Fluorinated liquid and preparation method thereof
By using hexafluoropolyether oligomer and hexafluoropropylene oligomer at a mild temperature, the perfluoropolyether fluoride solution was prepared, which solved the problems of process hazard, long reaction time and difficult product separation in the prior art. , achieving an efficient and safe preparation process and high yield.
Patent Information
- Application Number
- CN202211586447.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2022-12-09
- Publication Date
- 2025-02-18
- Estimated Expiration
- 2042-12-09
AI Technical Summary
The prior art has process hazards, long reaction time, low reaction yield, difficult product separation and high pressure for three waste treatment when preparing perfluoropolyether fluoride liquid, resulting in few manufacturers and expensive prices, which seriously hinders the product's application.
Hexafluoropropylene oxide oligomer and hexafluoropropylene as starting materials. Under the action of a catalyst, a perfluoropolyether fluoride solution is quickly obtained at a mild temperature through a one-step reaction. The reaction conditions include the use of acetonitrile or diethylene diethyl. The temperature of solvents such as alcohol dimethyl ether is controlled from -25 to 10°C. The catalyst is sodium fluoride, etc., and the molar ratio of hexafluoropropylene to the catalyst is between 1:0.8-1:1.0.
It achieves fast reaction speed, high reaction yield, safe process, almost no waste production, and yield rate as high as more than 90%, making the industrial production of this product easier.
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Figure CN116178123B_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the field of fluorine chemical industry, and specifically relates to a fluorinated liquid and a preparation method thereof. Background Art
[0002] Perfluoropolyether fluorinated liquid is a compound containing only fluorine, carbon and oxygen in its molecular structure. It is widely used in submerged coolants due to its excellent dielectric constant, stable chemical inertness, good thermal conductivity, extremely low surface tension and kinematic viscosity, and excellent material compatibility. It also has broad prospects in the fields of electronics, semiconductors, lithium batteries, etc.
[0003] At present, there are two methods for preparing perfluoropolyether fluorinated liquid:
[0004] 1.
[0005] The main chain structure of Rf is perfluoropolyether of krtox or Fomblin. This method requires the use of fluorine gas at a high temperature of about 200°C to stabilize the end groups of perfluoropolyether carboxylic acid, which is a dangerous process and places great pressure on the treatment of three wastes. At the same time, this method easily produces by-products, and the purification of the products after the reaction is difficult.
[0006] 2.
[0007] The main chain structure of Rf is perfluoropolyether of krtox or Fomblin. The method uses electrolytic fluorination to prepare perfluoropolyether fluorinated liquid. The raw materials of this method are difficult to obtain and the process is highly dangerous. At the same time, the yield will not exceed 50%, and the product separation is difficult, which makes this method difficult to realize industrialization.
[0008] These two methods use fluorine gas or hydrogen fluoride in the preparation of perfluoropolyether fluorinated liquid. Not only are the processes dangerous, the reaction time long, and the reaction yield low, but a large number of post-treatment measures are also required to deal with the three wastes. Therefore, there are very few manufacturers and the price is high, which seriously hinders the application of this product. Summary of the invention
[0009] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a fluorinated liquid and a preparation method thereof.
[0010] To achieve the above object, the technical solution adopted by the present invention is:
[0011] A method for preparing a fluorinated liquid comprises the following steps: using hexafluoropropylene oxide oligomers and hexafluoropropylene as starting materials and placing them in a solvent, and reacting them under the catalysis of a catalyst to obtain a perfluoropolyether fluorinated liquid; the reaction formula is shown in formula (I):
[0012]
[0013] Here, n is an integer from 2 to 4.
[0014] The catalyst is one of sodium fluoride, potassium fluoride, potassium difluoride, rubidium fluoride and cesium fluoride.
[0015] The solvent is one of acetonitrile, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and sulfolane or a mixture of several of them.
[0016] The temperature during the reaction was controlled at -25 to 10°C.
[0017] The molar ratio of hexafluoropropylene to the catalyst is 1:0.8-1:1.0.
[0018] The mass ratio of hexafluoropropylene to the solvent is 1:0.5-1:2.0.
[0019] The molar ratio of hexafluoropropylene to hexafluoropropylene oxide oligomer is 1:0.7-1:1.0.
[0020] The present invention also includes a fluorinated liquid obtained by the preparation method.
[0021] Compared with the prior art, the present invention has the following beneficial effects:
[0022] The preparation method of the fluorinated liquid of the present application adopts a conventional reaction operation process, uses hexafluoropropylene oxide oligomers (mainly tetramers, pentamers, and hexamers) and hexafluoropropylene as starting materials, and obtains the final product through a one-step reaction. The reaction temperature is mild, the reaction speed is fast, and the reaction yield is high. The process is safe and almost no three wastes are generated, making it easy to scale up the product. DETAILED DESCRIPTION
[0023] In order to enable those skilled in the art to better understand the technical solution of the present invention, the present invention is further described in detail below in conjunction with the best embodiment.
[0024] Example 1: Acetonitrile (100 ml) and potassium fluoride (55 g) were added to a 1L reactor. The reactor was cooled to -15°C and then the reactor was quickly evacuated to -0.095 MPa. After stirring was turned on, hexafluoropropylene (150 g) was gradually introduced into the reactor within 1 h, during which the temperature in the reactor was kept at -15°C. Then, hexafluoropropylene oxide tetramer (600 g) was introduced into the reactor at a speed of 300 g / h, during which the temperature in the reactor was kept at -15°C. After the addition of hexafluoropropylene oxide tetramer, stirring was continued for 30 minutes. Then, the reactor was opened, the lower layer of liquid was separated and washed with 5% sodium hydroxide solution and deionized water in turn, and the washed crude product was distilled to obtain a perfluoropolyether fluorinated liquid (678 g) with a boiling point of 200°C, with a yield of 92.1%.
[0025] Example 2: Tetraethylene glycol dimethyl ether (2.5L) and cesium fluoride (1.4Kg) were added to a 10L reactor. The reactor was cooled to -20°C and then the reactor was quickly evacuated to -0.095Mpa. After stirring was turned on, hexafluoropropylene (1.5Kg) was gradually introduced into the reactor within 1h, during which the temperature in the reactor was kept at -20°C. Then, hexafluoropropylene oxide hexamer (9Kg) was introduced into the reactor at a speed of 3Kg / h, during which the temperature in the reactor was kept at -20°C. After the hexafluoropropylene oxide hexamer was added, stirring was continued for 30 minutes. Then, the reactor was opened, the lower layer of liquid was separated and washed with 5% sodium hydroxide solution and deionized water in turn, and the washed crude product was distilled under reduced pressure to obtain a perfluoropolyether fluorinated liquid (9.5Kg) having a boiling point of 108-110°C / 1mm Hg, with a yield of 91.7%.
[0026] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.
Claims
1. A method for preparing a fluorinated liquid, characterized in that: The reaction formula is shown in formula (I): （I）； Wherein, n is an integer from 2 to 4; The catalyst is one of sodium fluoride, potassium fluoride, potassium dihydrogen fluoride, rubidium fluoride and cesium fluoride; The solvent is one or a mixture of acetonitrile, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and cyclopentane; The temperature during the reaction was controlled at -25 to 10°C; The molar ratio of hexafluoropropylene to catalyst is 1:0.8-1:1.0; The mass ratio of hexafluoropropylene to solvent is 1:0.5-1:2.0; Hexafluoropropylene and The molar ratio is 1:0.7-1:1.
0.
2. A fluorinated liquid obtained by the preparation method according to claim 1.
Citation Information
Patent Citations
Method of removing hexafluoropropylene dimers
CN1802338A
Novel polyfluoro-substituted ketones and their preparation from polyfluoro acid fluorides
US3185734A
Use of fluorinated ketones in fire extinguishing compositions
WO2001005468A2