SU1761758A1 - Of hexakis-(2,2,2-trifluoroethoxy)-cyclotriphosphazene synthesis - Google Patents

Abstract

Use: as modifying additives for synthetic and natural polymers, lubricant additives, agents for treating magnetic powders. The essence of the invention: the product is hexakis- (2,2,2-trifluoroethoxy) cyclotri-phosphazene Y3R3 (OCH2CH3) e. BF S12N12R- | 8№ObRz. Exit 98%. Reagent 1: No. РзС1е. Reagent 2: СРзСЬОН. Reagent 3: alkali. Reaction conditions: in a two-phase system, water is an organic solvent at 40-60 ° C in the presence of an interphase transfer catalyst — bromide or tetrabutylammonium iodide together with a linear or cyclic aliphatic polyester with a molar ratio of 1: (); the molar ratio of bromide or tetrabutylammonium iodide, reagent 1 and reagent 2 equal to (0.04-0.06): 1: (7-9), volume ratio of aqueous and organic phases equal to (0.5-1.5) : 1, the concentration of the reagent is 1-0.05-0.15 mol / l, the concentration of the reagent is 3 0.5-0.9 mol / l for 4-6 h 1 table. sl C

Description

The invention relates to the chemistry of elemental compounds, specifically to the synthesis of cyclic oligomeric phosphazenes, in which all halogen atoms are replaced by 2,2,2-trifluoroethoxy groups, used as modifying additives for synthetic and natural polymers, additives lubricants, agents for the treatment of magnetic powders.

A known method of producing hexacid (2,2,2-trifluoroethoxy) cyclotriphosphazene (GFEF) by reacting hexachlorocyclotriophosphazene (HCFC) with sodium trifluoroethylate in a medium of sulfuric ether, however, this method is of low technology, since it involves the presence of drying steps. ether purification, also alcohol preparation. In addition, it is highly explosive and

fire hazard due to the use of ether and metallic sodium

The closest to the proposed method is the preparation of HFEF by a phase separation reaction between a solution of 0.05 mol of HCFC in 100 ml of chlorobenzene and a solution of 0.3 mol of potassium hydroxide, 0.3 mol of trifluoroethanol and 0.018 mol of tetrabutylammonium bromide at 70UC in for 21 hours. At the same time, GEFE is obtained with a yield of 30.3 g (91.3% of theory).

The disadvantage of this method should be considered a longer process time and rather significant product losses.

The aim of the invention is to reduce the duration of the process and increase the yield of the target product,

The goal is achieved by the fact that these derivatives receive interactions

I- M

SL

ioo

:

HCFC dissolved in an organic solvent which is immiscible or partially miscible with water, with a solution of trifluoroethanol in an aqueous solution of alkali metal hydroxides, in the presence of a phase transfer catalyst — bromide or tetrabutylammonium iodide (KMP-1), together with linear or cyclic aliphatic polyhydroxyfluoride. (alkylene - ethylene or propylene) mol.m. 150-600, dicyclohexayl-18-crown-6, dibenzo-18-crown-6) (KMP-2) with a ratio of KMP-1 and KMP-2 (in mol x on mole alkylene oxide unit) 1: 4-6, molar ratio Yenia KMP-1 and HCF 0.06-0.04: 1, the volume ratio of the aqueous and organic phases is 0.5-1.5: 1, the molar ratio of trifluoroethanol and HCFC is 7-8: 1, the concentration of HCF is 0.05- 0.15 mol / l, alkali concentration 0.5-0.9 mol / l, reaction temperature 40-60 ° C, for 4-6 hours

The difference between the inventive method and the known one lies in the use of phase transfer of bromide or iodide tetradbutylammonium together with a linear or cyclic aliphatic polyether at a molar ratio of 1: 4-6 and a process described in the claims. Their joint use enhances the activity of each of them, i.e. there is a synergistic effect (see examples 19-20).

In determining the ranges of variation of the indicated factors, we were guided by the following: the yield of pure GEF should be 97% and there should be no loss of HCFC due to hydrolysis, i.e. The overall yield of the crude HCFC product should be 100%.

Assuming the remaining conditions remain constant, at a molar ratio of KPM-2 and KMP-1 4: 1, the loss of HCFC due to hydrolysis tends to increase, and with a further increase in the content of KMP-2 with respect to KMP-1 6: 1, the results of the experiment remain unchanged.

A decrease in the molar ratio of KMP-1 and HCFC of 0.04 leads to a decrease in the yield of HPF, and an increase of 0.06 to an increase in the degree of hydrolysis of HCFC. Similar effects cause respectively a decrease in the concentration of HCFC in the organic phase of 0.05 mol / l and an increase of 0.15 mol / l; an increase in the volume ratio of the aqueous and organic phases of 1.5: 1 and a decrease of 0.5: 1, a decrease in the reaction temperature of 40 ° and an increase of 60 °, a decrease in alkali concentration of 0.5

mol / l and an increase of 0.9 mol / l. With a decrease in the reaction time of 4 hours and a molar ratio of trifluoroethanol and HCFC 7: 1, the yield decreases

5 of pure HFPE, and an increase in the reaction time of 6 hours and a molar ratio of phenol and HCP 9: 1, the results of the reaction do not change.

Thus, the modified method allows obtaining an HEFE with a yield of 97% and without HCFC loss for hydrolysis, using all the advantages of the reaction at the phase separation, thanks to the discovered synergistic effect of the above-mentioned phase transfer catalysts when they are used together.

Example 1 To a solution of 3.48 g (0.01 mol) of HCFC in 100 ml of benzene (HCFC concentration

0 0.1 mol / l) solution is poured into 100 ml of water (volume ratio of aqueous and organic phases 1: 1) 3.2 g of sodium hydroxide (concentration 0.8 mol / l), 8.00 g of trifluoroethanol (0.08 mole mole ratio

5 trifluoroethanol and HCF 8: 1), 0.16 g of tetrabutylammonium bromide and HCF 0.05: 1) and 0.11 g of polyethylene glycol with a molecular weight of 600 (per ethylene oxide unit of 0.0025 mole, molar ratio

0 KMP-2 and KMP-1 5: 1) and react with stirring for 4 hours at 50 ° C. The organic layer is then separated, the solvent is distilled off under vacuum, and 7.20 g of product are obtained containing 98% of hexakis (2.2.25 trifluoroethoxy) cyclotriphosphazene and 2% of pentakis (2.2,2-trifluoroethoxy) chlorocyclotrifosphazene. The composition of the mixture was determined from the total integrated intensity of the line of the corresponding components on the NMR 31 P spectrum and elemental analysis data, Examples 2-20.

Examples are similar to example 1 in the sequence of operations. The specific conditions of their conduct and the results are given in the table.

Thus, the claimed method allows to obtain hexakis (2,2,2-trifluoroethoxy) cyclotriposphene with an increased rate with a yield of 97%, without loss of the chloro cyclotrophosphazene hex0 due to hydrolysis.

Claims (1)

The method of obtaining hexakis (2,2,2-trifluoroethoxy) cyclotriphosphazene by the interaction of hexachlorocyclotriphosphazene with 2,2,2-trifluoroethanol and alkali in a two-phase water-organic solvent system in the presence of an interfacial transfer catalyst - tetrabutylammonium halide with 40 tetra-butylammonium at 40 x and 40 ml, with an alkali; C, characterized in that, in order to reduce the duration of the process and increase the yield of the target product, bromide or tetrabutylammonium iodide together with linear or cyclic are used as phase transfer catalyst. with a molar ratio of 1: 4-6, and the process is carried out with a molar ratio of tetrabutylammonium bromide or iodide, hexachlorocycotri-phosphazene and 2,2,2-trifluoroethanol, 0.04-0.06: 1 : 7–9, the volume ratio of the aqueous and organic phases is 0.5–1.5: 1, the concentration of hexachlorocyclotriposphenase 0.05–0.15 mol / l, the concentration of alkali 0.5–0.9 mol / l within 4-6 hours polyethylene ikoli mol.n. 150. 300, 400 and 600, respectively, BCP 200, 250 - polypropylene pichogi. 200 and 250, respectively, in Examples 18-20 & the reaction product of HPEO was not detected; in Example 19, the molar coo-bearing of the CMP-2 (calculated on the alkylene oxide unit) and HCFC is given