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CN-122010729-A - Continuous production process of E-conjugated diene alcohol ester compound

CN122010729ACN 122010729 ACN122010729 ACN 122010729ACN-122010729-A

Abstract

The invention discloses a continuous production process of E-conjugated diene alcohol ester compounds, which relates to the technical field of enol ester compound production and comprises the following steps of (1) conveying an alkali solution into a first reactor, cooling to a reaction temperature, (2) conveying the alkali solution cooled in the step (1) and an aldehyde solution into a first mixer for mixing, conveying the mixed solution into a second reactor for reaction, (3) conveying the reaction solution in the step (2) and an acyl chloride solution into a second mixer for mixing, and then conveying the mixed solution into a third reactor for reaction.

Inventors

  • ZHU SHIFA
  • MAO XIAONING
  • ZHANG FENGPING

Assignees

  • 现代纺织技术创新中心(鉴湖实验室)

Dates

Publication Date
20260512
Application Date
20251217

Claims (10)

  1. 1. A continuous production process of E-conjugated diene alcohol ester compounds is characterized by comprising the following steps: (1) Conveying the alkali solution into a first reactor, and cooling to a reaction temperature; (2) The cooled alkali solution in the step (1) and aldehyde solution are conveyed to a first mixer for mixing, and the mixed solution is conveyed to a second reactor for reaction; (3) And (3) mixing the reaction solution obtained in the step (2) with an acyl chloride solution through a second mixer, and then conveying the mixture to a third reactor for reaction to prepare the E-conjugated dienol ester compound.
  2. 2. The continuous production process of E-conjugated diene alcohol ester compounds according to claim 1, wherein the alkali solution is selected from any one of potassium hydroxide, sodium hydride, potassium hydride, sodium ethoxide, potassium ethoxide, sodium n-butoxide, potassium n-butoxide, sodium tert-butoxide, potassium tert-butoxide dimethyl sulfoxide, dimethylformamide, dimethylacetamide and tetrahydrofuran solution, the aldehyde solution is selected from any one of dimethyl sulfoxide, dimethylformamide, dimethylacetamide and tetrahydrofuran solution of alpha, beta-unsaturated aldehyde, and the acyl chloride solution is selected from any one of dimethyl sulfoxide, dimethylformamide, dimethylacetamide and tetrahydrofuran solution of aliphatic acyl chloride or aromatic acyl chloride.
  3. 3. The continuous production process of E-conjugated diene alcohol ester compounds according to claim 1, wherein the first reactor, the second reactor and the third reactor are single tubular reactors or series or parallel of a plurality of tubular reactors, and the first mixer and the second mixer are selected from any one of T-type mixer, Y-type mixer and Venturi-type mixer.
  4. 4. The continuous production process of E-conjugated diene alcohol ester compounds according to claim 1, wherein in the step (1), the cooling temperature is-80 ℃ to-20 ℃ and the residence time of the first reactor is 5-20 minutes.
  5. 5. The continuous production process of E-conjugated diene alcohol ester compound according to claim 4, wherein in the step (1), the cooling temperature is-40℃and the residence time in the first reactor is 5 minutes.
  6. 6. The continuous production process of E-conjugated diene alcohol ester compounds according to claim 1, wherein in the step (2), the reaction temperature is-80 ℃ to-20 ℃ and the residence time of the second reactor is 5-20 minutes.
  7. 7. The continuous production process of E-conjugated diene alcohol ester compound according to claim 6, wherein in the step (2), the reaction temperature is-80℃and the residence time in the second reactor is 10 minutes.
  8. 8. The continuous production process of E-conjugated diene alcohol ester compounds according to claim 1, wherein in the step (3), the reaction temperature is-80 ℃ to-20 ℃ and the residence time of the second reactor is 5-20 minutes.
  9. 9. The continuous production process of E-conjugated diene alcohol ester compound according to claim 6, wherein in the step (3), the reaction temperature is-80℃and the residence time in the second reactor is 20 minutes.
  10. 10. A continuous production device of E-conjugated diene alcohol ester compounds is characterized by comprising a first reactor, a second reactor and a third reactor which are connected in series, The first reactor and the second reactor are connected through a first mixer, and the second reactor and the third reactor are connected through a second mixer; the first liquid storage tank is connected with the first reactor through a first fluid delivery pump, and the first liquid storage tank, the first fluid delivery pump and the first reactor form a first reaction unit; The second liquid storage tank is connected with the first mixer through a second fluid delivery pump, and the second liquid storage tank, the second fluid delivery pump, the first mixer and the second reactor form a second reaction unit; The third liquid storage tank is connected with the second mixer through a third fluid delivery pump, and the third liquid storage tank, the third fluid delivery pump, the second mixer and the third reactor form a third reaction unit; The first liquid storage tank is used for storing a first reaction liquid, wherein the first reaction liquid is an alkali solution, and the alkali solution is any one of potassium hydroxide, sodium hydride, potassium hydride, sodium ethoxide, potassium ethoxide, sodium n-butoxide, potassium n-butoxide, sodium tert-butoxide and potassium tert-butoxide, dimethyl formamide, dimethyl acetamide or tetrahydrofuran solution; The second liquid storage tank is used for storing a second reaction liquid, the second reaction liquid is aldehyde solution, and the aldehyde solution is any one of dimethyl sulfoxide, dimethylformamide, dimethylacetamide or tetrahydrofuran solution of alpha, beta-unsaturated aldehyde; And the third liquid storage tank is used for storing a third reaction liquid, the third reaction liquid is an acyl chloride solution, and the acyl chloride solution is selected from any one of dimethyl sulfoxide, dimethylformamide, dimethylacetamide or tetrahydrofuran solution of aliphatic acyl chloride or aromatic acyl chloride.

Description

Continuous production process of E-conjugated diene alcohol ester compound Technical Field The invention belongs to the field of organic chemical industry, and particularly relates to a continuous production process of an E-conjugated diene alcohol ester compound. Background The E-conjugated dienol ester compound is a key intermediate for providing high stereoselectivity and multifunction for the fields of organic synthesis, material chemistry and the like, and can form a polymer with double bonds on a main chain through polymerization reaction. Chinese patent CN104031191a discloses that polymers containing double bonds in the main chain have wide application in the polymer field. Such as further polymerization of double bonds to form crosslinked or hyperbranched polymers, or further functionalization of polymers by chemical reactions. E-conjugated diene alcohol ester compounds are generally produced by adopting a batch production mode, in the batch operation process, firstly, alkali liquor is cooled to the reaction temperature, then, unsaturated aldehyde solution is slowly added into the alkali liquor in a dropwise manner, and after the reaction is completed, acyl chloride solution is slowly added in a dropwise manner. The batch production process consumes long material, is complex to operate and has low production efficiency. The unsaturated aldehyde and acyl chloride react with strong heat release, and the side reaction and the main reaction are in parallel competition, so the heat exchange and micro mixing degree in the reaction process have great influence on the yield of the target product, and the heat exchange and mixing process of the reaction is enhanced to be beneficial to the main reaction. The intermittent kettle has limited heat and mass transfer process, which results in obvious product yield reduction and increased safety risks such as temperature runaway. Neier et al (Synthesis 2007, 15, 2379-2387 x) report a method for synthesizing E-conjugated dienol esters using crotonaldehyde and different types of acid chlorides, which adopts a kettle type batch dropping operation, the selectivity of the product is 53-81%, and Zhu et al (org. Lett. 2023, 25, 3573-3577) report a method for synthesizing E-conjugated dienol esters using acetylene and different types of acid chlorides, which has the advantages of high selectivity and high atom economy, but the rhodium-based catalyst used is expensive and is difficult to realize industrial production. Chinese patents CN 221208000U and CN 114773241a disclose a method for continuous synthesis of carboxylic esters by using a microchannel reactor, but the microchannel reactor has the disadvantages of small flux, easy blockage, large equipment investment, difficult amplification, etc., and the synthesis of E-conjugated dienol ester compounds requires extremely low temperature (usually below-20 ℃), water or other impurities in the reaction solution are easy to exist in a solid state form, and thus the microchannel is blocked. Disclosure of Invention The invention aims to solve the defects of the E-conjugated diene alcohol ester compound production process, and provides a safe and efficient E-conjugated diene alcohol ester compound continuous production process which is simple to operate, easy to amplify, small in equipment investment and high in target product yield. The technical scheme adopted by the invention is as follows: A continuous production process of E-conjugated diene alcohol ester compounds comprises the following steps: (1) Conveying the alkali solution into a first reactor, and cooling to a reaction temperature; (2) The cooled alkali solution in the step (1) and aldehyde solution are conveyed to a first mixer for mixing, and the mixed solution is conveyed to a second reactor for reaction; (3) And (3) mixing the reaction solution obtained in the step (2) with an acyl chloride solution through a second mixer, and then conveying the mixture to a third reactor for reaction to prepare the E-conjugated dienol ester compound. The further arrangement is that: The alkali solution is selected from any one of potassium hydroxide, sodium hydride, potassium hydride, sodium ethoxide, potassium ethoxide, sodium n-butoxide, potassium n-butoxide, sodium tert-butoxide, dimethyl sulfoxide of potassium tert-butoxide, dimethylformamide, dimethylacetamide and tetrahydrofuran solution. The aldehyde solution is selected from any one of dimethyl sulfoxide, dimethylformamide, dimethylacetamide and tetrahydrofuran solution of alpha, beta-unsaturated aldehyde. The acyl chloride solution is selected from any one of dimethyl sulfoxide, dimethylformamide, dimethylacetamide and tetrahydrofuran solution of aliphatic acyl chloride or aromatic acyl chloride. The reaction equation is as follows: Wherein R 1、R2、R３ is independently any one of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, heterocyclic ring, oxygen-containing/nitrogen-containing group, etc. The first reacto