PROCESS OF PREPARING FLUOROETHER COMPOUNDS WITH UNSATURATED END GROUPS

Abstract

The present invention relates to a process of preparing polyfluoroether compounds with unsaturated end groups and to compounds prepared by said process.

Claims

1. A process for preparing a compound of formula I
(Rf(CHF—CF.sub.2Y).sub.m).sub.nL(X).sub.k  I by reacting a compound of formula II
Rf(CHF═CF.sub.2).sub.m  II with a compound of formula III
(HY).sub.nL(X).sub.k  III in the presence of a base, wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings Rf is a perfluorinated alkyl or alkylene group that optionally contains one or more hetero atoms, Y is O or S, L is a single bond or an at least divalent organic group, X is an ethylenically unsaturated group, m is 1 or 2, n is 1, 2 or 3, o is 1, 2 or 3.

2. The process according to claim 1, characterized in that Rf is a perfluorinated C1-C30 alkyl or alkylene group that optionally contains one or more hetero atoms.

3. The process according to claim 1, characterized in that m is 1 Rf is selected from the following groups CF.sub.3—(CF.sub.2).sub.0-3—, CF.sub.3—(CF.sub.2).sub.0-3—O—, CF.sub.3—(CF.sub.2).sub.0-3—O—(CF.sub.2).sub.1-3—, CF.sub.3—(CF.sub.2).sub.0-3—O—(CF.sub.2).sub.1-3—O—, CF.sub.3—(CF.sub.2).sub.0-3—O—(CF.sub.2).sub.1-3—O—CF.sub.2—, CF.sub.3—(CF.sub.2).sub.0-3—O—(CF.sub.2—O).sub.1-8— and CF.sub.3—(CF.sub.2).sub.0-3—O—(CF.sub.2—O).sub.1-8—CF.sub.2—.

4. The process according to claim 1, characterized in that m is 1 and Rf is selected from the following groups CF.sub.3—(CF.sub.2).sub.1-2—, CF.sub.3—(CF.sub.2).sub.1-2—O—, CF.sub.3—O—(CF.sub.2).sub.1-3—, CF.sub.3—O—(CF.sub.2).sub.1-2—O—, CF.sub.3—(CF.sub.2).sub.1-2—O—CF.sub.2—, CF.sub.3—O—(CF.sub.2).sub.1-2—O—CF.sub.2—, CF.sub.3—O—(CF.sub.2—O).sub.1-8— and CF.sub.3—O—(CF.sub.2—O).sub.1-8—CF.sub.2—.

5. The process according to claim 1, characterized in m is 2 and Rf is selected from the following groups —(CF.sub.2).sub.0-4—, —O—(CF.sub.2).sub.0-3—O—, —(CF.sub.2).sub.1-3—(CF.sub.2).sub.0-3—O—(CF.sub.2).sub.1-3—, —O—(CF.sub.2).sub.1-3—(CF.sub.2).sub.0-3—O—(CF.sub.2).sub.1-3—O—, —(CF.sub.2).sub.1-3—O—(CF.sub.2).sub.1-3—O—CF.sub.2—, —CF.sub.2—(CF.sub.2).sub.0-3—O—(CF.sub.2—O).sub.1-8— and CF.sub.2—(CF.sub.2).sub.0-3—O—(CF.sub.2—O).sub.1-8—CF.sub.2—.

6. The process according to claim 1, characterized in that m is 2 and Rf is selected from the group consisting of —(CF.sub.2).sub.1-3—, —(CF.sub.2).sub.1-3—O—, —O—(CF.sub.2).sub.1-3—O—, —CF.sub.2—O—(CF.sub.2).sub.1-2—O—, —CF.sub.2—(CF.sub.2).sub.1-2—O—CF.sub.2—, —CF.sub.2—O—(CF.sub.2).sub.1-2—O—CF.sub.2—, —CF.sub.2—O—(CF.sub.2—O).sub.1-8— and —CF.sub.2—O—(CF.sub.2—O).sub.1-8—CF.sub.2—.

7. The process according to claim 1, characterized in that X is an acrylate or methacrylate group or an ethynyl group.

8. The process according to claim 1, characterized in that L is a single bond or a saturated C1-C20 alkylene group that is straight-chain or branched, optionally contains one or more heteroatoms, preferably one or more O atoms, and optionally contains one or more functional groups.

9. The process according to claim 1, characterized in that L is selected from the group consisting of methylene, ethylene, propylene, isopropylene, n-butylene, isobutylene, sec-butylene, t-butylene, or pentylene or hexylene which are straight-chain or branched.

10. The process according to claim 1, characterized in that m is 1 and Rf is selected from CF.sub.3—(CF.sub.2).sub.1-2—, CF.sub.3—(CF.sub.2).sub.1-2—O—, CF.sub.3—O—(CF.sub.2).sub.1-3—, CF.sub.3—O—(CF.sub.2).sub.1-3—O—, CF.sub.3—(CF.sub.2).sub.1-2—O—CF.sub.2—, CF.sub.3—O—(CF.sub.2).sub.1-2—O—CF.sub.2—, CF.sub.3—O—(CF.sub.2—O).sub.1-8— and CF.sub.3—O—(CF.sub.2—O).sub.1-8—CF.sub.2—, or m is 2 and Rf is selected from —(CF.sub.2).sub.1-4—, —O—(CF.sub.2).sub.1-3—O—, —(CF.sub.2).sub.1-3—(CF.sub.2).sub.0-3—O—(CF.sub.2).sub.1-3—, —O—(CF.sub.2).sub.1-3—(CF.sub.2).sub.0-3—O—(CF.sub.2).sub.1-3—O—, —(CF.sub.2).sub.1-3—O—(CF.sub.2).sub.1-3—O—CF.sub.2—, —CF.sub.2—(CF.sub.2).sub.0-3—O—(CF.sub.2—O).sub.1-8— and CF.sub.2—(CF.sub.2).sub.0-3—O—(CF.sub.2—O).sub.1-8—CF.sub.2—, and L is a C1-C6 alkylene group that is straight-chain or branched and optionally contains one or more hetero atoms, preferably one or more O atoms, and optionally contains a functional group.

11. The process according to claim 1, characterized in that the compounds of formula I are selected from the following formulae: ##STR00011## ##STR00012## wherein i is 2-10.

12. The process according to claim 1, characterized in that the compounds of formula II are selected from the following formulae: ##STR00013##

13. The process according to claim 1, characterized in that the compounds of formula III are selected from the following formulae: ##STR00014## ##STR00015## wherein i is 2-10.

14. The process according to claim 1, characterized in that the reaction of compounds II and III is carried out in an organic solvent selected from linear or cyclic alkyl ethers, or aliphatic or aromatic hydrocarbons.

15. The process according to claim 14, characterized in that the solvent is selected from dioxane, tetrahydrofurane or methyl-tert-butylether, or mixtures thereof, or toluene.

16. The process according to claim 1, characterized in that the base is selected from alkali carbonates, alkaline earth carbonates or alkali hydroxides.

17. The process according to claim 1, characterized in that the reaction mixture is heated to a temperature above room temperature and stirred.

18. A compound of formula I or its subformulae as defined in claim 1, wherein X is an ethynyl group.

Description

EXAMPLE 1

[0075] Compound (1) is prepared as follows.

##STR00009##

[0076] 0.255 g (0.78 mmol) of caesium carbonate and 0.01 g (0.05 mmol) of 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) are initially introduced in a round-bottomed flask. 0.33 g (2.52 mmol) of 2-hydroxyethyl methacrylate and 0.75 g (2.82 mmol) of perfluoropropylvinyl ether (PPVE) in 3.34 g of dioxane are then added dropwise. The reaction mixture is subsequently heated to 100° C. and stirred at this temperature for 20 h. The product can be obtained directly from the reaction mixture by distillation.

[0077] Yield 0.73 g (73%), purity 98%.

EXAMPLE 2

[0078] Compound (2) is prepared as follows.

##STR00010##

[0079] In 150 ml stainless steel pressure reactor 7.96 g (0.03 mol) of Perfluoro propylvinyl ether (PPVE) was added to a solution consisting of 2.52.g (0.04 mol) 3-Butin-1-ol, 2.18 g (0.04 mol) KOH and 25 ml of 1,4 Dioxane. The mixture was heated to 75° C. and kept at this temperature for 20 h. For the work up the reaction mixture was diluted with 30 ml water and 30 ml MTBE, the organic layer was separated and the aqueous layer washed twice with 30 ml MTBE. The combined organic phases were washed with 20 ml saturated NaCl and dried over Na.sub.2SO.sub.4. The product was carefully stripped from the solvents by distilling off the MTBE in a rotary evaporator.

[0080] Yield: 4.89 g (48%), purity 95%.