SU513968A1 - The method of obtaining acrylic or methacrylic esters of polyfluorinated alcohols - Google Patents

Description

-50 ° C, pour 150 ml of freon-12, then 70 g (0.2 g-mol) of 1,1-dihydroperfluorpeptyl alcohol and 21.7 g (0.24 g-mol) of acrylic acid chloride. The reaction mass is stirred for 2-3 minutes, after which the dosage of 27 g (0.24 g-mol) of 50% aqueous potassium hydroxide solution is started for 10-15 minutes. The temperature of the reaction mixture was kept constant from -26 to -27 ° C. At the end of the dosage, the temperature of the reaction mass is brought to room temperature, while the freon is completely removed.

After removing the freon, an equal volume of water is added to the reaction mass, the contents are stirred for 2-3 minutes, and after separation the organic layer is separated. The water washing operation is repeated 2-3 times. Potassium chloride, potassium acrylate, excess silk, if any, are removed from the reaction mixture by washing. The organic phase, after washing with water and drying over CAL, according to GLC, contains 98.5% (80 g) of 1,1-dihydroperfluoroheptylacrylate and 1.5% of unreacted alcohol. The yield is 97.5%.

Example 2. The reaction is carried out as in Example 1, in Freon-12. From 50 g (0.2 g-mol) of 1,1-dihydroperfluoroamyl alcohol and 21.7 g (0.24 g-mol) of acrylic acid chloride with the addition of 27 g (0.24 g-mol) of a 50% aqueous solution potassium hydroxide for 10-15 minutes with constant stirring of the reaction mixture, 60 g of the substance are obtained, which according to GLC contains 98.8% 1,1-dihydroperfluoroamyl acrylate. The yield is 97.8%.

Example 3. In the same way as in examples 1 and 2, the experiment was carried out with 150 ml of Freon-C318. At the same time, the temperature of the cooling mixture is maintained in the reflux from -20 to -30 ° C, and the temperature of the reaction mixture is -2, -3 ° C. From 70 g (0.2 g-mol) of 1,1-dihydroperfluorpeptyl alcohol and 21.7 g (0.24 g-mol) of acrylic acid chloride, 80 g of a substance containing, according to GLC, 97.5% of 1.1- dihydroperfluorpeptilacrylate. The yield is 96.5%.

Example 4. In a flask with a vacuum jacket and a reflux condenser cooled with running tap water, pour 150 ml of freon-11, 70 g (0.2 g-mol) 1,1-dihydropertorgeptyl alcohol and 25 g (0.24 g-mol ) methacrylic acid chloride with constant movement. After the reaction mixture has been moved, a dosage of 27 g (0.24 g-mol) of a 50% aqueous solution of potassium hydroxide is started over a period of 10-15 minutes within 2-3 minutes. The temperature of the reaction mixture during dosing is set at 23-25 ° C. At the end of the alkali dosage, the reaction mass is washed with water to a neutral medium of wash water, dissolved over calcium chloride, then the freon is distilled.

Table 1

table 2

five

in a water bath at a temperature not exceeding 60 ° C, the residue of freon is removed in a water jet pump vacuum. 83 g of product are obtained with a content according to GLC of 97.5%, 1,1-dihydropertorgentilmethacrylate. The yield is 96.5%. Physico-chemical properties of the products are given in table. one.

The structure of the obtained products was proved using elemental analysis, IR spectroscopy and gas-liquid chromatography. Khar;: the characteristics of the freons used are given in Table. 2

In all the basic examples after the completion of the reaction, the freon is removed, heating the reaction mass. Condensed vaporized freon (freon-12 at, freon-11 at 10 ° C, freop-142 and C-318 at -35 ° C) and again, 3-5 times used for the same purpose. Deviations in the results of the experiments were not noticed. Loss of freons (the amount of fra, onov remaining in the raw product) when they are used again is, kg of freon per 1 kg of acrylate:

F-120,015-0,025

F-110.03-0.04

5139

6

Ф-С3180,020-0,035

F-1420,20-0,030

The process losses of freons, which are mainly associated with recondensation, constitute in addition to the specified 0.02-0.05 kg of freon and 1 kg of the finished product.

The inventive method for the production of polyfluoroalcohol acrylates was also tested on a pilot plant in a displacement reactor with a propeller mixer and a working volume of 20 liters and showed the same results as in the examples. Lipėna, the rotation speed of the broom is 1.6-3.5 m / s.

Claims (1)

Invention Formula A method of producing acrylic or methacrylic esters of polyfluorinated alcohols by reacting the acid chlorides of these acids with polyfluorinated alcohols in the presence of an aqueous solution of an inorganic base, characterized in that, in order to intensify the process and simplify its technology, the process is conducted in a boiling freon medium.