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CN-116332731-A - Environment-friendly hydrofluoroether compound and preparation method thereof

CN116332731ACN 116332731 ACN116332731 ACN 116332731ACN-116332731-A

Abstract

The invention discloses an environment-friendly hydrofluoroether compound and a preparation method thereof, wherein the method comprises the following steps: dissolving a silicon-terminated modified catalyst in an organic solvent, adding the catalyst into a high-pressure reaction kettle which has deoxidized and dehydrated, and then adding polyfluoroolefin; continuously introducing hydroxyl-containing organic compound, polyfluoroalkene and organic solvent at a constant speed, then keeping the mixture at a constant temperature for reaction, and cooling after the reaction is finished; and finely dividing the obtained material to obtain the environment-friendly hydrofluoroether compound. The preparation method has the advantages of stable and quick reaction, easy control, high efficiency, good selectivity, product purity of over 99.75 percent, selectivity of over 97.0 percent, recycling of materials, recycling of the catalyst for over 30 times, simple separation, large difference of properties such as boiling points of the solvent and the catalyst, and the solvent and the product, and easier recycling. In addition, the method has high comprehensive efficiency, simple and convenient operation and low production cost, and is more suitable for the development trend of the current industry.

Inventors

  • CHEN ZHAOWU
  • XIE LIN

Assignees

  • SHENZHEN JIASHUNYI IND CO LTD

Dates

Publication Date
20230627
Application Date
20230325
Priority Date
20230325

Claims (10)

  1. 1. The preparation method of the environment-friendly hydrofluoroether compound is characterized by comprising the following steps: (1) Dissolving a silicon-terminated modified catalyst in an organic solvent, adding the catalyst into a high-pressure reaction kettle which has deoxidized and dehydrated, and then adding polyfluoroolefin; (2) Continuously introducing hydroxyl-containing organic compound, polyfluoroalkene and organic solvent at a constant speed, then keeping the mixture at a constant temperature for reaction, and cooling after the reaction is finished; (3) Finely separating the material obtained in the step (2) to obtain the environment-friendly hydrofluoroether compound.
  2. 2. The method for producing an environmentally friendly hydrofluoroether compound of claim 1, wherein in step (1), the silicon-terminated modified catalyst is 0.5 to 8 parts by weight, the organic solvent is 30 to 50 parts by weight, and the polyfluoroolefin is 25 to 50 parts by weight.
  3. 3. The method for producing an environmentally friendly hydrofluoroether compound of claim 2, wherein in step (2), the hydroxyl-containing organic compound is 40 to 80 parts by weight.
  4. 4. The method for producing an environment-friendly hydrofluoroether compound of claim 3, wherein in step (2), the ratio of the inlet speeds of the hydroxyl-containing organic compound, the polyfluoroolefin and the organic solvent is 1:1 to 1.5:0.8-1.2.
  5. 5. The method for producing an environment-friendly hydrofluoroether compound of claim 4, wherein in step (2), the reaction temperature is 40 to 90℃and the reaction time is 1 to 2 hours.
  6. 6. The method for producing an environmentally friendly hydrofluoroether compound of claim 5, wherein said hydroxyl-containing organic compound comprises at least one of trifluoroethanol, trifluoropropanol, pentafluoropropanol and octafluoropentanol.
  7. 7. The method for preparing an environment-friendly hydrofluoroether compound of claim 6, wherein the silicon-terminated modified catalyst is a modified basic ionic compound having a structure represented by the following formula (I): wherein the RSi group is vinyl terminated silicone oil group, the molecular weight Mn is 400-1200, rc is linear alkyl with the number of C atoms not more than 4, and R-is selected from carbonate, acetate or hydroxide.
  8. 8. The method for producing an environment-friendly hydrofluoroether compound of claim 7, wherein the organic solvent comprises at least one of N, N dimethylformamide, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dimethyl sulfoxide, or any combination thereof.
  9. 9. The method for producing an environmentally friendly hydrofluoroether compound of claim 8, wherein the polyfluorene comprises at least one of trifluoroethylene, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, hexafluoropropylene and chlorotrifluoroethylene.
  10. 10. An environmentally friendly hydrofluoroether compound, characterized in that it is obtainable by a process according to any one of claims 1-9.

Description

Environment-friendly hydrofluoroether compound and preparation method thereof Technical Field The invention relates to the technical field of preparation of new fluorine-containing materials, in particular to an environment-friendly hydrofluoroether compound and a preparation method thereof. Background CFCs (chlorofluorocarbons) are the first chemically stable substances used in the refrigeration and cleaning industry, but are one of the major ozone-destroying substances, causing greenhouse effect and global warming, and directly causing an increase in ultraviolet radiation into the atmosphere, with considerable damage to humans, animals and plants. In recent years, global symbiosis and green industry are achieved at home and abroad, and many efforts are made to develop CFCs substitutes. The hydrofluoroether type substance is ideal substance in modern industry because it does not contain ozone-consuming elements such as chlorine, bromine, etc., is a heteroatom compound composed of C, H, F, O, etc., and has the advantages of no toxicity, incombustibility, stability, very low ODP value and GWP value. Hydrofluoroethers have a variety of synthetic routes such as fluoride of ethers or higher metal fluorides, electrochemical fluorination of ethers, substitution reactions of alcohols with halogenated hydrocarbons, addition reactions of alcohols with fluoroolefins, and the like. Although F is used in the ether fluorination method 2 The activity was highest, but the selectivity was also worst. Metal fluorides have high yields of fluorination but are expensive and limited in use. The electrochemical method can synthesize the isolated hydrofluoroether, but has high power consumption, generally needs a large amount of anhydrous hydrogen fluoride in the process, and the product contains a large amount of isomer with similar properties, can not be separated effectively, and is not suitable for industrial application. The substitution reaction of alcohol and halohydrocarbon has the advantages of harsh conditions such as high temperature and high pressure, low yield, long period and basically no need. The addition reaction of the alcohol and the fluoroolefin has relatively simple operation and mild reaction conditions, and is a synthetic preparation mode with industrialized prospect at present. For example, chinese patent CN112142572a discloses a continuous process device and method for synthesizing hydrofluoroether, in which raw material alcohol containing catalyst and tetrafluoroethylene are continuously introduced into a reaction kettle to react, continuous discharge is separated by an evaporator, the product and raw material enter a rectification system to further separate, the separated raw material returns to a raw material tank, the remaining solvent returns to be used, and the conversion rate of raw material alcohol is 80-93%. The process product contains a large amount of raw material alcohol, and is difficult to separate. For another example, chinese patent application CN113929562a discloses a process for preparing fluoroethers by reacting an alcohol or phenol with a fluoroolefin in a solvent to produce fluoroethers, the molar ratio of fluoroolefin to alcohol or phenol being from 0.8 to 1.2:1, the molar ratio of catalyst to alcohol or phenol being from 0.03 to 0.1:1, the mass ratio of solvent to alcohol or phenol being from 0.5 to 4:1, 50 to 100% of the molar amount of alcohol or phenol being added in a continuous make-up after the reaction has begun. However, the method does not avoid the generation of vinyl ether compounds, is not easy to separate, the loss of the catalyst is large, the catalyst can not be recycled basically, and the solubility of the catalyst is limited, so that the uniformity of the reaction is limited, and the method is also a factor causing side reactions. The synthesis preparation method in the prior art has the problems of low efficiency, poor selectivity, poor batch-to-batch stability, high production cost and difficult separation of product materials caused by the generation of byproducts such as vinyl ether, and is difficult to meet the current industrial production requirements. Disclosure of Invention Aiming at the technical problems in the prior art, the invention provides the preparation method of the environment-friendly fluoroether compound, which solves the problems of long period and low yield in the prior art, has higher selectivity, fewer byproducts and easier separation, ensures stable reaction process and recycling, reduces the cost and is beneficial to realizing industrial production. Specifically, the present invention includes the following. In a first aspect of the present invention, there is provided a process for preparing an environmentally friendly hydrofluoroether compound comprising: (1) Dissolving a silicon-terminated modified catalyst in an organic solvent, adding the catalyst into a high-pressure reaction kettle which has deoxidized and dehydrated, and then add