SU424855A1 - METHOD OF OBTAINING MONO- OR DIPOLIFTOR-ALKYL ETHERS OF GLYCOL - Google Patents

Description

one

This invention relates to a process for the production of glycol polyfluoroalkyl ethers, in particular ethylene glycol, diethylene glycol, which can be used as solvents, hydraulic fluids, plasticizers, and are also used to produce stable lubricants and heat transfer fluids.

A method of producing ethylene glycol mono-polyfluoroalkyl esters is known by reacting an alcohol of the general formula H (CP2 CP2) pCH2OH, where l is 1-5 with ethylene oxide in the presence of sodium hydride at 140-150 ° C. The yield of the target products is 60%.

In order to increase the yield and expand the range of end products, a method has been proposed for the preparation of mono- or di-polyfluoroalkyl ethers of glycols of the general formula

H (CF2) mCH20CH2CH2 nOR, (1)

where m - 2, 4, 6;

p - I or 2;

R is hydrogen with p 1 and a bond with p 2, meaning that the fluorine-containing alcohol of the general formula

H (CF2) ™ CH20H (2)

(where w 2, 4, 6) is subjected to interaction with chlorox or ethylene chlorohydrin in an alkaline medium when heated. The desired product is isolated by known techniques. The yield of final products reaches 85%. In comparison with the known method, the proposed method does not require the use of hazardous alkali metal hydrides with a lower reaction temperature. According to this method, new dipolyfluoroalkyl ethers of diethylene glycol are obtained, when in formula (1) n 2, R is a bond. The temperature in this case is 80-110 ° С. The introduction of polyfluoroalkyl substituents leads to a change in the properties of diethylene glycol ethers in comparison with hydrocarbon

analogues. In particular, polyfluoroalkyl esters have a significantly higher boiling point, are insoluble in water and less flammable. Upon receipt of monopolyfluoroalkyl

ethylene glycol ethers, i.e. when in the formula (1), the reaction temperature is maintained from 70 to 100 ° C.

Example 1. Synthesis of di-1,1,3-trihydrotetrafluoropropyl ether diethylene glycol.

500 ml (740 g: 5.6 mol) of 1,1,3-trihydrotetrafluoropropyl alcohol are poured into the flask with a blender and reflux condenser and injected in portions with stirring and at a temperature of 70-80 ° C. 224 g (4 mol) of hydrate

potassium oxide until dissolved. 236 ml (288 g, 2 mol) of hlorex are added to the obtained alcohol at 95–100 ° C and under stirring with dripping for 3.5–4 hours, the reaction mass is kept at the indicated temperature and stirred for 1–2 hours, cooled and neutralized 4.7 N hydrochloric acid (190 ml). The precipitate is filtered off, the filtrate is poured into a separating funnel and after settling, the lower organic layer is separated, which is dried with anhydrous calcium chloride. The resulting raw material (630 ml) is rectified with iodine by vacuum, and the following main fractions are collected at boiling points:

54-58 ° C / 78 mm Hg v .; V 264 ml; Excessive and unreacted 1,1,3-trihydrotetrafluoropropyl alcohol.

74-80 ° C / 15 mm Hg. v .; V 90 ml; Unreacted Chlorex.

104-110 ° C / 10 mmHg v .; V 122 ml; The main component is | 3-C1, p-1,3,3-trihydrotetrafluoropropoxy ethyl ether; NSRGSRGNSOSNaSNgOSNgSNgS.

132--136 ° C / 10 mm Hg. v .; V 119 ml.

The last fraction is subjected to additional rectification and get 112 ml (155 g) of di-1,1,3-trihydrotetrafluoropropyl ether diethylene glycol:

(HCFaCFaCHaOCHaCHa) 2O;

m.p. 134-135 ° C / 10 mm Hg. v .; d | ° 1,379 g / cm3; nif 1.3615; purity io GLC 98.6%. The yield of reacted alcohol is -36%. Found,%: C 36.22; H 4.23; F 45.50.

ClO14P8Oz.

Calculated,%: C 36.16; H 4.21; F 45.31. The structure was confirmed by NMR spectra H

F19.

The product has a kinematic viscosity coefficient of 6.25 eats (23 ° C), does not freeze at minus 75 ° C.

Example 2. Synthesis of di-1,1,5-triG | Diethylene glycol Idroooctafluoropentyl ether.

In a flask equipped with a stirrer and reflux condenser, pour 505 ml (838 g, 3.6 mol) of 1,1,5-trihydrooctafluoropentanol, 10 ml of distilled water, and add 168 g in portions with stirring at 80-90 ° C. 3 mol) of potassium hydroxide until completely dissolved. At the end of the process, the temperature is raised to 100-105 ° C and with vigorous stirring 170 ml (208 g, 1.45 mol) of chlorine is added dropwise over 2.5-3 hours for another 0.5-1 hour, cooled, and 170 ml is added. 5 NHC1 until neutral. Then 350 ml of distilled water is poured to dissolve the precipitate, the mass is poured into a separating funnel, the lower organic layer is separated and washed with 0.5 times volume of water. After settling, 625 ml of raw material are obtained. Raw is rectified under vacuum with the selection of the following main fractions, boiling at

51-55 ° C / 8 mm Hg Art. (V 260 ml of the original alcohol); 64-70 ° C / 7 mm Hg. Art. (V 40 ml of Chlorex); 115-120 ° C / 8 mm Hg. Art. (V 130 ml | 3-C1, | 3-1,1,5-trihydrooctafluoropentoxy acid 5 ethyl ester:

And (CF2) 4CH20CH2CH20CH2CH2C1);

160-162 ° C / 8 mm Hg. Art. (V 160 ml di-1,1,5 trihydro-octafluoropentyl ether diethylene H (CF2) 4CH20Cn2CH2 20; d.f. 0 glycol

L566 G / CM 1,349).

The purity of the product by GLC is more than 98%. The yield on the reacted alcohol is 53%.

Found,%: C 32.38; H 2.72; F 57.17.

Ci.HuFisOs.

Calculated,%: C 31.68; H 2.63; F 56.73.

The structure was confirmed by NMRN and FI spectra.

The product has a viscosity of 13.0 eats (22 ° C) and does not freeze at -75 ° C.

Example 3. Synthesis of mono-1,1,5-trihydro-octafluoropentyl ether of ethylene glycol.

140 ml (232 g, 1 mol) 1,1,5 trihydro-octafluoropentanol are poured into a flask with a stirrer and reflux condenser and injected in portions with stirring and at a temperature of 60–80 ° C with 56 g (1 mol) of potassium hydroxide moistened with 15 ml distilled water. 67 ml (80.5 g; 1 mol) of ethylene chlorohydrin is added dropwise over 3.5–4 hours to the obtained alcohol at 90–95 ° C and stirring. Then the reaction mass is cooled, washed twice with an equal volume of distilled water, the organic layer is separated and dried with anhydrous sodium sulfate. Raw rectified under vacuum, allocating 67 g of the original 1,1,5-triG | IDrooktafluoropentanol and the target product. 92.5 ml (143 g; 0.52 mol) of ethylene glycol mono-1,1,5-trihydro-octafluoropentyl ether were obtained:

H (CP2) 4CH2OCH2CH2OH;

m.p. 116-118 ° C / 40 mm Hg. v .; d | g 1,544 g / cm3; Pr 1,348. Output to the reacted

alcohol is 73%. Found,%: C 30.53; H 2.84; F 55.44.

C7H8F802.

0 Calculated,%: C 30.44; H 2.93; F 55.06.

The structure was confirmed by HI and.

Example 4. Synthesis of mono-1,1,7-trihydrodo5 decafluoroheptyl ether of ethylene glycol.

56 g (1 mol) of potassium hydroxide, 4 ml of distilled water and 332 g (1 mol) of 1,1,7-trihydrododefluoroheptanol are loaded into a flask with a stirrer. The components under stirring are heated to 85 ° C and are held until the potassium hydroxide is completely dissolved. 67 ml (80.5 g, 1 mol) of ethylene chlorohydrin is added dropwise over 3.5-4 hours to the obtained alcohol at the indicated temperature and stirring. Then the reaction mass is cooled, washed with distilled water (2 X 250 ml), the organic layer is dried with anhydrous sodium sulfate. The raw material (213 ml) is rectified under vacuum, separating 76 ml of the original 1.1 .T-trihydrododecaftahepanol and the desired product. 111 ml (182 g; 0.484 mol) of ethylene glycol mono-1,1,7-trihydrododecaftafluoride ether ethylene glycol: H (CP2) bCH20CH2CH2OH, t. Bales were obtained. 106-108 ° C / 6 mm Hg v .; 1.642 and 1.334; The yield on the reacted alcohol is 81%.

Found,%: C 28.58; H 2.10; F 60.66.

C9H8P1202.

Calculated,%: C 28.72; H 2.15; F 60.62. The structure was confirmed by the HI and F “NMR spectra.

Subject invention

The method of producing mono- or dipolyfluoroalkyl ethers of glycols of the general formula (H (CF2) mCH20CH2CH2) nOR,

where m - 2, 4, 6;

n - 1 or 2;

R - means hydrogen at p 1 and a bond at p2, characterized in that, in order to increase the yield and expand the range of target products, fluorine-containing alcohol of the general formula

H (CF2) mCH20H,

where m 2, 4, 6 is subjected to interaction with chlorex or ethylene chlorohydrin when heated in an alkaline medium with the selection of the target product by known methods.