- JHXJMPVUVKIGKC-UHFFFAOYSA-N 1-(4-tert-butylphenyl)-2-hydroxy-2-methylpropan-1-one Chemical compound CC(C)(C)C1=CC=C(C(=O)C(C)(C)O)C=C1 JHXJMPVUVKIGKC-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a method for producing a photoinitiator UV-1173 by a condensation method, belonging to the technical field of fine chemical engineering. Benzoic acid and isobutyric acid are used as raw materials, and Mn is that 2+ In the presence of salt, the condensation reaction is carried out at the temperature of 200-400 ℃ to generate the intermediate product isobutyryl benzene in one step, and then the isobutyryl benzene is subjected to chlorination and alkaline hydrolysis to prepare the photoinitiator UV-1173. The method reduces the use of dangerous chemicals, reduces the output of three wastes, and is an environment-friendly production process. Experiments show that the yield of isobutyryl benzene can reach more than 97 percent (calculated by benzoic acid). At the same time, with Mn 2+ The salt is used as a catalyst to realize continuous production, which is beneficial to prolonging the production period, and experiments show that 2.5kg of Mn 2+ 200kg of salt was continuously fed without deactivation of the catalyst. Mn of 2000kg 2+ The salt is continuously fed for 400 days, and isobutyryl benzene 632t can be produced. After the catalyst is deactivated, about 4200kg of solid waste is produced, namely only 6.6kg of solid waste is required to be produced per ton of isobutyryl benzene, and the production amount of the solid waste is greatly reduced.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a method for producing a photoinitiator UV-1173 by a condensation method.
Background
The photoinitiator UV-1173 (2-hydroxy-2-methyl-1-phenyl-1-propanone) is a novel photoinitiator with excellent performance, has the advantages of high initiation efficiency, good thermal stability, yellowing resistance, no peculiar smell and the like, and has outstanding position in photocuring
The method is characterized in that isobutyric acid is used as a raw material, and is subjected to acylation reaction, friedel-crafts reaction, chlorination reaction and alkaline hydrolysis reaction to prepare 2-hydroxy-2-methyl-1-phenyl-1-propanone, which is a main production method of a photoinitiator UV-1173. For example, chinese patent Nos. 201110200666.8 and 201810893357.5 each describe a process for producing the photoinitiator UV-1173 in a similar process.
However, the process not only needs to use a large amount of dangerous chemicals such as phosphorus trichloride, aluminum trichloride, chlorine and the like, but also generates a large amount of three-waste substances in the process such as high-phosphorus wastewater, aluminum water generated by Friedel-crafts reaction hydrolysis treatment, hydrogen chloride gas, hydrochloric acid wastewater and the like, which is not beneficial to environmental protection.
In order to overcome the problems, the Chinese patent No. 201810727673.5 provides a preparation process of a photoinitiator 1173, which takes benzoic acid and isobutyric acid as raw materials, dehydrates and decarbonates at high temperature under the action of a metal salt catalyst to obtain isobutyryl benzene, and then takes the isobutyryl benzene as an intermediate product, takes carbon tetrachloride and sodium hydroxide as reagents and tetrabutylammonium bromide as a phase transfer catalyst to carry out one-pot chlorination and alkaline hydrolysis reaction to obtain 2-hydroxy-2-methyl-1-phenyl-1-propanone. The process reduces the use of dangerous chemical substances and reduces the generation amount of three wastes, however, the reaction yield is lower and the catalyst needs to be frequently replaced due to the selection of the catalyst and the reaction temperature, which is not beneficial to long-time stable production and generates a large amount of solid wastes.
Disclosure of Invention
Based on the above, the invention provides a method for producing a photoinitiator UV-1173 by a condensation method, which aims to solve the technical problems that the yield is lower and the production cannot be stably carried out for a long time when the photoinitiator UV-1173 is produced by taking benzoic acid and isobutyric acid as raw materials in the prior art.
The technical scheme for solving the technical problems is as follows:
a method for producing a photoinitiator UV-1173 by condensation, comprising the steps of:
s10, mixing isobutyric acid with benzoic acid to prepare a raw material mixed solution A, wherein the mass ratio of isobutyric acid to benzoic acid is 1 (0.6-1.0);
s20, the raw material mixed solution A contacts with a catalyst, and condensation reaction is carried out at a first reaction temperature to generate isobutyryl benzene; wherein the catalyst is Mn 2+ One or more of the salts;
s30, synthesizing 2-hydroxy-2-methyl-1-phenyl-1-acetone by using isobutyryl benzene.
Preferably, in step S20, the "raw material mixed solution a contacts with a catalyst, and performs a condensation reaction at a first reaction temperature to generate isobutyryl benzene" includes the following steps:
s21, catalyst activation: heating the raw material mixed solution A to an activation temperature, adding a catalyst, fully mixing, and preserving heat for a first time;
s22, condensation reaction: after the heat preservation is finished, dropwise adding a raw material mixed solution A at a first reaction temperature to perform condensation reaction; condensing and collecting gas phase fractions to obtain a crude product B;
s23, a separation stage: unreacted raw material isobutyric acid and benzoic acid and isobutyryl benzene were separated from crude B.
Preferably, the first reaction temperature is 200 ℃ to 400 ℃.
Preferably, in step S21, the activation temperature is 200 ℃ to 400 ℃.
Preferably, in the step S22, after the heat preservation is finished, the raw material mixed solution A is dropwise added at the first reaction temperature at the dropwise adding rate of 40g/h to 75g/h of catalyst per kilogram to carry out condensation reaction.
Preferably, in step S21, the mass ratio of the catalyst to the raw material mixture A is 1 (1-1.5).
Preferably, in step S10, the ratio of the amounts of the substances of isobutyric acid to benzoic acid is 1 (0.83-0.90).
Preferably, the catalyst is MnO, mnCl, mn (NO 3 ) 2 、MnSO 4 、MnCO 3 One or more of manganese (II) benzoate and manganese (II) acetate.
Preferably, in step S30, the "synthesis of 2-hydroxy-2-methyl-1-phenyl-1-propanone with isobutyrophenone" comprises the steps of: isobutyryl benzene is used as a raw material, and 2-hydroxy-2-methyl-1-phenyl-1-acetone is prepared through a chlorination reaction and an alkaline hydrolysis reaction.
Preferably, in step S30, the "synthesis of 2-hydroxy-2-methyl-1-phenyl-1-propanone with isobutyrophenone" comprises the steps of:
s31, chlorination reaction: introducing Cl into isobutyryl benzene at a chlorination reaction temperature of 50-80 DEG C 2 Carrying out chlorination reaction to obtain chloroketone A;
s32, alkaline hydrolysis reaction: and (3) adding chloroketone A into liquid alkali, and stirring to perform alkaline hydrolysis reaction.
Compared with the prior art, the invention has at least the following advantages:
benzoic acid and isobutyric acid are used as raw materials, and Mn is that 2+ In the presence of salt, the condensation reaction is carried out at the temperature of 200-400 ℃ to generate the intermediate product isobutyryl benzene in one step, and then the isobutyryl benzene is subjected to chlorination and alkaline hydrolysis to prepare the 2-hydroxy-2-methyl-1-phenyl-1-acetone (namely the photoinitiator UV-1173). The method provided by the invention synthesizes isobutyryl benzene by a one-step method, reduces the use of dangerous chemicals and reduces three wastes compared with the Friedel-crafts reaction processThe output is an environment-friendly production process. In Mn 2+ As the salt is used as a catalyst, experiments show that the yield of the photoinitiator UV-1173 is improved, and the yield of the UV-1173 can reach more than 90 percent (calculated by benzoic acid). At the same time, with Mn 2+ The salt is used as a catalyst to realize continuous production, which is beneficial to prolonging the production period, and experiments show that 2.5kg of Mn 2+ 200kg of salt was continuously fed without deactivation of the catalyst. Industrial production practice shows that 2000kg of Mn 2+ The salt is continuously fed for 400 days, and isobutyryl benzene 632t can be produced. After the catalyst is deactivated, about 4200kg of solid waste is produced, namely only 6.6kg of solid waste is required to be produced per ton of isobutyryl benzene, and the production amount of the solid waste is greatly reduced.
Detailed Description
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other. The technical scheme of the present invention will be further described below in conjunction with the embodiments of the present invention, and the present invention is not limited to the following specific embodiments.
In one embodiment, a method for producing a photoinitiator UV-1173 by condensation comprises the steps of:
s10, mixing isobutyric acid with benzoic acid to prepare a raw material mixed solution A, wherein the mass ratio of isobutyric acid to benzoic acid is 1 (0.6-1.0).
Preferably, the ratio of the amounts of the substances isobutyric acid to benzoic acid is 1 (0.90-0.98), the corresponding mass ratio of benzoic acid to isobutyric acid is 1 (1.25-1.35): 1, that is to say, the isobutyric acid is in excess in the starting material system of the reaction.
S20, the raw material mixed solution A contacts with a catalyst, and condensation reaction is carried out at a first reaction temperature to generate isobutyryl benzene; wherein the catalyst is Mn 2+ One or more of the salts.
Preferably, the first reaction temperature is 200 ℃ to 400 ℃, and further, the first reaction temperature is 280 ℃ to 320 ℃. The condensation reaction process is shown as a formula I:
at 200-400 deg.C, mn 2+ The salt is used as a catalyst, and the benzoic acid and the isobutyric acid are subjected to condensation reaction to generate isobutyryl benzene, and water and carbon dioxide are simultaneously generated. At high temperature, water and carbon dioxide are discharged from the reaction system in a gas phase form, which is advantageous for the reaction.
For example, catalyst Mn 2+ The salt may be MnO, mnCl, mn (NO) 3 ) 2 、MnSO 4 、MnCO 3 One or more of manganese (II) benzoate and manganese (II) acetate. For example, catalyst Mn 2+ The salt can be MnO and MnCO 3 Is a mixture of (a) and (b). Preferably, mn 2+ The salt may be manganese (II) benzoate.
Specifically, the above process comprises the steps of:
s21, catalyst activation: and heating the raw material mixed solution A to an activation temperature, adding a catalyst, fully mixing, and preserving heat for a first time.
In one embodiment, the feedstock mixture a is first warmed to an activation temperature, for example, 200 ℃ to 400 ℃, condensed and the vapor phase is collected to establish total reflux. After the temperature is raised to the target temperature, adding a catalyst Mn 2+ The salt, preferably the catalyst, is added in an amount of 1 to 1.5 times the mass of the raw material mixture A. Sufficiently stirring to make the catalyst Mn 2+ The salt is fully mixed with the raw material mixture A, and the temperature is kept for 6 to 24 hours.
S22, condensation reaction: after the heat preservation is finished, dropwise adding a raw material mixed solution A at a first reaction temperature to perform condensation reaction; condensing and collecting gas phase fractions to obtain crude product B.
To catalyst Mn 2+ And (3) dropwise adding the raw material mixed solution A into a reaction system after the heat preservation and activation of the salt are finished, and performing condensation reaction. And condensing and collecting gas phase fractions, wherein part of the gas phase fractions are returned to the reaction system as reflux liquid phase, and the other part of the gas phase fractions are extracted to be used as crude products containing isobutyryl benzene. Preferably, the first reaction temperature is 200 ℃ to 400 ℃. The raw material mixture A should be slowly added dropwise into the reaction system, preferably 40g/h to 75g/h per kg of catalystAnd (3) dropwise adding the raw material mixed solution A at a certain rate to perform condensation reaction. It is to be noted that the "dropping raw material mixture A at a dropping rate of 40g/h to 75g/h per kg of catalyst" should be understood as: if the catalyst content in the system is 1kg, the dropping rate of the raw material mixed solution A is 40g/h-75g/h; if the catalyst content in the system is 2kg, the dropping rate of the raw material mixed solution A is 80g/h-150g/h; if the catalyst content in the system is 1000kg, the dropping rate of the raw material mixed liquid A is 40kg/h-75kg/h, and so on.
S23, a separation stage: unreacted raw material isobutyric acid and benzoic acid and isobutyryl benzene were separated from crude B.
For example, the raw isobutyric acid and the intermediate isobutyryl benzene are separated from the crude product B by distillation, wherein the purity of isobutyryl benzene is not less than 99%.
S30, synthesizing 2-hydroxy-2-methyl-1-phenyl-1-acetone by using isobutyryl benzene.
2-hydroxy-2-methyl-1-phenyl-1-propanone can be synthesized by various means using isobutyryl benzene as a starting material. For example, 2-hydroxy-2-methyl-1-phenyl-1-propanone can be prepared by one-pot chlorination and alkaline hydrolysis in a system using isobutyryl benzene as raw material and carbon tetrachloride and sodium hydroxide as reagents and tetrabutylammonium bromide as phase transfer catalyst as proposed in Chinese patent No. 201810727673.5. Or the chloroketone can be obtained by the prior chlorination reaction described in Chinese patent No. 201810893357.5, and then the crude product of the 2-hydroxy-2-methyl-1-phenyl-1-acetone can be prepared by the alkaline hydrolysis reaction.
Preferably, in step S30, the "synthesis of 2-hydroxy-2-methyl-1-phenyl-1-propanone with isobutyryl benzene" comprises the steps of:
s31, chlorination reaction: introducing Cl into isobutyryl benzene at a chlorination reaction temperature of 50-80 DEG C 2 And (3) carrying out chlorination reaction to obtain chloroketone A.
Introducing Cl into isobutyryl benzene 2 Chloridizing to prepare chloroketone A (chemical formula is shown as formula II). During the chlorination process, HCl and Cl are produced 2 And (3) the tail gas of the catalyst is absorbed by water to obtain hydrochloric acid as a byproduct.
S32, alkaline hydrolysis reaction: and (3) adding chloroketone A into liquid alkali, and stirring to perform alkaline hydrolysis reaction.
And (3) adding the chloroketone A into liquid alkali (NaOH solution, 0.1M), stirring to perform alkaline hydrolysis, and ending the alkaline hydrolysis when the content of the chloroketone A in the system is less than 0.2%. Washing with water to neutrality to obtain coarse 2-hydroxy-2-methyl phenyl propane-1-ketone product.
The 2-hydroxy-2-methylphenyl propane-1-ketone crude product is further processed by rectification and the like to obtain a 2-hydroxy-2-methylphenyl propane-1-ketone finished product with the purity of more than or equal to 95 percent, namely a photoinitiator UV-1173.
It should be appreciated by those skilled in the art that the concepts of the present invention may also be applied to the preparation of other α -hydroxy ketone photoinitiators, such as UV-184 (1-hydroxycyclohexylphenyl ketone), UV-2959 (2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropenyl acetone), photoinitiator 185 (2-hydroxy-2-methyl-1- [4- (tert-butyl) phenyl)]-1-propanone). For example, in Mn 2+ The salt is used as a catalyst, and benzoic acid and cyclohexanecarboxylic acid are used as raw materials for preparing 1-hydroxycyclohexyl phenyl ketone, so as to prepare a photoinitiator UV-184.
For another example, a method of producing the photoinitiator 185 includes the steps of:
t10. mixing isobutyric acid with tert-butylbenzoic acid to prepare a raw material mixture a, wherein the ratio of the amounts of isobutyric acid and tert-butylbenzoic acid is 1 (0.6-1.0).
Preferably, the ratio of the amounts of isobutyric acid to t-butylbenzoic acid is 1 (0.83-0.90), that is, the isobutyric acid is in excess in the starting material system of the reaction.
T20 the raw material mixture A is contacted with a catalyst to generate condensation reaction at a first reaction temperature to generate 2-methyl-1- [4- (tertiary butyl) phenyl]-1-propanone; wherein the catalyst is Mn 2+ One or more of the salts.
Preferably, the first reaction temperature is 200 ℃ to 400 ℃, and further, the first reaction temperature is 280 ℃ to 320 ℃.
At 200-400 deg.C, mn 2+ The salt is used as a catalyst for the condensation reaction of tert-butylbenzoic acid and isobutyric acid to generate 2-methyl-1- [4- (tert-butyl) phenyl]-1-propanone with simultaneous production of water and carbon dioxide. At high temperature, water and carbon dioxide are discharged from the reaction system in a gas phase form, which is advantageous for the reaction.
For example, catalyst Mn 2+ The salt may be MnO, mnCl, mn (NO) 3 ) 2 、MnSO 4 、MnCO 3 One or more of manganese (II) benzoate and manganese (II) acetate. For example, catalyst Mn 2+ The salt can be MnO and MnCO 3 Is a mixture of (a) and (b). Preferably, mn 2+ The salt may be manganese (II) benzoate.
Specifically, the above process comprises the steps of:
t21. catalyst activation stage: and heating the raw material mixed solution A to an activation temperature, adding a catalyst, fully mixing, and preserving heat for a first time.
In one embodiment, the feedstock mixture a is first warmed to an activation temperature, for example, 200 ℃ to 400 ℃, condensed and the vapor phase is collected to establish total reflux. After the temperature is raised to the target temperature, adding a catalyst Mn 2+ The salt, preferably the catalyst, is added in an amount of 1 to 1.5 times the mass of the raw material mixture A. Sufficiently stirring to make the catalyst Mn 2+ The salt is fully mixed with the raw material mixture A, and the temperature is kept for 6 to 24 hours.
T22. condensation reaction stage: after the heat preservation is finished, dropwise adding a raw material mixed solution A at a first reaction temperature to perform condensation reaction; condensing and collecting gas phase fractions to obtain crude product B.
To catalyst Mn 2+ And (3) dropwise adding the raw material mixed solution A into a reaction system after the heat preservation and activation of the salt are finished, and performing condensation reaction. Condensing and collecting gas phase fraction, partially returning to the reaction system as reflux liquid phase, partially extracting to obtain the product containing 2-methyl-1- [4- (tert-butyl) phenyl]Crude 1-propanone. Preferably, the first reaction temperature is 200 ℃ to 400 ℃. The raw material mixed solution A should be slowly droppedPreferably, the raw material mixed solution A is added dropwise into the reaction system at a dropping rate of 40g/h to 75g/h per kg of catalyst to carry out condensation reaction. It is to be noted that the "dropping raw material mixture A at a dropping rate of 40g/h to 75g/h per kg of catalyst" should be understood as: if the catalyst content in the system is 1kg, the dropping rate of the raw material mixed solution A is 40g/h-75g/h; if the catalyst content in the system is 2kg, the dropping rate of the raw material mixed solution A is 80g/h-150g/h; if the catalyst content in the system is 1000kg, the dropping rate of the raw material mixed liquid A is 40kg/h-75kg/h, and so on.
T23. separation stage: unreacted starting isobutyric acid was separated from the crude B with tert-butylbenzoic acid and 2-methyl-1- [4- (tert-butyl) phenyl ] -1-propanone.
For example, the raw isobutyric acid and the intermediate 2-methyl-1- [4- (tert-butyl) phenyl ] -1-propanone are separated from the crude B by distillation.
T30. photoinitiator 185 (2-hydroxy-2-methyl-1- [4- (tert-butyl) phenyl ] -1-propanone) was synthesized as 2-methyl-1- [4- (tert-butyl) phenyl ] -1-propanone.
The technical scheme and technical effects of the present invention are further described below through specific experimental examples.
Experimental example 1
Raw material mixed solutions A1, A2 and A3 are respectively prepared according to the mass ratio of benzoic acid to isobutyric acid of 1.35:1, 1.25:1 and 1.15:1. 2.5kg of mixed acid and 2kg of catalyst MnO are added into a kettle-type reactor for experiment, and stirring, heating and activating are carried out. And slowly rising the temperature, and when the temperature reaches 300 ℃, starting to dropwise add the prepared raw material mixed solutions A1, A2 and A3 into the experimental kettle type reactor according to the dropwise adding flow rate of 100g/h to perform condensation reaction. And (3) feeding, condensing and collecting fractions generated by the condensation reaction through a condenser, collecting condensate for rectification, and recovering excessive cyclohexanecarboxylic acid to be used in a mixed acid configuration to obtain an intermediate isobutyryl benzene with the content of more than 99%. The obtained isobutyryl benzene is subjected to chlorination, alkaline hydrolysis and rectification to obtain the 2-hydroxy-2-methyl-1-phenyl-1-acetone photoinitiator.
The purity of the obtained isobutyryl benzene (before rectification) was examined, and the yield of isobutyryl benzene was calculated as shown in table 1.
TABLE 1 purity and yield of isobutyryl benzene obtained in Experimental example one
| Sequence number | Benzoic acid: isobutyric acid | Mixed acid feeding amount | Weight of fraction | Purity of | Yield (calculated as benzoic acid) |
| A1 | 1.35:1 | 200kg | 128.4kg | 98.2％ | 90.37％ |
| A2 | 1.25:1 | 200kg | 132.1kg | 99.5％ | 97.41％ |
| A3 | 1.15:1 | 200kg | 126.2kg | 99.2％ | 96.36％ |
As can be seen from Table 1, the purity of the obtained isobutyryl benzene can reach more than 99% under the catalysis of MnO, and the yield of the isobutyryl benzene can reach 96% when the isobutyric acid is excessive. Meanwhile, the catalyst is continuously produced until the total feeding amount is more than 200kg, and still keeps higher catalytic activity.
Experimental example two
And preparing a raw material mixed solution A4 according to the mass ratio of benzoic acid to isobutyric acid of 1.25:1. 2.5kg of mixed acid and 2kg of catalyst MnCO are taken 3 Adding the mixture into a reactor for experiments, and stirring, heating and activating the mixture. And slowly rising the temperature, and when the temperature reaches 320 ℃, starting to dropwise add the prepared raw material mixed solution A4 into the experimental kettle type reactor according to the dropwise adding flow rate of 80g/h to perform condensation reaction. And (3) feeding, condensing and collecting fractions generated by the condensation reaction through a condenser, collecting condensate for rectification, and recovering excessive cyclohexanecarboxylic acid to be used in a mixed acid configuration to obtain an intermediate isobutyryl benzene with the content of more than 99%. The obtained isobutyryl benzene is subjected to chlorination, alkaline hydrolysis and rectification to obtain the 2-hydroxy-2-methyl-1-phenyl-1-acetone photoinitiator.
The purity of the obtained isobutyryl benzene (before rectification) was examined, and the yield of isobutyryl benzene was calculated as shown in table 2.
Experimental example III
And preparing a raw material mixed solution A4 according to the mass ratio of benzoic acid to isobutyric acid of 1.25:1. 2.5kg of mixed acid and 2kg of catalyst manganese (II) benzoate are added into a kettle-type reactor for experiment, and stirring, heating and activating are carried out. Slowly raising the temperature, and when the temperature reaches 280 ℃, starting to dropwise add the prepared raw material mixed solution A4 into the experimental kettle type reactor according to the dropwise adding flow rate of 80g/h to perform condensation reaction. And (3) feeding, condensing and collecting fractions generated by the condensation reaction through a condenser, collecting condensate for rectification, and recovering excessive cyclohexanecarboxylic acid to be used in a mixed acid configuration to obtain an intermediate isobutyryl benzene with the content of more than 99%. The obtained isobutyryl benzene is subjected to chlorination, alkaline hydrolysis and rectification to obtain the 2-hydroxy-2-methyl-1-phenyl-1-acetone photoinitiator.
The purity of the obtained isobutyryl benzene (before rectification) was examined, and the yield of isobutyryl benzene was calculated as shown in table 2.
TABLE 2 purity and yield of isobutyrylbenzene obtained in Experimental examples two and three
| Sequence number | Benzoic acid: isobutyric acid | Mixed acid feeding amount | Weight of fraction | Purity of | Yield (calculated as benzoic acid) |
| A4 | 1.25:1 | 200kg | 133.7kg | 99.4％ | 97.58％ |
| A4 | 1.25:1 | 200kg | 134.3kg | 99.0％ | 97.23％ |
As can be seen from Table 2, mnCO 3 And the purity of the obtained isobutyryl benzene can reach more than 99% under the catalysis of the manganese (II) benzoate, the yield of the isobutyryl benzene can reach more than 97% when the isobutyric acid is excessive, and particularly, the yield of the isobutyryl benzene can reach more than 97% under the catalysis of the manganese (II) benzoate. Meanwhile, the catalyst is continuously produced until the total feeding amount is more than 200kg, and still keeps higher catalytic activity.
Experimental example four
And preparing a raw material mixed solution A4 according to the mass ratio of benzoic acid to isobutyric acid of 1.25:1. 2500kg of mixed acid and 2000kg of catalyst MnO (G1) and MnCO are taken 3 (G2) Manganese (II) benzoate (G3), mnO and MnCO 3 (1:1 ratio of the amounts of substances) (G4) was added to a volume of 10m 3 In the tank reactor, stirring, heating and activating are carried out. Slowly raising the temperature, and when the temperature reaches 300 ℃, starting to dropwise add the prepared raw material mixed solution A4 into the experimental kettle type reactor according to the dropwise adding flow rate of 100kg/h to perform condensation reaction. And (3) feeding, condensing and collecting fractions generated by the condensation reaction through a condenser, collecting condensate for rectification, and recovering excessive cyclohexanecarboxylic acid to be used in a mixed acid configuration to obtain an intermediate isobutyryl benzene with the content of more than 99%.
Statistics when the catalyst activity was significantly reduced (the content of isobutyryl benzene in the produced condensate was reduced), the number of days for continuous and stable operation of the apparatus, the total amount of isobutyryl benzene produced, and the amount of residual liquid at the bottom of the reaction vessel were counted, and the amount of solid waste produced per unit mass of isobutyryl benzene produced was calculated, as shown in table 3.
Table 3 statistical results of Experimental example four
| Lot number | Catalyst feed | Run time | Yield of isobutyryl benzene | Residue of kettle | Residue of kettle for ton products |
| G1 | 2000kg | 404 days | 632 ton | 4200kg | 6.6kg |
| G2 | 2000kg | 452 days | 780 ton | 4150kg | 5.3kg |
| G3 | 2000kg | 420 days | 720 ton | 3820kg | 5.3kg |
| G4 | 2000kg | 512 days | 825 tons | 4230kg | 5.1kg |
As can be seen from Table 3, mnO (G1) and MnCO 3 (G2) Manganese (II) benzoate (G3), mnO and MnCO 3 The mixture (the ratio of the substances is 1:1) (G4) is used as a catalyst for industrial large-scale production, the activity of the catalyst can maintain the continuous and stable operation of the kettle reactor for more than 400 days, and the mass of solid waste produced by each ton of isobutyryl benzene production is only 5.1kg-6.6kg, so that the catalyst is an environment-friendly production process.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A method for producing a photoinitiator UV-1173 by condensation, comprising the steps of:
s10, mixing isobutyric acid and benzoic acid to prepare a raw material mixed solution A, wherein the ratio of the amounts of substances of the benzoic acid to the isobutyric acid is (1.15-1.25): 1;
s20, the raw material mixed solution A contacts with a catalyst, and condensation reaction is carried out at a first reaction temperature to generate isobutyryl benzene; wherein the catalyst is MnO and MnCO with the mass ratio of 1:1 3 Is a mixture of (a) and (b);
s30, synthesizing 2-hydroxy-2-methyl-1-phenyl-1-acetone by using isobutyryl benzene;
in step S20, the "raw material mixture a contacts with a catalyst and undergoes a condensation reaction at a first reaction temperature to produce isobutyryl benzene" includes the following steps:
s21, catalyst activation stage: heating the raw material mixed solution A to an activation temperature, adding a catalyst, fully mixing, and preserving heat for a first time;
s22, condensation reaction stage: after the heat preservation is finished, dropwise adding a raw material mixed solution A at a first reaction temperature to perform condensation reaction; condensing and collecting gas phase fractions to obtain a crude product B;
s23, separation: unreacted raw material isobutyric acid and benzoic acid and isobutyryl benzene were separated from crude B.
2. The method of producing a photoinitiator UV-1173 according to claim 1, wherein the first reaction temperature is 200 ℃ to 400 ℃.
3. The method for producing a photoinitiator UV-1173 according to claim 1, wherein the activation temperature is 200 ℃ to 400 ℃ in step S21.
4. The method for producing a photoinitiator UV-1173 according to claim 1, wherein in the step S22, after the heat preservation is finished, the raw material mixed solution A is dropwise added at a first reaction temperature at a dropwise adding rate of 40g/h to 75g/h per kg of the catalyst to carry out the condensation reaction.
5. The method for producing a photoinitiator UV-1173 according to claim 1, wherein the mass ratio of the catalyst to the raw material mixture A in the step S21 is 1 (1-1.5).
6. The method for producing a photoinitiator UV-1173 according to any one of claims 1 to 5, wherein the synthesis of 2-hydroxy-2-methyl-1-phenyl-1-propanone from isobutyrophenone in step S30 comprises the steps of: isobutyryl benzene is used as a raw material, and 2-hydroxy-2-methyl-1-phenyl-1-acetone is prepared through a chlorination reaction and an alkaline hydrolysis reaction.
7. The method for producing a photoinitiator UV-1173 according to claim 6, wherein the synthesis of 2-hydroxy-2-methyl-1-phenyl-1-propanone from isobutyryl benzene in step S30 comprises the steps of:
s31, chlorination reaction: introducing Cl into isobutyryl benzene at a chlorination reaction temperature of 50-80 DEG C 2 Carrying out chlorination reaction to obtain chloroketone A;
s32, alkaline hydrolysis reaction: and (3) adding chloroketone A into liquid alkali, and stirring to perform alkaline hydrolysis reaction.
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| CN107513012A (en) * | 2016-06-15 | 2017-12-26 | 江苏英力科技发展有限公司 | A kind of continuous method for preparing 1 (4 chlorphenyl) 1 butanone |
| CN108863769A (en) * | 2018-08-07 | 2018-11-23 | 宁夏沃凯珑新材料有限公司 | A kind of preparation method of photoinitiator 2- hydroxy-2-methyl phenyl-propane -1- ketone |
| CN108892605A (en) * | 2018-07-04 | 2018-11-27 | 大丰鑫源达化工有限公司 | A kind of preparation process of photoinitiator 1173 |
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| CN106518638A (en) * | 2016-11-02 | 2017-03-22 | 怀化金鑫新材料有限公司 | New synthesis technology for photoinitiator1173 |
| CN108892605A (en) * | 2018-07-04 | 2018-11-27 | 大丰鑫源达化工有限公司 | A kind of preparation process of photoinitiator 1173 |
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