FLUORINE COMPOUNDS

Abstract

The present invention relates to fluorine compounds (I), (II) and (III), to processes for the preparation thereof, and to the use thereof.

Claims

1. Compounds of the formula (I), (II) or (III) ##STR00012## where Rf is a fluorinated, linear or branched alkyl group, optionally containing further heteroatoms.

2. Compounds according to claim 1, characterised in that Rf is a group of the formula
CF.sub.3(CF.sub.2).sub.aO.sub.b(CF.sub.2).sub.cO.sub.d, where a=0, 1, 2 or 3, b=0 or 1, c=0, 1, 2 or 3 and d=0 or 1.

3. Compounds according to claim 1, characterised in that Rf is a group of the formula CF.sub.3(CF.sub.2).sub.0-3or CF.sub.3(CF.sub.2).sub.0-3O.

4. Process for the preparation of compounds of the formula (I) of claim 1 ##STR00013## by reaction of compounds of the formula (IV) with glycidol (V) to give compounds of the formula (II) ##STR00014## where Rf is a fluorinated, linear or branched alkyl group, optionally containing further heteroatoms.

5. Process for the preparation of compounds of the formula (II) of claim 1 ##STR00015## by reaction of compounds of the formula (IV) with compounds of the formula (VI) to give compounds of the formula (II) ##STR00016## where Rf is a fluorinated, linear or branched alkyl group, optionally containing further heteroatoms.

6. Process for the preparation of compounds of the formula (III) of claim 1 ##STR00017## by reaction of compounds of the formula (IV) with compounds of the formula (VII) to give compounds of the formula (II) ##STR00018## where Rf is a fluorinated, linear or branched alkyl group, optionally containing further heteroatoms.

7. Process according to claim 4, characterised in that Rf is a group of the formula
CF.sub.3(CF.sub.2).sub.aO.sub.b(CF.sub.2).sub.cO.sub.d, where a=0, 1, 2 or 3, b=0 or 1, c=0, 1, 2 or 3 and d=0 or 1.

8. A method for the preparation of compounds of the formula (VIII) ##STR00019## where Rf is a fluorinated, linear or branched alkyl group, optionally containing further heteroatoms, Rs is an optionally fluorinated alkyl group and n is equal to 5 to 20, which comprises reacting a compoud of the formula (I) of claim 1.

9. A method for the preparation of compounds of the formula (IX) ##STR00020## where Rf is a fluorinated, linear or branched alkyl group, optionally containing further heteroatoms, and n is equal to 5 to 20, which comprises reacting a compound of the formula (II) of claim 1.

10. A process for the preparation of compounds of the formula (X) ##STR00021## where Rf is a fluorinated, linear or branched alkyl group, optionally containing further heteroatoms, and n is equal to 5 to 20, which comprises reacting a compound of the formula (III) of claim 1.

11. Compounds of the formulae (XI) to (XVI) ##STR00022## ##STR00023## where Rf is a fluorinated, linear or branched alkyl group, optionally containing further heteroatoms, and n is equal to 5 to 20.

12. Compounds according to claim 11, characterised in that Rf is a group of the formula
CF.sub.3(CF.sub.2).sub.aO.sub.b(CF.sub.2).sub.cO.sub.d, where a=0, 1, 2 or 3, b=0 or 1, c=0, 1, 2 or 3 and d=0 or 1.

13. Compound according to claim 11, characterised in that Rf is a group of the formula CF.sub.3(CF.sub.2).sub.0-3 or CF.sub.3(CF.sub.2).sub.0-3O.

14. Additives in paints, coatings, printing inks, protective coatings, special coatings in electronic or optical applications, photoresists, top antireflective coatings or bottom antireflective coatings, developer solutions and wash solutions and photoresists for photolithographic processes, cosmetic products, agrochemicals, floor polishes, photographic coatings or coatings of optical elements, comprising a compound of claim 11.

15. Composition comprising one or more compounds according to claim 11 and a vehicle which is suitable for the respective application and optionally further specific active substances.

16. Composition according to claim 15, characterised in that the composition is paint and coating preparations, fire-extinguishing compositions, lubricants, washing and cleaning compositions, de-icers, developer solutions and wash solutions and photoresists for photolithographic processes, cosmetic products, agrochemicals, floor polishes or hydrophobicising compositions for textile finishing or glass treatment.

17. Coated article whose coating has been produced using at least one compound according to claim 11.

Description

EXAMPLES

[0059] The NMR spectra are measured using a Bruker 400 MHz spectrometer with internal standard.

[0060] The IR spectra are measured using a Bruker Alpha Platinum-ATR spectrometer.

[0061] Determination of the Static Surface Tension

[0062] The static surface tensions of aqueous surfactant solutions having various concentrations c (grams per litre) are determined.

[0063] Instrument: Dataphysics tensiometer (model DCAT 11)

[0064] Temperature of the measurement solutions: 200.2 C.

[0065] Measurement method employed: measurement of the surface tension using the Wilhelmy plate method in accordance with DIN EN 14370.

[0066] Plate: platinum, length=19.9 mm

[0067] In the plate method, the surface or interfacial tension of the surfactant solution is calculated from the force acting on the wetted length of a plate, in accordance with the following formula:

[00001]$=\frac{F}{L.Math.\cos .Math..Math.}=\frac{F}{L}$

[0068] =interfacial or surface tension; F=force acting on the balance; L=wetted length (19.9 mm); =contact angle. The plate consists of roughened platinum and is thus optimally wetted so that the contact angle is close to 0 . The term cos therefore reaches approximately the value 1, so that only the measured force and the length of the plate have to be taken into account.

Abbreviations

[0069] EO ethylene oxide units

[0070] THF tetrahydrofuran

[0071] MTBE tert-butyl methyl ether

[0072] PPVE perfluoropropyl vinyl ether

[0073] b.p. boiling point

[0074] wt % per cent by weight

Example 1:

[0075] ##STR00008##

[0076] 21.78 g of glycidol, 93.86 g of PPVE, 12.19 g of potassium carbonate; 130 ml of dioxane

[0077] The starting materials are combined in a 300 ml pressure reactor and stirred at 110 C for 24 h. At the beginning of the reaction, a pressure of 4.5 bar becomes established, this drops to 0.5 bar overnight. Water and MTBE are added to the reaction mixture, and the phases are separated. The aqueous phase is extracted with 230 ml of MTBE and the combined organic phase is washed with 40 ml of water and 40 ml of saturated NaCl solution. The extract is dried over sodium sulfate and the solvent is distilled off. Product weight: 90.87 g The product was distilled in vacuo.

TABLE-US-00001 T.sub.bath C. T.sub.head C. p mbar 50.3 24.1 0.80

Example 2:

[0078] ##STR00009##

[0079] 10.5 g of 1,4-butenediol and 80.0 g of PPVE 2.01 g of KOH and 40 g of acetonitrile are combined in a pressure reactor and the mixture is heated to 80 C. After 16 hours, the reaction is complete. Water and MTBE are added to the reaction mixture and the phases are separated. The aqueous phase is extracted with 230 ml of MTBE. The combined organic phase is washed with 50 ml of water and 50 ml of saturated NaCl solution. The extract is dried over sodium sulfate. The solvent is removed in vacuo. Yield: m=56.26 g .sup.1H-NMR: 7.2 ppm (dt, 2 H, CFH); 5.9 ppm (t, 1.5H, CH=CH); 5.7 ppm (t, 0.5H, CHCH) 4.6 ppm (d, 1H, CH.sub.2O); 4.5 ppm (d, 3H, CH2O); 1 HNMR: 7.2 ppm (d, 1 H, CH.sub.2O); 4.5 ppm (d, 3H, CH.sub.2O);

Example 3:

[0080] ##STR00010##

[0081] 10 g of the olefin from Example 2 is initially introduced in 40 ml of acetonitrile in a three-necked flask under protective-gas atmosphere. 7 g of m-chloroperbenzoic acid is subsequently added with cooling and the reaction mixture is stirred at 80 C. for 20 hours. Water and MTBE are added to the reaction mixture and the phases are separated. The aqueous phase is extracted with 230 ml of MTBE. The combined organic phase is then washed with in each case 40 ml of water and 40 ml of saturated NaCl solution. The extract is subsequently dried over sodium sulfate and the solvent is distilled off. A white solid remains as residue. Product weight: 15.22 g

Example 4:

[0082] ##STR00011##

[0083] The epoxide prepared in Example 1 is reacted with NaBHa and Nal complex as initiator at 120 C. in a steel autoclave to give the corresponding PEG. The molecular weight can be adjusted via the amount of initiator and the reaction time/temperature.