SU729173A1 - Method of preparing glycidylic fluoroethers - Google Patents

Description

The invention relates to a process for the preparation of glycidyl fluoroethers of the general formula. R About - CM - ORgOCH -CH - CH, II / where Rt H - (CFg-CFj) - SI. a 1-3; F} (CH2) 2, (CH3) - O - (CHj). These compounds are new, not described in the literature, and can be used as starting monomers for the production of adhesives, compounds, coatings, lubricants, as well as for processing fabrics and paper in order to achieve water and oil repellency. A known method for producing glycidyl fluoroether of the formula; (C) (n) () -CF- (X: H, CH-CH2, where R is R - H, halogen, alkyl, haloalkyl, cycloalkyl, halogenloxyalkyl l. These compounds are obtained by reacting a ketone, containing lightly) at least 2 fluorine atoms attached to carbon atoms adjacent to the carbonyl group with alkali metal fluoride in an inert organic solvent (acetonitrile, dioxane, THF, tetramethylenesulfone, di1-p; m and others) at temperatures up to 35 ° С The resulting intermediates react with epyuorhydrin at 20-1EP, to form fluoroalkylglycene or ethyl ester. The disadvantages of this method include the need for deep cooling of the system, the additional energy consumption associated with it, the duration of the synthesis, the use of explosive solvents, the presence of waste water (after repeated washing with ether with water), and the complexity of the instrumentation process. Known is xaioice, a method for preparing esters by a formula; JC (R) (R СХ: Р „С (Х) (У) СН5СН-СН9 where F {and R. are F or perhalogenated Cf-Cg alknly alkfly Cf-Cg; X -H, C1, Br, F; Y –Y or P 2. These compounds are obtained by reacting esters of the general formula: PC (F () (R) (X) (y), where H, H, X and Y - have the indicated values -i, with alkyl alcohol or allyl acetate at 50- .100 ° C followed by treatment of the reaction products of an alkali metal hydroxide. The disadvantage of this method is the length of the process and the large energy consumption (stirring and heating for 72 hours), a multistage process, a low yield of non-alcoholic products. producing glycidyl fluoroethers general formula; H- (C F2-CF2) n-CH OCH CH-CH, TOEP 1 - by reacting 1Mol H- (H2OH with 0.5–20 moles of epichloro epifluorohydrin in an alkaline medium at 50–100 ° С 3. The main disadvantages of this method are the work with a large amount of Calcium ehydrate, the use of a large excess of deficient epichlorvdrin, the need to cool the reaction system and neutralize wastewater, the presence of wastewater. The purpose of the invention is to develop a process for the preparation of new compounds of glycol fluoride esters of the general formula;

R, -O-CH-0-F g-OCH -CH-CHA,

WITH

where R, H- (CF-CFJ-CHj ,, n 1-3; R2 (CHj) 2, (CH2), j.-0- (CH, j) i, lshyeno these disadvantages.

This is achieved by the fact that glycidyl ethers of & tsi formula -,

H, -Ot-C H-ORj-OC H-j-C H — C H 2

where (CF2-CFg,) -CHi, P. -1 - 3; (CH2) e, (CH;,) 4-0- (CH2),

M-CF.iCF (i CH20CHCCHj) OCHiCMiOCH, iCH-CK2,

0

0.24 g of perfluorobutyric acid is added to the mixture of 51 g (0.35 M) of vinylox and 47g (O, 35M) of 2.2.3.3, tetrafluoropropyl yla-1, and stirred (heated to). When the reaction mass is cooled to room temperature, its distillation is under vacuum, and 81.7 g are recovered.

(84%) of product, bp. (1mm),

/ RO90

44 1.2605, Pd 1.3984.

MND found 52.87, Calculated 52, ZR. is obtained by reacting fluorine-containing alcohols of the corresponding structure with 1-vinyloxyethoxy-propylene-2, oxide (vinylox) or 1-vinyloxy-ethoxy-ethoxy-propylene-2,3 oxide (vinylox-D) in the presence of perfluorocarboxylic acid as catalyst, taking the amount of 0.2 - O, 3% weight, The reaction proceeds at room temperature and a simple shift of equimolar amounts of reagents. The desired product is isolated in high yield (84-93% and above) by fractionating the reaction mixture under vacuum. The process is single-stage, technologically advanced, does not require solvents, complex instrumentation, energy consumption for moving and heating reaction mass, consists of a minimum of operations (mixing of initial reagents and isolation of the product by perehchenkoy) and does not produce wastewater and waste, in some cases the connection is almost quantitative , and the resulting product can be successfully used (for example in the synthesis of epoxy resins) without any distillation at all. According to the developed method, fluoro-glycidyl esters can be obtained on the basis of any fluorine-containing hydro-strong compound. Synthesis of glycidyl fluoro-efficacy — odorless, colorless and odor-free liquids that are stable during storage (for many months) are non-toxic (LjD Q 12OO-25OO mg / kg) and soluble in most organic solvents (ether, acetone, alcohol, toluene, and t .P,). Example. 1- / 2 (glCIDIloxy) ethoxy / 2,2,3,3-tetrafluoropropanolol-1 ethyl ester.

Claims (1)

Formula of the invention ⁵⁰ A method for producing glycidyl silt fluoroethers of the general formula: R, -O-CH-OR ^ -OCHp-CH-CHg, ¹ I ^Z \ / CH O _v wherein R, = H- (CF ₂ -CF _{2) n} -CH _2, C ₆ F _I3 CH _2; P = 1 - 3; Ρ = (CH), (CH) -0- (CH), which implies that fluorine-containing alcohols of the corresponding structure are reacted with 1-vinyloxyethoxypropylene-2,3-oxide or 1-vi * nyloxy ethoxy and ethoxypropylene-2,3-oxide in the presence of perfluorocarboxylic acid as a catalyst, taken in an amount of 0.2 - 0.3 wt.%.