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CN-121972221-A - Catalyst for green synthesis of detoxicated quinolizine and preparation method thereof

CN121972221ACN 121972221 ACN121972221 ACN 121972221ACN-121972221-A

Abstract

The invention provides a catalyst for green synthesis of detoxicated quinol and a preparation method thereof, belonging to the technical field of catalysts, wherein the catalyst comprises a polymer skeleton carrier and an active component loaded on the carrier, the polymer skeleton carrier is a super-crosslinked polystyrene porous network, the active component is 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, and the 1,5, 7-triazabicyclo [4.4.0] dec-5-ene is fixedly loaded on the polymer skeleton carrier through a covalent bond. The invention utilizes covalent bond to fix organic alkali 1,5, 7-triazabicyclo [4.4.0] dec-5-alkene on super-crosslinked polystyrene skeleton with rigid pore canal, thus constructing a heterogeneous catalyst with reaction activity and structural stability.

Inventors

  • XU XIZHI
  • YU LIGUO
  • LIU ZHEN
  • GONG XUGAN
  • PAN YONGCHENG
  • LU KANG
  • LV BAOWEI
  • ZHAO TIAN
  • YANG HAISONG

Assignees

  • 新沂市永诚化工有限公司

Dates

Publication Date
20260505
Application Date
20260121

Claims (10)

  1. 1. A catalyst for the green synthesis of detoxified quinol, characterized in that it comprises a polymeric backbone support and an active component carried on said support; the polymer skeleton carrier is a super-crosslinked polystyrene porous network; the active component comprises 1,5, 7-triazabicyclo [4.4.0] dec-5-ene; the 1,5, 7-triazabicyclo [4.4.0] dec-5-ene is immobilized on the polymer skeleton carrier through a covalent bond.
  2. 2. The catalyst according to claim 1, characterized in that the specific surface area of the catalyst is 800-1200m 2 /g.
  3. 3. The catalyst according to claim 1, wherein the loading of the active component in the catalyst is 2.0-3.0mmol/g in terms of nitrogen element.
  4. 4. A process for preparing a catalyst according to any one of claims 1 to 3, comprising the steps of: S1, carrying out suspension polymerization on p-chloromethyl styrene and divinylbenzene serving as monomers in the presence of an inert diluent to obtain copolymer microspheres; S2, in the presence of a Lewis acid catalyst, carrying out a crosslinking reaction on the copolymer microsphere obtained in the step S1 to obtain a super-crosslinking microsphere with partial chloromethyl groups reserved; s3, dispersing the super-crosslinked microspheres obtained in the step S2 in an organic solvent, adding excessive 1,5, 7-triazabicyclo [4.4.0] dec-5-alkene for nucleophilic substitution reaction, immobilizing the 1,5, 7-triazabicyclo [4.4.0] dec-5-alkene on a framework, and carrying out post-treatment on the product to obtain the catalyst.
  5. 5. The preparation method according to claim 4, wherein in the step S1, the mass ratio of the p-chloromethylstyrene to the divinylbenzene is 40:1 to 60:1, the inert diluent is a mixture of toluene and n-heptane, and in the step S2, the Lewis acid catalyst is anhydrous ferric trichloride, and the addition amount of the Lewis acid catalyst is 5-15% of the mass of the copolymerization microsphere.
  6. 6. Use of a catalyst according to any one of claims 1 to 3 for the preparation of decoquinate.
  7. 7. A method for synthesizing cloquintocet mexyl using the catalyst according to any one of claims 1-3, comprising the steps of: Dissolving 5-chloro-8-hydroxyquinoline and chloroacetic acid-2-heptyl ester in a hydrophobic organic solvent, adding the catalyst and auxiliary inorganic base, carrying out etherification reaction under a heating condition, continuously removing reaction in the reaction process to generate water, and carrying out solid-liquid separation and crystallization after the reaction is finished to obtain the cloquintocet-mexyl.
  8. 8. The method according to claim 7, wherein the hydrophobic organic solvent is methyl isobutyl ketone, the reaction temperature is 85-120 ℃, and the reaction is separated and removed in real time by a water diversion device to produce water.
  9. 9. The method of claim 7, wherein the auxiliary inorganic base is anhydrous sodium carbonate for neutralizing acid generated during catalysis and forming a solid salt.
  10. 10. The method of claim 7, further comprising the steps of recovering and applying the catalyst and solvent: Filtering at the temperature of not lower than 60 ℃ after the reaction is finished, washing the obtained solid filter cake with water to remove byproduct salt, recovering the catalyst, concentrating the obtained filtrate to remove part of solvent, cooling and crystallizing to obtain a product, and returning the crystallization mother liquor to the next batch of reaction system for recycling.

Description

Catalyst for green synthesis of detoxicated quinolizine and preparation method thereof Technical Field The invention belongs to the technical field of catalysts, and particularly relates to a catalyst for green synthesis of detoxicated quinolizine and a preparation method thereof. Background The cloquintocet-mexyl (Cloquintocet-chlorol-8-quinolyl) acetate-1-methyl hexyl ester is an important herbicide safener and is mainly used for protecting crops from herbicide injury. Currently, the mainstream technology for industrially synthesizing cloquintocet-mexyl generally adopts a strategy of 'esterification before etherification' or 'etherification before hydrolysis and esterification'. Among them, the key etherification reaction step generally adopts 5-chloro-8-hydroxyquinoline and chloroacetic acid-2-heptyl ester (or other chloroacetic acid derivatives) to react in a polar aprotic solvent (such as N, N-Dimethylacetamide (DMAC) or N, N-Dimethylformamide (DMF)) by taking inorganic base (such as potassium carbonate) as an acid-binding agent. Although this process technology is relatively mature, there are serious technical drawbacks and environmental problems as follows: First, a large amount of high-salt wastewater is produced. In the conventional process, hydrogen chloride generated by the neutralization reaction of potassium carbonate produces a large amount of potassium chloride salt. Because of the miscibility of the reaction solvent DMAC with water, these inorganic salts are typically removed industrially by extensive water washing, resulting in 10-15 tons of high chemical oxygen demand, high salt wastewater per 1 ton of product produced. The wastewater is difficult to biochemically treat, the evaporation desalination energy consumption is huge, and the treatment cost is high. Second, accumulation of reaction-generated water in the system leads to serious side reactions and unstable product quality. In the hydrophilic solvent systems of the prior art, the water generated by the etherification reaction is difficult to remove. Under the high temperature and strong alkaline environment, the retained water attacks the ester bond of chloroacetic acid-2-heptyl ester to hydrolyze, so that the yield is reduced, and on the other hand, the oxidation of the phenolic raw materials is increased to generate dark impurities and tar. This forces the post-treatment to rely on a large amount of activated carbon for repeated decolorization, which not only increases the working hours, but also generates a large amount of dangerous solid wastes. In order to solve the above problems, there is an urgent need in the art to develop a green synthesis process capable of replacing the conventional inorganic base and polar aprotic solvent system. Specifically, it is necessary to develop an immobilized catalyst with high catalytic activity, excellent mechanical strength and rigid pore structure, and construct a high-efficiency synthesis process based on the catalyst, which can effectively avoid water accumulation and inhibit side reactions, and is a technical problem to be solved in the field of detoxication quinoline synthesis at present. Disclosure of Invention In view of the foregoing, it is an object of the present invention to provide a catalyst for green synthesis of detoxified quinol and a preparation method thereof, which at least partially solve the problems set forth in the background art. The technical scheme adopted by the invention is as follows: the first aspect of the invention provides a catalyst for green synthesis of detoxified quinoline, the catalyst comprising a polymer backbone support and an active component supported on the support; the polymer skeleton carrier is a super-crosslinked polystyrene porous network; the active component comprises 1,5, 7-triazabicyclo [4.4.0] dec-5-ene; the 1,5, 7-triazabicyclo [4.4.0] dec-5-ene is immobilized on the polymer skeleton carrier through a covalent bond. In some embodiments of the invention, the catalyst has a specific surface area of 800-1200m 2/g. In some embodiments of the invention, the loading of the active component in the catalyst is 2.0 to 3.0mmol/g as elemental nitrogen. The second aspect of the present invention provides a method for preparing the catalyst, comprising the following steps: S1, carrying out suspension polymerization on p-chloromethyl styrene and divinylbenzene serving as monomers in the presence of an inert diluent to obtain copolymer microspheres; S2, in the presence of a Lewis acid catalyst, carrying out a crosslinking reaction on the copolymer microsphere obtained in the step S1 to obtain a super-crosslinking microsphere with partial chloromethyl groups reserved; s3, dispersing the super-crosslinked microspheres obtained in the step S2 in an organic solvent, adding excessive 1,5, 7-triazabicyclo [4.4.0] dec-5-alkene for nucleophilic substitution reaction, immobilizing the 1,5, 7-triazabicyclo [4.4.0] dec-5-alkene on a framework, and carrying out po