SU380637A1 - METHOD OF OBTAINING MONO- OR DI-a-FLUOROCRYLATES - Google Patents

Description

one

The invention relates to a process for the preparation of new MONO- and di-a-fluoro-acrylates ethylene glycol, which can be used in the synthesis of polymers.

A known general method for the preparation of esters of carboxylic acids, including esters of acrylic acid, by esterifying them with alcohols in the presence of a catalyst.

However, the resulting polymers do not have high resistance when working in aggressive environments.

Based on the known reaction of the proposed method of obtaining mono - and di-a-fluoroacrylates of ethylene glycol formula

CH, CF - C - O - SNS.SI, - R,

II Oh

where R-OH or CH2 CF-C-O-, concludes II

ABOUT

c in that a-fluoro-p-chloroporpoxylic acid is treated with ethylene glycol in an inert organic solvent, for example benzene, in the presence of a catalyst, for example g-toluenesulfonic acid, at a temperature above the boiling point of the solvent, followed by dehydrochlorination of the resulting mono- di-a-fluoro-p-chloropropiopta ethylene glycol and the selection of target products by known methods.

It is best to use organic bases, such as triethylamine, in the presence of a polimerylization inhibitor, nianpiiMep copper chloride, for dehydrochlorinated mono- and di-aftor-p-chloronopionates of ethnlene glycol.

The resulting polypropylene di-α-fluoroacrylates ethylene glycol are superior in terms of a number of properties to the known fluoroacrylates, for example, glycdol ephr a-fluoroacrylic acid.

Example 1. Getting mono-a-fluoroacrylate ethylene glycol.

100 g (0.8 Mo.ib α-fluoro-p-chloropropionic acid, 150 g (2.2 mol) ethylene glycol, 500 ml of dry benzene are heated for 12 hours in the presence of 2 g of p-toluenesulfonic acid at a temperature of benzene benzene. The separated water caught by known methods

for example, in a Dean-Stark nozzle.

At the end of the reaction (with BE dividing the maximum amount of water), the solvent is distilled off, the residue is fractionated in vacuo to obtain 86 g (65%) of a viscous colorless

liquid, t. Kip. 133-136 ° C / 10 mm or 90- 92 ° C / 0.005 mm; n ° 1,4579; fiff 1.41702.

According to the data of elemental analysis and I1 of spectroscopy, the most important substance is ethylene glycol mono-cc-fluoro-p-chloro-inroinonate. Found,%: C 35.83; 35.38; H 4.84; 4.84; C1 20.91; 20.74; 32.84. CsHeClFOs. Calculated,%: C 35.21; H 4.73; C1 20.79; 33.23. To a solution of 47.5 g (0.28 mol) of mono-a-fluoro | 3-chloropropionate ethylene glycol in 250 ml of dry benzene at a temperature of 28 hours (0.28 mol) of triethylamine, heated at a temperature of boiling benzene in the presence of 0.1 g of copper chloride, filtered off, the solvent is distilled off in the presence of 0.1 g of copper chloride, the solvent is distilled off, the residue is distilled twice in vacuo and 20.2 g (55%) of colorless, lightly mobile liquid, t. Kip. 90-9GS / 10 lsh; 40 1,4341; df 1.23118. According to the elementary analysis and IR spectroscopy, the substance obtained is ethylene glycol mono-a-fluoroacrylate. Found,%: C 44.38; 44.46; H 5.31; 5.30; 28.37. QHyFOj. Calculated,%: C, 44.78; H 5.72; 27.90. Example 2. Getting di-a-fluoroacrylate ethylene glycol. 25.3 g (0.2 mol) of a-fluoro-p-chloropropionic acid, 6.2 g (0.1 mol) of ethylene glycol and 200 ml of dry benzene are heated for 6 hours in the presence of 1 g of α-toluene sulfonic acid at the boiling point of benzene. At the end of the reaction, the solvent is distilled off, the residue is fractionated in vacuo, a viscous, colorless substance is isolated, i.e. 128-130 ° C / 0.005 mm, crystallized on standing. After double recrystallization from chloroform, 21 g (75%) of a white crystalline substance are obtained, t. Nl. 64-66 ° C, which, according to elementary analysis and IR spectroscopy, is ethylene glycol di-afluoro-p-chloropropionate. Found,%: C 34.28; 34.44; H 3.61; 3.43; C1 25.55; 25.42. C8HioCl2F2O4. Calculated,%: C 34.34; H 3.62; C1 25.42. 8.7 g (0.086 mol) of triethylamine are poured into a solution of 12 g (0.043 mol) of di-a-fluoro-chloropronionate of ethylene glycol in 150 ml of dry benzene at room temperature and without stirring, heated for 4 hours with stirring at the boiling point of benzene in the presence of 0 , 05 g of copper chloride, the triethnlamine hydrochloride is filtered off, the solvent is distilled off from the filtrate in the presence of copper chloride, the residue is fractionated in vacuo and 7 g (80%) of a colorless mobile liquid is obtained, t. 50-52 ° C / 0.01 mm; 1.4345; df 1,27845. According to the elementary analysis and IR spectroscopy, the substance obtained is ethyla glycol dia-fluoroacrylate. Found,%: C 46.41; 46.16; H 4.26; 4.24; , 87. C8H8F204. Calculated,%: C 46.62; H 3.92; M, Ro 41.31. The subject of the invention. A method for producing mono- or di-α-fluoroacrylates of ethylene glycol of the general formula CH, CF — C — O — CH, CH, —R, II O where R — OH or CH 2 CF — C — O-, characterized in that Phor-P-chloropronionic acid is treated with ethylene glycol in an inert organic solvent, for example benzene, in the presence of a catalyst, for example p-toluenesulfonic acid, at a temperature not higher than the boiling point of the solvent, followed by dehydrochlorination of the mono- and di-a-fluoro-chloro ethylene glycol p-chloropropionate and isolation of desired products famous tricks.