Method for producing fluorinated compounds

Abstract

The present invention relates to a process for the preparation of fluorinated compounds, to novel compounds containing fluorinated end groups, to the use thereof and to compositions comprising novel compounds containing fluorinated end groups.

Claims

1. A compound of formula (I′) ##STR00021## where Rf is CF.sub.3—(CF.sub.2).sub.a—O.sub.b—(CF.sub.2).sub.c—O.sub.d—, a=1 or 2, b=1, c=0, d=0, R is a linear or branched alkyl or siloxane group, optionally containing one or more heteroatoms, or a group Rf′, Rf′ is a fluorinated, linear or branched alkyl group, optionally containing one or more heteroatoms, and, if R is a group Rf′, Rf and Rf′ are different, or of formula (VI′) ##STR00022## where Rf is a fluorinated, linear or branched alkyl group, optionally containing one or more heteroatoms, R is a linear or branched alkyl or siloxane group, optionally containing one or more heteroatoms, L is a single bond or a divalent organic group, and X is a cationic, amphoteric or anionic group.

2. A compound of formula (I′) ##STR00023## where Rf is CF.sub.3—(CF.sub.2).sub.a—O.sub.b—(CF.sub.2).sub.c—O.sub.d—, a=1 or 2, b=1, c=0, d=0, R is a linear or branched alkyl or siloxane group, optionally containing one or more heteroatoms, or a group Rf′, Rf′ is a fluorinated, linear or branched alkyl group, optionally containing one or more heteroatoms, and, if R is a group Rf′, Rf and Rf′ are different.

3. The compound according to claim 2, wherein Rf is CF.sub.3—(CF.sub.2)—O—.

4. The compound according to claim 2, wherein R is a C1-C20 alkyl group.

5. The compound according to claim 2, wherein Rf′ is of the following formula
CF.sub.3—(CF.sub.2).sub.a—O.sub.b—(CF.sub.2).sub.c—O.sub.d—(CR.sup.1R.sup.2).sub.e—(CR.sup.3R.sup.4).sub.f—O.sub.g—, where R.sup.1, R.sup.2, R.sup.3 and R.sup.4, independently of one another, are hydrogen or an alkyl group, a=0, 1, 2 or 3, b=0 or 1, c=0, 1, 2 or 3, d=0 or 1, e=0, 1, 2, 3 or 4, f=0, 1, 2, 3 or 4 and g=0 or 1.

6. The compound according to claim 2, wherein Rf is CF.sub.3—(CF.sub.2).sub.2—O—.

7. The compound according to claim 1, which is a compound of formula (VI′).

8. The compound according to claim 4, wherein Rf is CF.sub.3—(CF.sub.2).sub.0-3— or CF.sub.3—(CF.sub.2).sub.0-3—O—.

9. The compound according to claim 7, wherein R is a C1-C20 alkyl group.

10. The compound according to claim 7, which is a compound of formula (VI′), wherein Rf is CF.sub.3—(CF.sub.2).sub.0-3—O—.

11. A product selected from the group consisting of 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 and coatings of optical elements, comprising a compound according to claim 7.

12. A composition comprising one or more compounds according to claim 7 and a vehicle which is suitable for an application.

13. The composition according to claim 12, which is selected from the group consisting of paints, coating preparations, fire-extinguishing compositions, lubricants, washing compositions, cleaning compositions, de-icers, developer solutions, wash solutions, photoresists for photolithographic processes, cosmetic products, agrochemicals, floor polishes, hydrophobicising compositions for textile finishing and hydrophobicising compositions for glass treatment.

14. A compound of formula (VI′) ##STR00024## wherein Rf′ is of the following formula
CF.sub.3—(CF.sub.2).sub.a—O.sub.b—(CF.sub.2).sub.c—O.sub.d—(CR.sup.1R.sup.2).sub.e—(CR.sup.3R.sup.4).sub.f—O.sub.g—, where R.sup.1, R.sup.2, R.sup.3 and R.sup.4, independently of one another, are hydrogen or an alkyl group, a=0, 1, 2 or 3, b=0 or 1, c=0, 1, 2 or 3, d=0 or 1, e=0, 1, 2, 3 or 4, f=0, 1, 2, 3 or 4, and g=0 or 1, R is a linear or branched alkyl or siloxane group, optionally containing one or more heteroatoms, or a group Rf′, Rf′ is a fluorinated, linear or branched alkyl group, optionally containing one or more heteroatoms, L is a single bond or a divalent organic group, and X is a cationic, non-ionic, amphoteric or anionic group, and, if R is a group Rf′, Rf and Rf′ are different.

15. A compound of formula (VI′) ##STR00025## wherein Rf is CF.sub.3—(CF.sub.2).sub.0-3—, R is a linear or branched alkyl or siloxane group, optionally containing one or more heteroatoms, or a group Rf′, Rf′ is a fluorinated, linear or branched alkyl group, optionally containing one or more heteroatoms, L is a single bond or a divalent organic group and X is a cationic, non-ionic, amphoteric or anionic group and, if R is a group Rf′, Rf and Rf′ are different.

16. A method for preparing a compound of formula (VI) ##STR00026## where Rf is a fluorinated, linear or branched alkyl group, optionally containing one or more heteroatoms, R is a linear or branched alkyl group, optionally containing one or more heteroatoms, or a group Rf′, Rf′ is a fluorinated, linear or branched alkyl group, optionally containing one or more heteroatoms, L is a single bond or a divalent organic group and X is a cationic, non-ionic, amphoteric or anionic group, comprising reacting a compound of formula (I) ##STR00027## where Rf is a fluorinated, linear or branched alkyl group, optionally containing one or more heteroatoms, R is a linear or branched alkyl or siloxane group, optionally containing one or more heteroatoms, or a group Rf′, and Rf′ is a fluorinated, linear or branched alkyl group, optionally containing one or more heteroatoms.

Description

EXAMPLES

(1) Abbreviations

(2) PPVE perfluoropropyl vinyl ether MTBE tert-butyl methyl ether PPOL-1 2,2,3-trifluoro-3-heptafluoropropyloxypropan-1-ol
Determination of the Static Surface Tension

(3) The static surface tensions γ of aqueous surfactant solutions having various concentrations c (grams per litre) are determined. Instrument: Dataphysics tensiometer (model DCAT 11) Temperature of the measurement solutions: 20°±0.2° C. Measurement method employed: measurement of the surface tension using the Wilhelmy plate method in accordance with DIN EN 14370. Plate: platinum, length=19.9 mm

(4) 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:

(5) $\gamma =\frac{F}{L.Math.\cos \theta }=\frac{F}{L}$

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

Example 1

(7) ##STR00016##

(8) 21.78 g of glycidol, 93.86 g of PPVE, 12.19 g of potassium carbonate; 130 ml of dioxane

(9) 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 2×30 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.

(10) TABLE-US-00001 T.sub.bath T.sub.head p ° C. ° C. mbar 50.3 24.1 0.80

(11) ##STR00017##

(12) 3.40 g of the fluoroepoxide from Example 1, 8.94 g of fluoroalcohol (PPOL-1) and 0.36 g of sodium (elemental)

(13) PPOL-1 is initially introduced in a round-bottomed flask. Elemental sodium is added with cooling. For complete dissolution of the sodium, the reaction mixture is heated gently. The reaction mixture is subsequently called again and the epoxide is added. When the addition is complete, the reaction mixture is stirred at 80° C. for 20 h. MTBE and water are added to the reaction mixture and the phases are separated. The aqueous phase was extracted with 2×30 mL of MTBE. The combined organic phase is washed with in each case 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: 15.04 g.

(14) The product is distilled in vacuo.

(15) TABLE-US-00002 p T.sub.bath T.sub.head mbar ° C. ° C. 0.80 105.4 78.3

(16) Product weight: 4.7 g

Example 2

(17) ##STR00018##

(18) The starting materials are combined in a 50 ml pressure reactor and slowly heated to 130° C. After 20 h, the reaction is terminated and water and MTBE are added to the reaction mixture. The phases are separated and the aqueous phase is extracted with 2×25 mL of MTBE. The combined organic phases is subsequently washed with in each case 30 ml of water and 30 ml of saturated NaCl solution. The extract is dried over sodium sulfate and the solvent is distilled off. The reaction mixture is purified by distillation. Product weight: 6.55 g

(19) GC MS shows 82.77% of product and 6.81% of isomer.

Example 3

(20) ##STR00019##

(21) The starting materials are combined in a 50 ml pressure reactor and slowly heated to 130° C. After 20 h, the reaction is terminated and water and MTBE are added to the reaction mixture. The phases are separated and the aqueous phase is extracted with 2×25 mL of MTBE. The combined organic phases is subsequently washed with in each case 30 ml of water and 30 ml of saturated NaCl solution. The extract is dried over sodium sulfate and the solvent is distilled off.

(22) GC MS shows: 87.82% of product.

Example 4

(23) ##STR00020##

(24) The starting materials are combined in a 50 ml pressure reactor and slowly heated to 130° C. After 20 h, the reaction is terminated and water and MTBE are added to the reaction mixture. The organic phase exhibits an orange coloration. The phases are separated and the aqueous phase is extracted with 2×25 mL of MTBE. The combined organic phases is subsequently washed with in each case 30 ml of water and 30 ml of saturated NaCl solution. The extract is dried over sodium sulfate and the solvent is distilled off. GC MS by means of PCI has a mass peak of 488. This peak corresponds to about 50% of the peak areas. This corresponds to the product plus adducted ammonium.