CN112707830A - Method for preparing tetraethyl mikrolon - Google Patents

Method for preparing tetraethyl mikrolon Download PDF

Info

Publication number
CN112707830A
CN112707830A CN202011576161.7A CN202011576161A CN112707830A CN 112707830 A CN112707830 A CN 112707830A CN 202011576161 A CN202011576161 A CN 202011576161A CN 112707830 A CN112707830 A CN 112707830A
Authority
CN
China
Prior art keywords
diethylaniline
reaction
catalyst
lewis acid
added
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202011576161.7A
Other languages
Chinese (zh)
Other versions
CN112707830B (en
Inventor
赵国锋
张齐
毛桂红
张志鹏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin Jiuri New Materials Co ltd
Original Assignee
Tianjin Jiuri New Materials Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tianjin Jiuri New Materials Co ltd filed Critical Tianjin Jiuri New Materials Co ltd
Priority to CN202011576161.7A priority Critical patent/CN112707830B/en
Publication of CN112707830A publication Critical patent/CN112707830A/en
Application granted granted Critical
Publication of CN112707830B publication Critical patent/CN112707830B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • B01J27/10—Chlorides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7815—Zeolite Beta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/02—Formation of carboxyl groups in compounds containing amino groups, e.g. by oxidation of amino alcohols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions

Abstract

The invention relates to a method for preparing tetraethyl mikrolon, which comprises the steps of taking N, N-diethylaniline and solid phosgene as raw materials, carrying out acyl chlorination reaction on the N, N-diethylaniline and the raw materials in a solvent to obtain a reaction intermediate product, and then taking a supported catalyst containing Lewis acid as a catalyst to react with the N, N-diethylaniline to obtain a target reaction product tetraethyl mikrolon; the method can effectively reduce the occurrence of side reactions, thereby improving the yield of the target product; and after the reaction is finished, the catalyst is collected through solid-liquid separation, so that the separation efficiency is high, and further the subsequent cyclic utilization is facilitated.

Description

Method for preparing tetraethyl mikrolon
Technical Field
The invention belongs to the field of preparation of photoinitiators, and relates to a preparation method of tetraethyl michaelis ketone.
Background
Tetraethyl michigan ketone, also known as 4,4' -bis (diethylamino) benzophenone, is a high-efficiency II-type free radical photoinitiator and can initiate oligomer polymerization reaction under the irradiation of ultraviolet light; in addition, tetraethyl mikrolon is also an intermediate for producing alkaline brilliant blue dye BO and triphenylmethane chemicals, and is one of the widely used chemical raw materials in China.
The prior art discloses a method for preparing tetraalkyl michelson by taking N, N-dialkyl (methyl) aniline and phosgene as raw materials through condensation reaction, which specifically comprises the following steps: the N, N-dialkyl aniline and phosgene react to produce dialkyl amino benzoyl chlorobenzene, and the dialkyl amino benzoyl chlorobenzene is reacted with ZnCl2Under the catalytic action, the compound is continuously combined with N, N-dialkyl aniline to generate tetraalkyl michaelis ketone; because phosgene is a highly toxic substance, the risk of the operation process is high, and the yield of the preparation process is insufficient;
the reaction equation of the preparation process of the prior art is shown as follows:
Figure BDA0002864035630000011
in addition, the prior art also discloses a method for preparing tetraethyl ketone by using N, N-dialkyl aniline and formaldehyde as raw materials through an oxidation process, which specifically comprises the following steps: under the action of a catalyst, reacting N, N-dialkyl aniline with formaldehyde to obtain 4,4' -bis (dialkyl amino) diphenylmethane, and then carrying out catalytic oxidation in an oxygen atmosphere to obtain tetraethyl mikrolon; the defects of the scheme are high requirements on reaction equipment and poor safety and reaction stability.
The reaction equation of the preparation process of the prior art is shown as follows:
Figure BDA0002864035630000021
therefore, the development of a method for preparing tetraethyl mikrolone with high yield of target products and mild reaction conditions still has important significance.
Disclosure of Invention
The invention aims to provide a method for preparing tetraethyl mikrolon, which takes N, N-diethylaniline and solid phosgene as raw materials, the N, N-diethylaniline and the solid phosgene are subjected to acyl chlorination reaction in a solvent to obtain a reaction intermediate product, and then a supported catalyst containing Lewis acid is used as a catalyst to react with the N, N-diethylaniline to obtain a target reaction product tetraethyl mikrolon; the method can effectively reduce the occurrence of side reactions, thereby improving the yield of the target product; and after the reaction is finished, the catalyst is collected through solid-liquid separation, so that the separation efficiency is high, and further the subsequent cyclic utilization is facilitated.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of tetraethyl mikrolon, which comprises the following steps:
(1) mixing N, N-diethylaniline with a solid phosgene solution, and reacting to obtain a reaction intermediate product shown in the following formula (a);
Figure BDA0002864035630000022
(2) mixing the reaction intermediate product obtained in the step (1), N-diethylaniline and a catalyst, and reacting to obtain tetraethyl ketone;
wherein the catalyst is selected from supported catalysts comprising Lewis acids.
Here, the N, N-diethylaniline in step (2) is selected from two addition modes, the first: adding in the step (1); and the second method comprises the following steps: after the reaction in the step (1) is finished, adding a catalyst, and then adding N, N-diethylaniline; and preferably adopting a second adding mode; the adoption of the second material adding mode is beneficial to improving the yield of the target product; and (2) adding the reaction raw material N, N-diethylaniline in a second material adding mode in sections, namely adding part of the N, N-diethylaniline in the step (1), adding the rest N, N-diethylaniline after the acylation reaction is completed and adding the catalyst, which is favorable for reducing the generation of impurities such as triphenyl compounds and improving the yield of the target product.
In the invention, the reaction process equation of the preparation method of tetraethyl mikrolon is shown as follows;
Figure BDA0002864035630000031
as can be seen from the above reaction equation, in the present invention, N-diethylaniline and phosgene are used as the reaction raw materials; performing acyl chlorination reaction on N, N-diethylaniline and solid phosgene in a solvent to generate a reaction intermediate product; then the intermediate product, N-diethylaniline and catalyst are mixed and reacted to generate tetraethyl michael ketone; in the above reaction, AlCl, a conventional Lewis acid, is used3Or ZnCl2When the product is directly used as a system catalyst, the target product tetraalkyl michaelis ketone can not be obtained or the yield is low, and the production requirement can not be met; in order to solve the technical problems, the invention discovers, through research, that the specific type of lewis acid is fixed on the surface of a specific carrier, and the obtained supported catalyst containing the lewis acid is used as the catalyst in the step (2), so that the occurrence of side reactions can be obviously reduced, the generation of triphenyl compounds can be reduced, and the yield of the target product tetraethyl mikrone can be further improved.
The research on the reaction process in the step (2) in the preparation method discovers that the Lewis acid AlCl is directly adopted3、ZnCl2When the catalyst is used as a catalyst, the reaction intermediate product generated in the first step of reaction in the reaction process is very easy to further react with N, N-diethylaniline to generate a triphenyl compound due to high activity, so that the yield of a reaction target product is low or cannot be obtained; book (I)According to the invention, the specific carrier-supported Lewis acid is used as the catalyst, so that the generation of the triphenyl compound can be effectively inhibited, the selectivity of the reaction on the target product is obviously improved, and the yield of the product is further improved.
After the reaction is finished in the preparation method, the catalyst is collected by solid-liquid separation, so that the separation efficiency is high, and the subsequent cyclic utilization is facilitated.
The preparation method has the characteristic of high yield of target reaction products, the yield of the tetraethyl mikrolon can reach more than 85 percent, and the subsequent catalyst is convenient to separate and recycle.
Preferably, the lewis acid in the supported catalyst comprising a lewis acid is selected from AlCl3、ZnCl2、BiCl3、TiCl4、FeCl3And FeCl2At least one of; preferably BiCl3And/or TiCl4。
Preferably, the support of the supported catalyst comprising a lewis acid is selected from at least one of silica and molecular sieves.
Silica here refers to a silica support that does not have a molecular sieve structure.
According to the invention, the carrier is compounded with Lewis acid and used as a catalyst for the reaction in the step (2), compared with the method of directly adopting Lewis acid as a catalyst, the generation of triphenyl byproducts is effectively inhibited, and the yield of the target product is obviously improved.
Preferably, the molecular sieve is selected from an all-silica molecular sieve, preferably at least one of a Silicalite-1 molecular sieve, an all-silica MCM-41 molecular sieve and an all-silica Beta molecular sieve.
In the present invention, the molecular sieve as the carrier is preferably in the above range, and the yield of the target product obtained by the catalytic reaction of the molecular sieve and the catalyst obtained by complexing the molecular sieve with the lewis acid is higher.
Preferably, the catalyst is prepared by a method comprising: and (3) activating the carrier, then soaking the carrier in a Lewis acid solution, evaporating to remove the solvent, and drying to obtain the catalyst.
Herein LewisThe selection of the solvent in the acid solution and the dissolving temperature are determined according to the type of the Lewis acid; when Lewis acid selects AlCl3The solvent can be selected from ethanol, toluene and the like, and is heated for dissolution; when the Lewis acid selects ZnCl2、FeCl3、FeCl2、BiCl3The solvent can be selected from ethanol and the like; when the Lewis acid selects TiCl4In the case, the solvent may be selected from dichloromethane, toluene, etc., and is not particularly limited.
Preferably, the activating treatment method comprises the steps of immersing the carrier in a strong base and weak acid salt aqueous solution, carrying out solid-liquid separation, and roasting in a protective atmosphere.
The invention adopts the activation step, which can strengthen the binding force of the Lewis acid and the carrier and simultaneously improve the selectivity of the catalytic reaction on the target product.
Preferably, the strong and weak acid carbonate in the aqueous solution of strong and weak acid carbonate is at least one selected from the group consisting of alkali metal carbonate, alkali metal bicarbonate and alkali metal acetate.
Preferably, the alkali metal carbonate is selected from sodium carbonate and/or potassium carbonate.
Preferably, the alkali metal bicarbonate is selected from sodium bicarbonate and/or potassium bicarbonate.
Preferably, the alkali metal acetate is selected from sodium acetate and/or potassium acetate.
Preferably, the protective atmosphere is selected from at least one of nitrogen, argon and helium.
Preferably, the temperature of the calcination is 300 ℃ to 500 ℃, such as 350 ℃, 400 ℃, 450 ℃, or the like.
Preferably, the roasting time is 2h to 6h, such as 3h, 4h or 5 h.
In the invention, the temperature of the activation treatment is in the range, which is beneficial to strengthening the bonding force of the Lewis acid and the carrier, and improving the selectivity of the catalytic reaction on the target product, thereby improving the product yield.
Preferably, the temperature of the evaporation to remove the solvent is 20 ℃ to 65 ℃, such as 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃ or 60 ℃.
Preferably, the drying is vacuum drying.
Preferably, the amount of lewis acid supported on the catalyst is 5% to 50%, for example 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or the like, preferably 20% to 35%, based on 100% by mass of the support.
In the invention, when the content of the Lewis acid on the catalyst is in the range, the selectivity of the obtained catalyst on a target product in a catalytic reaction is higher, thereby being beneficial to obtaining higher yield.
Preferably, the solvent of the solid phosgene solution in the step (1) comprises dichloroethane.
Preferably, the method for mixing N, N-diethylaniline with the solid phosgene solution in the step (1) to carry out the reaction comprises the following steps: under the condition that the temperature is-10 ℃ to 0 ℃, for example, -9 ℃, 8 ℃, 7 ℃, 6 ℃, 5 ℃,4 ℃, 3 ℃, 2 ℃ or-1 ℃, the solid phosgene solution is dripped into N, N-diethylaniline, and then the temperature is raised for reaction.
Preferably, the temperature of the temperature-raising reaction is 10 ℃ to 65 ℃, for example, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃ or 60 ℃, and the like, preferably 60 ℃ to 65 ℃.
Preferably, the temperature-raising reaction process is a step-by-step temperature raising process, and comprises the following steps: heating to 10-15 deg.C, such as 11 deg.C, 12 deg.C, 13 deg.C or 14 deg.C, performing a first heat-preservation reaction, further heating to 30-35 deg.C, such as 31 deg.C, 32 deg.C, 33 deg.C or 34 deg.C, performing a second heat-preservation reaction, and then heating to 60-65 deg.C, such as 61 deg.C, 62 deg.C, 63 deg.C or 64 deg.C, and performing a third heat-preservation reaction.
Preferably, the time of the first heat preservation reaction is 1-3 h, such as 1.5h, 2h or 2.5 h.
Preferably, the time of the second heat preservation reaction is 3-5 h, such as 3.5h, 4h or 4.5 h.
Preferably, the time of the third heat-preservation reaction is 3-5 hours, such as 3.5 hours, 4 hours or 4.5 hours.
In the invention, the acylation reaction in the step (1) adopts the operation conditions, which is beneficial to inhibiting the generation of N, N-diethylaniline ortho-position acylation chlorination products shown in the following formula (b), thereby improving the yield of target intermediate products.
Figure BDA0002864035630000071
Preferably, the N, N-diethylaniline in the step (2) is added in the step (1), and the molar ratio of the added N, N-diethylaniline in the step (1) to the solid phosgene is (7-12: 1), such as 8:1, 9:1, 10:1 or 11: 1.
Preferably, the N, N-diethylaniline in the step (2) is added after the catalyst is added in the step (2), and the molar ratio of the added N, N-diethylaniline in the step (1) to the solid phosgene is 3-5: 1, such as 1:3, 1:4 or 1: 4.5; the ratio of the amount of N, N-diethylaniline added in step (1) to the amount of N, N-diethylaniline added in step (2) is 1 (1 to 1.3), for example, 1:1.05, 1:1.1, 1:1.15, 1:1.2 or 1:1.25, preferably 1 (1.05 to 1.15). Here, the N, N-diethylaniline is added in the steps (1) and (2) in an amount satisfying the above-mentioned conditions, which contributes to the improvement of the yield of the objective product.
In the preparation method, the raw material N, N-diethylaniline is added in two steps, which is beneficial to controlling the reaction rate in the step (2), reducing the occurrence of side reactions and improving the yield of the target product.
Preferably, the N, N-diethylaniline in the step (2) is added after the catalyst is added, and the N, N-diethylaniline in the step (2) is added dropwise.
The dropwise adding mode is adopted, so that the generation of triphenyl compounds can be effectively reduced, and the yield of target products is improved.
Preferably, the ratio of the molar amount of the Lewis acid in the catalyst added in the step (2) to the molar amount of the phosgene solid in the step (1) is 1 (0.2-20), such as 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18 or 1:19, and preferably 1 (0.5-5).
Preferably, the temperature of the reaction in step (2) is 15 to 45 ℃, for example, 20 ℃, 25 ℃, 30 ℃, 35 ℃ or 40 ℃, and the like, preferably 25 to 35 ℃.
The temperature is controlled within the range, so that the occurrence of side reactions is reduced, and the yield of the target product is improved.
Preferably, the method further comprises the steps of recovering the catalyst by solid-liquid separation after the reaction in the step (2) is finished to obtain an organic phase, and then performing reduced pressure desolventizing and recrystallization to obtain the tetraethyl mikrolon.
Preferably, the recrystallization solvent is selected from at least one of methanol, ethanol, and an alkane including petroleum ether.
As a preferable technical scheme of the invention, the preparation method of the tetraethyl michael ketone comprises the following steps:
(1) adding N, N-diethylaniline into a reaction kettle, cooling to-10-0 ℃, dropwise adding a solid phosgene solution into the reaction kettle under the stirring condition, wherein the molar ratio of the N, N-diethylaniline to the solid phosgene is 3-5: 1, after dropwise adding is finished, heating the reaction kettle to 10-15 ℃, carrying out heat preservation reaction for 1-3 h, continuously heating to 30-35 ℃, carrying out heat preservation reaction for 3-5 h, then heating to 60-65 ℃, and carrying out heat preservation reaction for 3-5 h to obtain a reaction intermediate product;
(2) adding a supported catalyst containing Lewis acid and N, N-diethylaniline into the reaction intermediate product obtained in the step (1), and reacting at 15-45 ℃ to obtain tetraethyl michael ketone; wherein the ratio of the addition amount of the N, N-diethylaniline in the step (1) to the addition amount of the N, N-diethylaniline in the step (2) is 1 (1-1.3), and the ratio of the molar amount of the Lewis acid on the catalyst to the molar amount of the solid phosgene added in the step (1) is 1 (0.5-2).
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the preparation method, N-diethylaniline and solid phosgene are used as raw materials, the raw materials and the N, N-diethylaniline are subjected to an acyl chlorination reaction in a solvent to obtain a reaction intermediate product, and then a supported catalyst containing Lewis acid is used as a catalyst to react with the N, N-diethylaniline to obtain a target product tetraethyl mikrone; the method can effectively reduce the occurrence of side reactions, thereby improving the yield of the target product;
(2) after the reaction in the preparation method, the catalyst can be collected by solid-liquid separation, the separation efficiency is high, and the subsequent recycling is convenient.
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 tetraethyl ketone, which specifically comprises the following steps:
(1) adding N, N-diethylaniline into a reaction kettle, cooling to-5 ℃, dropwise adding a solid phosgene solution (dichloroethane as a solvent) into the reaction kettle under the stirring condition, wherein the molar ratio of the N, N-diethylaniline to the solid phosgene is 4:1, after dropwise adding is finished, heating the reaction kettle to 10 ℃, keeping the temperature for reaction for 2 hours, continuously heating to 30 ℃, keeping the temperature for reaction for 3 hours, then heating to 60 ℃, keeping the temperature for reaction for 3 hours, and obtaining a reaction intermediate product;
(2) adding xBiCl into the reaction intermediate product obtained in the step (1)3the/Silicalite-1 molecular sieve is used as a catalyst, then N, N-diethylaniline is dripped, and the temperature is controlled at 25 ℃ for reaction; wherein the ratio of the addition amount of the N, N-diethylaniline in the step (1) to the addition amount of the N, N-diethylaniline in the step (2) is 1:1.1, and the ratio of the molar amount of the Lewis acid on the catalyst to the molar amount of the solid phosgene added in the step (1) is 1: 1;
(3) and (3) carrying out solid-liquid separation on the reaction product in the step (2), recovering the catalyst to obtain an organic phase, then carrying out decompression desolventizing, recovering the solvent and unreacted N, N-diethylaniline, and carrying out recrystallization by using ethanol as a recrystallization solvent to obtain the tetraethyl mikrone.
In this example, xBiCl3BiCl in the/Silicalite-1 molecular sieve catalyst based on 100 percent of the mass of the Silicalite-1 molecular sieve3The supported amount x of (b) is 30%, and the preparation method specifically comprises the following steps:
dipping the Silicalite-1 molecular sieve in 0.5mol/L sodium carbonate aqueous solution for 4h, and roasting for 5h at 400 ℃ in a helium atmosphere after solid-liquid separation to obtain an activated carrier;
the activated carrier is soaked in 0.3mol/L BiCl3The solution is added for 3 hours, the solvent is removed by evaporation at 50 ℃, and vacuum drying is carried out to obtain 0.3BiCl3A Silicalite-1 molecular sieve catalyst.
Example 2
This example differs from example 1 in that the BiCl in the catalyst3The amount of supported catalyst (x) was 20%, and other parameters and conditions were exactly the same as those in example 1.
Example 3
This example differs from example 1 in that the BiCl in the catalyst3The amount of supported x was 50%, and other parameters and conditions were exactly the same as in example 1.
Example 4
This example differs from example 1 in that the BiCl in the catalyst3The amount of supported x was 5%, and other parameters and conditions were exactly the same as in example 1.
Example 5
This example differs from example 1 in that the support equivalent mass was replaced with an all-silica MCM-41 molecular sieve, and the other parameters and conditions were exactly the same as in example 1.
Example 6
This example is different from example 1 in that the carrier equivalent mass is replaced by the all-silicon beta molecular sieve, and other parameters and conditions are completely the same as those in example 1.
Example 7
This example differs from example 1 in that the support and the like are replaced by fumed silica, and the other parameters and conditions are exactly the same as in example 1.
Example 8
This example differs from example 1 in that the amount of Lewis acid or the like is replaced by TiCl4Other parameters and conditions were exactly the same as in example 1.
Example 9
This embodiment and examples1 is distinguished by replacing the Lewis acid or the like as the supporting amount with FeCl3Other parameters and conditions were exactly the same as in example 1.
Example 10
This example differs from example 1 in that the amount of Lewis acid or the like is replaced with AlCl3Other parameters and conditions were exactly the same as in example 1.
Example 11
This example is different from example 1 in that the amount of the Lewis acid or the like is replaced with ZnCl2Other parameters and conditions were exactly the same as in example 1.
Example 12
This example is different from example 1 in that the amount of the Lewis acid or the like is replaced with FeCl2Other parameters and conditions were exactly the same as in example 1.
Example 13
The difference between the present embodiment and embodiment 1 is that the temperature-raising reaction in step (1) does not carry out temperature raising in stages, but directly raises the temperature to 60 ℃ for 8 h; other parameters and conditions were exactly the same as in example 1.
Example 14
This example differs from example 1 in that the amount of catalyst added in step (2) is such that the ratio of the molar amount of Lewis acid on the catalyst to the molar amount of phosgene solid added in step (1) is 1:0.5, the other parameters and conditions being exactly the same as in example 1.
Example 15
The embodiment provides a preparation method of tetraethyl ketone, which specifically comprises the following steps:
(1) adding N, N-diethylaniline into a reaction kettle, cooling to-6 ℃, dropwise adding a solid phosgene solution (dichloroethane as a solvent) into the reaction kettle under the stirring condition, wherein the molar ratio of the N, N-diethylaniline to the solid phosgene is 3.5:1, after dropwise adding is finished, heating the reaction kettle to 15 ℃, keeping the temperature for reaction for 1h, continuously heating to 35 ℃, keeping the temperature for reaction for 4h, then heating to 65 ℃, keeping the temperature for reaction for 4h, and obtaining a reaction intermediate product;
(2) adding xBiCl into the reaction intermediate product obtained in the step (1)3the/Silicalite-1 molecular sieve is used as a catalyst, then N, N-diethylaniline is dripped, and the temperature is controlled at 35 ℃ for reaction; wherein the ratio of the addition amount of the N, N-diethylaniline in the step (1) to the addition amount of the N, N-diethylaniline in the step (2) is 1:1.2, and the ratio of the molar amount of the Lewis acid on the catalyst to the molar amount of the solid phosgene added in the step (1) is 1: 1;
(3) and (3) carrying out solid-liquid separation on the reaction product in the step (2), recovering the catalyst to obtain an organic phase, then carrying out decompression desolventizing, recovering the solvent and unreacted N, N-diethylaniline, and carrying out recrystallization by using ethanol as a recrystallization solvent to obtain the tetraethyl mikrone.
The catalyst in step (2) of this example was exactly the same as in example 1.
Example 16
This example differs from example 1 in that the molar ratio of N, N-diethylaniline to phosgene solids in step (1) was 10:1, in that N, N-diethylaniline was not added in step (2), and in that the other parameters and conditions were exactly the same as in example 1.
Example 17
This example is different from example 1 in that the catalyst recovered in step (3) in example 1 was washed with ethanol and dried in vacuum, and then used as the catalyst in this example, and other parameters and conditions were exactly the same as those in example 1.
Example 18
The difference between this example and example 1 is that the carrier of equal mass is replaced by beta molecular sieve with 82 Si/Al ratio, and other parameters and conditions are exactly the same as those in example 1.
The preparation method of the beta molecular sieve with the silicon-aluminum ratio of 82 in the embodiment refers to the embodiment 1 in CN 107804856A.
The Silicalite-1 molecular sieve, the MCM-41 molecular sieve and the all-silicon beta molecular sieve adopted in the embodiment are prepared by referring to embodiment 1 in CN108002396A, CN109987613A and CN105800624A respectively;
comparative example 1
This comparative example differs from example 1 in that the catalyst in step (2) was replaced with a non-supported catalyst BiCl3(same as the molar amount of Lewis acid in the catalyst of example 1), and other parameters and conditions are exactly the same as in example 1.
Comparative example 2
This comparative example differs from example 1 in that the catalyst in step (2) was replaced by the unsupported catalyst AlCl3(same as the molar amount of Lewis acid in the catalyst of example 1), and other parameters and conditions are exactly the same as in example 1.
Comparative example 3
This comparative example differs from example 1 in that the catalyst in step (2) was replaced by the unsupported catalyst ZnCl2(same as the molar amount of Lewis acid in the catalyst of example 1), and other parameters and conditions are exactly the same as in example 1.
Comparative example 4
This comparative example differs from example 1 in that the catalyst in step (2) was replaced with a non-supported catalyst FeCl3(same as the molar amount of Lewis acid in the catalyst of example 1), and other parameters and conditions are exactly the same as in example 1.
Comparative example 5
This comparative example differs from comparative example 1 in that the molar ratio of N, N-diethylaniline to phosgene solid in step (1) was 10:1, no N, N-diethylaniline was added in step (2), and other parameters and conditions were exactly the same as in comparative example 1.
And (3) performance testing:
the yield of the target product tetraethyl michael ketone in the products obtained in the above examples and comparative examples was tested by gas chromatography;
the yield (tetraethyl michler's ketone) was%;
wherein the theoretical amount of formation (tetraethyl ketone) is based on the amount of consumption of N, N-diethylaniline;
the above test results are shown in table 1:
TABLE 1
Figure BDA0002864035630000141
Figure BDA0002864035630000151
Figure BDA0002864035630000161
In the above table, "-" means that the yield of the objective product is 1% or less.
As can be seen from table 1 above, the supported catalyst containing lewis acid used in the preparation method of the present invention has high selectivity to the target product tetraethyl michael ketone, and further has high yield, wherein the yield can reach more than 80%.
As can be seen from comparative examples 1-4, when the supported amount of the Lewis acid on the surface of the catalyst is 5-50%, the yield of the corresponding target product is high, and the supported amount is preferably 20-35 wt%.
Comparing examples 1 and 5-7, it can be seen that the product yield is higher when all-silicon Silicalite-1 molecular sieve, all-silicon MCM-41 molecular sieve, all-silicon beta molecular sieve and non-molecular sieve type silicon oxide are used as carriers; and the preferred full-silicon molecular sieve is compared with the embodiment 18, and the adoption of the silicon-aluminum molecular sieve can be seen, the side reaction is increased, so that the yield of the target product is obviously reduced.
As can be seen from comparative examples 1 and 8 to 12, in the catalyst of the present invention, BiCl is used as the Lewis acid3、TiCl4、FeCl3、AlCl3、ZnCl2Or FeCl2When the yield of the target product is high, BiCl is preferred3、TiCl4(ii) a And the yield of the product meets the requirement of BiCl3＞TiCl4＞ZnCl2＞FeCl3＞FeCl2＞AlCl3Further comparison with comparative examples 1 to 5 shows that the Lewis acids according to the inventionThe catalytic reaction yield of the supported catalyst is obviously better than that of the comparative example in which Lewis acid is used as the catalyst alone.
Compared with the examples 1 and 13, the invention has the advantages that the reaction in the step (1) is facilitated by adopting the operation mode of sectional temperature rise, so that the yield of the target intermediate product is improved, and the yield of the target product tetraethyl michael ketone is further improved.
As can be seen from comparison of examples 1 and 14, further increase in the addition ratio of the catalyst has little effect on the yield of the reaction.
Comparing examples 1 and 15, it can be seen that the yield of the target product is higher by adjusting the operating parameters within the preferred parameter range defined in the present invention.
As can be seen by comparing examples 1, 16, the raw material N, N-diethylaniline was added in one portion in step (1), which had an adverse effect on the reaction yield.
Comparing examples 1 and 17, it can be seen that in the preparation method of the invention, the loss of the catalyst performance in the reaction process is small, and the method has recycling value.
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. A preparation method of tetraethyl mikrolon is characterized by comprising the following steps:
(1) mixing N, N-diethylaniline with a solid phosgene solution, and reacting to obtain a reaction intermediate product shown in the following formula (a);
Figure FDA0002864035620000011
(2) mixing the reaction intermediate product obtained in the step (1), N-diethylaniline and a catalyst, and reacting to obtain tetraethyl ketone;
wherein the catalyst is selected from supported catalysts comprising Lewis acids.
2. The method of claim 1, wherein the lewis acid in the supported catalyst comprising a lewis acid is selected from AlCl3、ZnCl2、BiCl3、TiCl4、FeCl3And FeCl2At least one of; preferably BiCl3And/or TiCl4；
Preferably, the support of the supported catalyst comprising a lewis acid is selected from at least one of silica and molecular sieves;
preferably, the molecular sieve is selected from an all-silica molecular sieve, preferably at least one of a Silicalite-1 molecular sieve, an all-silica MCM-41 molecular sieve and an all-silica Beta molecular sieve.
3. The method according to claim 1 or 2, wherein the catalyst is prepared by a method comprising: activating the carrier, then soaking the carrier in a Lewis acid solution, evaporating to remove the solvent, and drying to obtain the catalyst;
preferably, the method for activating treatment comprises the steps of immersing the carrier in a strong base and weak acid salt aqueous solution, carrying out solid-liquid separation, and roasting in a protective atmosphere;
preferably, the strong base weak acid carbonate in the strong base weak acid carbonate aqueous solution is selected from at least one of alkali metal carbonate, alkali metal bicarbonate and alkali metal acetate;
preferably, the alkali metal carbonate is selected from sodium carbonate and/or potassium carbonate;
preferably, the alkali metal bicarbonate is selected from sodium bicarbonate and/or potassium bicarbonate;
preferably, the alkali metal acetate is selected from sodium acetate and/or potassium acetate;
preferably, the protective atmosphere is selected from at least one of nitrogen, argon and helium;
preferably, the roasting temperature is 300-500 ℃;
preferably, the roasting time is 2-6 h.
4. The method of claim 3, wherein the temperature of the solvent removal by evaporation is 20 ℃ to 65 ℃;
preferably, the drying is vacuum drying;
preferably, the loading amount of the lewis acid on the catalyst is 5% to 50%, preferably 20% to 35%, based on 100% by mass of the carrier.
5. The production method according to any one of claims 1 to 4, characterized in that the solvent of the solid phosgene solution of step (1) comprises dichloroethane;
preferably, the method for mixing N, N-diethylaniline with the solid phosgene solution in the step (1) to carry out the reaction comprises the following steps: under the condition that the temperature is-10 ℃ to 0 ℃, dropwise adding a solid phosgene solution into N, N-diethylaniline, and then heating for reaction;
preferably, the temperature of the temperature rise reaction is 10-65 ℃, and preferably 60-65 ℃;
preferably, the temperature-raising reaction process is a step-by-step temperature raising process, and comprises the following steps: heating to 10-15 ℃, carrying out a first heat preservation reaction, continuously heating to 30-35 ℃, carrying out a second heat preservation reaction, then heating to 60-65 ℃, and carrying out a third heat preservation reaction;
preferably, the time of the first heat preservation reaction is 1-3 h;
preferably, the time of the second heat preservation reaction is 3-5 h;
preferably, the time of the third heat preservation reaction is 3-5 h.
6. The method according to any one of claims 1 to 5, wherein the N, N-diethylaniline in step (2) is added in step (1), and the molar ratio of the amount of the N, N-diethylaniline added in step (1) to the amount of the phosgene solid is (7-12: 1).
7. The method according to any one of claims 1 to 5, wherein the N, N-diethylaniline in step (2) is added after the catalyst is added in step (2), and the molar ratio of the N, N-diethylaniline added in step (1) to the phosgene solid is 3-5: 1; the ratio of the adding amount of the N, N-diethylaniline in the step (1) to the adding amount of the N, N-diethylaniline in the step (2) is 1 (1-1.3), and preferably 1 (1.05-1.15);
preferably, the N, N-diethylaniline in the step (2) is added after the catalyst is added, and the N, N-diethylaniline in the step (2) is added dropwise.
8. The process according to any one of claims 1 to 7, wherein the ratio of the molar amount of Lewis acid in the catalyst added in step (2) to the molar amount of phosgene solid in step (1) is 1 (0.2 to 20), preferably 1 (0.5 to 5).
9. The method according to any one of claims 1 to 8, wherein the temperature of the reaction in the step (2) is 15 to 45 ℃, preferably 25 to 35 ℃.
10. The method for preparing according to any one of claims 1 to 9, comprising the steps of:
(1) adding N, N-diethylaniline into a reaction kettle, cooling to-10-0 ℃, dropwise adding a solid phosgene solution into the reaction kettle under the stirring condition, wherein the molar ratio of the N, N-diethylaniline to the solid phosgene is 3-5: 1, after dropwise adding is finished, heating the reaction kettle to 10-15 ℃, carrying out heat preservation reaction for 1-3 h, continuously heating to 30-35 ℃, carrying out heat preservation reaction for 3-5 h, then heating to 60-65 ℃, and carrying out heat preservation reaction for 3-5 h to obtain a reaction intermediate product;
(2) adding a supported catalyst containing Lewis acid and N, N-diethylaniline into the reaction intermediate product obtained in the step (1), and reacting at 15-45 ℃ to obtain tetraethyl michael ketone; wherein the ratio of the addition amount of the N, N-diethylaniline in the step (1) to the addition amount of the N, N-diethylaniline in the step (2) is 1 (1-1.3), and the ratio of the molar amount of the Lewis acid on the catalyst to the molar amount of the solid phosgene added in the step (1) is 1 (0.5-2).
CN202011576161.7A 2020-12-28 2020-12-28 Preparation method of tetraethyl ketone Active CN112707830B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011576161.7A CN112707830B (en) 2020-12-28 2020-12-28 Preparation method of tetraethyl ketone

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011576161.7A CN112707830B (en) 2020-12-28 2020-12-28 Preparation method of tetraethyl ketone

Publications (2)

Publication Number Publication Date
CN112707830A true CN112707830A (en) 2021-04-27
CN112707830B CN112707830B (en) 2023-09-29

Family

ID=75545641

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011576161.7A Active CN112707830B (en) 2020-12-28 2020-12-28 Preparation method of tetraethyl ketone

Country Status (1)

Country Link
CN (1) CN112707830B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023165522A1 (en) * 2022-03-02 2023-09-07 艾坚蒙(安庆)科技发展有限公司 Benzophenone derivative, and preparation method therefor and use thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105367436A (en) * 2014-08-27 2016-03-02 天津久日新材料股份有限公司 Preparation method of N,N-dimethyl benzoate composite
CN106278842A (en) * 2016-07-18 2017-01-04 浙江永太药业有限公司 A kind of preparation method of fenofibrate key intermediate 4 chlorine 4 ' dihydroxy benaophenonel
CN107686450A (en) * 2017-10-27 2018-02-13 天津久日新材料股份有限公司 The preparation method of tetraethyl michaelis ketone

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105367436A (en) * 2014-08-27 2016-03-02 天津久日新材料股份有限公司 Preparation method of N,N-dimethyl benzoate composite
CN106278842A (en) * 2016-07-18 2017-01-04 浙江永太药业有限公司 A kind of preparation method of fenofibrate key intermediate 4 chlorine 4 ' dihydroxy benaophenonel
CN107686450A (en) * 2017-10-27 2018-02-13 天津久日新材料股份有限公司 The preparation method of tetraethyl michaelis ketone

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
沈永嘉: "《有机颜料 品种与应用》", 北京：化学工业出版社, pages: 446 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023165522A1 (en) * 2022-03-02 2023-09-07 艾坚蒙(安庆)科技发展有限公司 Benzophenone derivative, and preparation method therefor and use thereof

Also Published As

Publication number Publication date
CN112707830B (en) 2023-09-29

Similar Documents

Publication Publication Date Title
WO2022142710A1 (en) Spherical titanium silicalite molecular sieve catalyst and preparation method therefor
CN111574483B (en) Preparation method of 2, 5-furandimethanol
JPS6045941B2 (en) Method for producing mixed oxide oxidation catalyst
CN112707830A (en) Method for preparing tetraethyl mikrolon
US20120083641A1 (en) Catalyst for oxidative dehydrogenation of propane to propylene
TWI418542B (en) Process for preparation of n-methyl pyrrolidone
CN114249661A (en) Method for preparing amine ether compound by N-alkylation reaction of arylamine and alcohol ether substance
CN109293531A (en) A kind of method of aromatic amine selective oxidation synthesis azoxy compound
CN107963968B (en) Method for preparing phenyl acetate
CN113045375A (en) Method for preparing 2-pentylanthracene from diamyl anthracene through transalkylation
JPH029873A (en) Production of gamma-butyrolactone
CN112717941B (en) Ester hydrogenation catalyst and preparation method and application thereof
CN117024258B (en) Method for preparing beta-isophorone by catalysis of modified X-type molecular sieve
CN115232103B (en) Preparation method of cyclic sulfate
CN112939766B (en) Method for preparing glutaric acid
CN117185913B (en) Preparation method of 2-amyl anthraquinone
CN111974442B (en) Catalyst for producing acrylic acid and methyl acrylate, and preparation method and application thereof
CN111233657B (en) Method for preparing adipic acid and 2, 5-dihydroxy adipic acid from aldohexose diacid
CN107233885B (en) Preparation method of catalyst for air oxidation
JP4162915B2 (en) Preparation method of oxidation catalyst and production method of nitrile using the catalyst
CN109796391B (en) Preparation method of thiosulfonate compound in water phase
CN115672358A (en) Preparation method and application of core-shell oxide catalyst for preparing ethylene by oxidative dehydrogenation of ethane
CN115260039A (en) Method for preparing ethylenediamine
CN108250179B (en) Process for producing sulfolane
CN110270378A (en) The immobilized palladium catalyst CaPOP3@Pd of porous polymer and preparation method and application of triazine radical connection cup [4] aromatic hydrocarbons

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant