Search

CN-122010696-A - Preparation method of cyclohexyl ethyl vinyl ether

CN122010696ACN 122010696 ACN122010696 ACN 122010696ACN-122010696-A

Abstract

The invention relates to the technical field of chemical industry, in particular to a preparation method of cyclohexyl ethyl vinyl ether, which comprises the following steps of S1 taking phenethyl alcohol as a raw material, taking low-boiling-point alcohol (ethanol or isopropanol) as a solvent, carrying out hydrogenation reduction at 50-65 ℃ and 5-6MPa under the catalysis of nickel/ruthenium carbon to obtain cyclohexyl ethanol, recycling a catalyst and the solvent, S2 mixing the cyclohexyl ethanol with alkenyl ether (preferably butyl vinyl ether), alkali (pyridine or triethylamine), palladium catalyst (preferably palladium chloride) and ligand 1, 10-phenanthroline under the protection atmosphere, carrying out catalytic alcohol exchange at 100-110 ℃, and carrying out water washing, pH adjustment to 7 on a reaction solution, passing through a column and distilling to obtain a product. The method has the advantages of mild condition, low equipment requirement, no solid waste, environmental protection, less catalyst consumption, recycling of solvent, low cost, high product purity and high yield, and is suitable for industrial mass production.

Inventors

  • WANG LIPING
  • MA QINGQING

Assignees

  • 西安国际医学中心有限公司
  • 榆林市中医医院

Dates

Publication Date
20260512
Application Date
20260203

Claims (10)

  1. 1. A process for the preparation of cyclohexylethyl vinyl ether, comprising the steps of: S1, preparing cyclohexyl ethanol by hydrogenation reduction reaction of phenethyl alcohol serving as a raw material and alcohols with low boiling point serving as solvents under the catalysis of nickel/ruthenium carbon at 50-65 ℃ and 5-6 MPa; S2, adding alkenyl ether, alkali, palladium catalyst and ligand into the cyclohexyl ethanol prepared in the S1 under the atmosphere of protective gas, and preparing the cyclohexyl ethyl vinyl ether by catalytic alcohol exchange reaction at 100-110 ℃.
  2. 2. The method for preparing cyclohexylethyl vinyl ether according to claim 1, wherein in S1, the low boiling point alcohol solvent is ethanol or isopropanol; in S1, the mass ratio of the phenethyl alcohol to the low-boiling point alcohol solvent is 1:3-6; in S1, the catalyst is nickel with 10% of water or ruthenium carbon with 10% of water, and the mass ratio of the phenethyl alcohol to the catalyst is 1:0.03-0.06; s1, after the reaction is finished, filtering, recovering the catalyst, and concentrating and recovering the solvent at normal pressure; In S1, the recovered catalyst and the solvent can be recovered and reused.
  3. 3. The method for preparing cyclohexylethyl vinyl ether according to claim 1, wherein in S2, the molar ratio of the cyclohexylethanol to the alkenyl ether is 1:2-20.
  4. 4. The method for preparing cyclohexylethyl vinyl ether according to claim 1, wherein the base in S2 is pyridine or triethylamine.
  5. 5. The method for preparing cyclohexylethyl vinyl ether according to claim 1, wherein in S2, the molar ratio of the cyclohexylethanol to the alkali is 1:0.1-0.6.
  6. 6. The method for preparing cyclohexylethyl vinyl ether according to claim 1, wherein in S2, the palladium catalyst is any one of palladium chloride, palladium trifluoroacetate, palladium bis (dibenzylideneacetone), and 1,1' -bis (diphenylphosphino) ferrocene palladium dichloride.
  7. 7. The method for preparing cyclohexylethyl vinyl ether according to claim 1, wherein in S2, the molar ratio of the cyclohexylethanol to the catalyst is 1:0.001-0.003.
  8. 8. The method for preparing cyclohexylethyl vinyl ether according to claim 1, wherein in S2, the ligand is 1, 10-phenanthroline.
  9. 9. The method for preparing cyclohexylethyl vinyl ether according to claim 1, wherein the molar ratio of the cyclohexylethanol to the ligand in S2 is 1:0.002-0.006.
  10. 10. The method for preparing cyclohexylethyl vinyl ether according to claim 1, wherein S2 is carried out by adding water into reaction liquid, washing with water to adjust pH to 7, passing through column, and distilling; In S2, the alkenyl ether is any one of butyl vinyl ether, amyl vinyl ether, ethyl vinyl ether, propyl vinyl ether or other alkyl vinyl ether.

Description

Preparation method of cyclohexyl ethyl vinyl ether Technical Field The invention relates to the technical field of chemical industry, in particular to a preparation method of cyclohexyl ethyl vinyl ether. Background The cyclohexylethyl vinyl ether compound is an important raw material for chemicals such as medicines, agricultural chemicals, resist resins, and the like, and is also used as a reactive diluent for inks and paints. In addition, the cyclohexylethyl vinyl ether compound generally has cationic polymerizability, and is useful as a polymer material such as an optical resin and a transparent resin, a crosslinking agent, a UV hardener, an adhesive, and the like. Furthermore, the cyclohexylethyl vinyl ether compound has advantages such as high stability, low odor and less skin irritation, as compared with acrylic compounds and styrene compounds. However, the types of the cyclohexyl ethyl vinyl ether compounds are few at present, the price is high, and the market demand is large but the cyclohexyl ethyl vinyl ether compounds are not fully satisfied. Therefore, it is of great importance to study a process suitable for the large-scale industrial production of cyclohexylethyl vinyl ether. Japanese patent JP2012-020954A discloses a synthesis method in which cyclohexylethanol is used as a raw material, and a coupling reaction is performed under the catalysis of transition metal (iridium) to obtain cyclohexylethyl vinyl ether. The method has the defects that the price of the catalyst (1, 5-cyclooctadiene) iridium (I) dichloride is 870 yuan/g, the catalyst material ratio is 0.01eq, the production cost is high, and a closed system is needed in the reaction process, so that the method is not beneficial to industrialized mass production. The patent also discloses another synthesis method, which takes cyclohexyl ethanol and paraldehyde as raw materials, and synthesizes the cyclohexyl ethyl vinyl ether by three steps of acetal formation, acetyl chloride chlorination and triethylamine elimination. The biggest bottleneck of the method is that the second step of acetyl chloroacetalization and the conversion rate of chlorination are low, and 2mol of cyclohexyl ethanol can only produce 1mol of cyclohexyl ethyl vinyl ether according to 100 percent conversion rate, so that atom economy is low, and the third step of product cyclohexyl ethyl vinyl ether is difficult to separate from impurities generated in the reaction. In order to solve the cost problem, a plurality of methods are studied at present, which are prepared by taking cyclohexyl ethanol and other vinyl ether as raw materials under the catalysis of a catalyst Pd (4, 7-diphenyl-1, 10-phenanthroline) (OOCCF 3) 2. The catalyst used in the process has high price, is unfavorable for industrialized mass production, and has large molecular weight and large dosage. Disclosure of Invention Aiming at the problems in the prior art, the invention provides a preparation method of cyclohexyl ethyl vinyl ether, which adopts phenethyl alcohol as a raw material, and the cyclohexyl ethyl vinyl ether is obtained through catalytic hydrogenation, the reaction condition is mild, the catalyst and the solvent are applicable, and the cyclohexyl ethyl vinyl ether is obtained through alcohol exchange reaction between the obtained cyclohexyl ethyl alcohol and alkenyl ether under the catalysis of a palladium catalyst, so that the catalyst consumption is low, and the cost is lower. The technical scheme adopted for solving the technical problems is that the preparation method of the cyclohexyl ethyl vinyl ether comprises the following steps: S1, preparing cyclohexyl ethanol by hydrogenation reduction reaction of phenethyl alcohol serving as a raw material and alcohols with low boiling point serving as solvents under the catalysis of nickel/ruthenium carbon at 50-65 ℃ and 5-6 MPa; S2, adding alkenyl ether, alkali, palladium catalyst and ligand into the cyclohexyl ethanol prepared in the S1 under the atmosphere of protective gas, and preparing the cyclohexyl ethyl vinyl ether by catalytic alcohol exchange reaction at 100-110 ℃. Specifically, in S1, the low-boiling point alcohol solvent is ethanol or isopropanol; in S1, the mass ratio of the phenethyl alcohol to the low-boiling point alcohol solvent is 1:3-6; in S1, the catalyst is nickel with 10% of water or ruthenium carbon with 10% of water, and the mass ratio of the phenethyl alcohol to the catalyst is 1:0.03-0.06; s1, after the reaction is finished, filtering, recovering the catalyst, and concentrating and recovering the solvent at normal pressure; In S1, the recovered catalyst and the solvent can be recovered and reused. Specifically, in S2, the molar ratio of the cyclohexyl ethanol to the alkenyl ether is 1:2-20. Specifically, in S2, the base is pyridine or triethylamine. Specifically, in S2, the molar ratio of the cyclohexyl ethanol to the alkali is 1:0.1-0.6. Specifically, in S2, the palladium catalyst is palladium chloride, palladium tr