FLUORINE COMPOUNDS

Abstract

The present invention relates to compounds of the formula (I) (Rf—CHF—CF.sub.2—CHR).sub.m-L-(X).sub.n, where Rf=a perfluorinated alkyl group, optionally containing heteroatoms, R=H or an alkyl group, L=a single bond or a divalent organic group, X=an anchor group, m is ≧1 and n is ≧1, and to the use thereof in, for example, dirt-repellent coatings.

Claims

1. Compounds of the formula (I)
(Rf—CHF—CF.sub.2—CHR).sub.m—L—(X).sub.n   (I) where Rf=a perfluorinated alkyl group, optionally containing heteroatoms, R=H or an alkyl group, L=a single bond or a divalent organic group, X=an anchor group, m is ≧1 and n is ≧1.

2. Compounds according to claim 1, characterised in that the group Rf is selected from the 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—(CF2).sub.0-3—O—(CF.sub.2—O).sub.1-8—CF.sub.2-.

3. Compounds according to claim 1, characterised in that the group Rf is selected from the 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.1-2—, CF.sub.3—O—(CF.sub.2).sub.1-3—O, CF.sub.3—(CF.sub.2).sub.1-2O—-CF.sub.2—, CF.sub.3—O—(CF.sub.2).sub.1-2O—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-.

4. Compounds according to claim 1, characterised in that the group R is equal to H or C1-C3 alkyl.

5. Compounds according to claim 1, characterised in that the group R is equal to H or a methyl group.

6. Compounds according to claim 1, characterised in that the group L is a single bond or a saturated, branched or unbranched alkylene group, optionally containing heteroatoms and/or functional groups.

7. Compounds according to claim 1, characterised in that the group X is an ethylenically unsaturated group, an alkoxysilane group, a silanol group or a halosilane group.

8. Compounds according to claim 1, characterised in that the group X is an acrylate or methacrylate group.

9. Compounds according to claim 1, characterised in that the group X is equal to —SiR′.sub.3, where the groups R′ are, independently of one another, equal to alkyl, OH, halogen, alkoxy or aryloxy, where at least one group R′ is not an alkyl group.

10. Compounds according to claim 9, characterised in that R′ an alkoxy group OR″, where R″ equal to C1-C4-alkyl.

11. Compounds according to claim 10, characterised in that R″ is equal to C1- or C2-alkyl.

12. Compounds according to claim 1, characterised in that m and n, independently of one another, are equal to 1-3.

13. Compounds according to claim 1, characterised in that they conform to the formulae (II) to (VIII) ##STR00019## where Rf=a perfluorinated alkyl group, optionally containing heteroatoms, R″=C1-C4-alkyl and Rm′″=H or an alkyl group.

14. Compounds according to claim 13, characterised in that Rf is equal to 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.1-2- or CF.sub.3—O—(CF.sub.2).sub.1-3—O—.

15. A method for the production of functional coatings and surface modifications, which comprises including a compound according to claim 1 in a functional coating or surface modification.

16. Process for the degradation of fluorine-containing compounds comprising the following steps: a) biological and/or abiotic degradation of the carbon skeleton of the fluorine-containing compounds with formation of fluorine-containing compounds, b) conversion of the fluorine-containing compounds formed in step a) into a gas phase, c) degradation of the fluorine-containing compounds formed in step a) into low-molecular-weight compounds by UV irradiation in the gas phase, d) conversion of the low-molecular-weight compounds formed in step c) from the gas phase into a liquid and/or solid phase, e) mineralisation of the low-molecular-weight compounds formed in step c) in the liquid and/or solid phase.

17. Composition comprising at least one compounds according to claim 1 and a support which is suitable for the respective application and optionally further additives.

18. Coated article whose coating has been produced using at least one compound according claim 1.

Description

EXAMPLES

Abbreviations

[0061] TEMPO 2,2,6,6-tetramethylpiperidinyloxyl [0062] THF tetrahydrofuran [0063] MTBE tert-butyl methyl ether [0064] RT room temperature

Example 1

Synthesis of the Compound of Formula (IVa)

[0065] ##STR00005##

5 g of decafluoropentene are stirred with 8 g of ethanol and 0.2 g of benzoyl peroxide at 100° C. in an autoclave for 18 h. The crude product is distilled. Yield: 2.5 g b.p. 50° C. at 3.5 mbar.

[0066] The hydrofluoroalcohol is warmed under reflux at 110° C. with methacrylic acid and toluene on a water separator for 24 h. The catalyst employed is p-toluenesulfonic acid and TEMPO.

[0067] The product is subsequently distilled.

Example 2

Synthesis of the Compound of the Formula (IIIa)

[0068] ##STR00006##

4.0 g of 2,3-epoxypropyl methacrylate and 10.9 g of 2,2,3-trifluoro-3-heptafluoropropyloxypropan-1-ol are initially introduced in a two-necked flask. 3.2 g of potassium tert-butoxide in 20.3 g of THF are added dropwise with cooling. The reaction mixture is subsequently heated to 100° C. and stirred at this temperature for 24 h.

[0069] 20 ml of water and 20 ml of 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.

[0070] Product weight: 14.02 g

[0071] 1H-NMR: 6.8 ppm (dt, 2 H, —CFH); 6.4 ppm (d, 2H, ═CH2); 4.2-4.4 ppm (m, 3H, —CH2—CHO); 3.4-3.6 ppm (m, 4H, CF2—CH2—O—CH2); 2.0 ppm (s, 3 H, —CH3);

Example 3

Synthesis of the Compound of the Formula (Va)

[0072] ##STR00007##

Example 3a

[0073] ##STR00008##

2.0 g of propylene oxide and 13.4 g of 2,2,3-trifluoro-3-heptafluoropropyl-oxypropan-1-ol are initially introduced in a pressure container, and 0.19 g of potassium tert-butoxide in 0.6 g THF is added dropwise. The reaction mixture is subsequently heated at 100° C. for 24 hr.

[0074] After cooling to room temperature, 10 ml of water and 10 ml of 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.

[0075] Yield: 14.0g

[0076] 1 H-NMR: 6.7 ppm (dt, 2 H, —CFH); 4.0 (m, 1H, —CH) 3.4-3.6 ppm (m, 4H, CF2—CH2—O—CH2); 2.4 ppm (s, 1H, —COH); 2.0 ppm (d, 3 H, —CH3);

Example 3b

[0077] ##STR00009##

[0078] 100 ml of toluene, 1.9 g of p-toluenesulfonic acid, 9.3 of methacrylic anhydride and 16.0 g of fluoroalcohol are initially introduced in a two-necked flask. The reaction mixture is subsequently stirred under reflux on a water separator for 6 h.

[0079] 75 ml of water are added to the mixture, the phases are separated, and the organic phase is in each case washed with 2×20 ml of MTBE. The combined organic phase is dried over sodium sulfate, and the solvent is distilled. The substance is purified by column chromatography, (silica gel: EA:hexane 1:5)

[0080] Yield: 15.0 g

[0081] 1H-NMR: 6.8 ppm (dt, 2 H, —CFH); 6.5 ppm (d, 2H, ═CH2); 5.0 ppm (m, 6H, —CH ); 3.4-3.6 ppm (m, 4H, CF2—CH2—O—CH2); 2.0 ppm (s, 3 H, ═C—CH3); 1.4 ppm (d, 3 H, —CH3)

Example 4

Synthesis of the Compound of the Formula (Via)

[0082] ##STR00010##

Example 4a

[0083] ##STR00011##

[0084] 2.13 g of epichlorohydrin and 17.14 g of 2,2,3-trifluoro-3-heptafluoropropyl-oxypropan-1-ol are initially introduced in a two-necked flask. 3.87 g of potassium tert-butoxide in 16 g of THF are added dropwise with cooling. The reaction mixture is subsequently heated to the boiling temperature and stirred for 24 h.

[0085] 10 ml of water and 10 ml of 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

[0086] 40 ml of saturated NaCl solution. The extract is dried over sodium sulfate, and the solvent is distilled.

[0087] Product weight: 14.0 g

[0088] 1H-NMR: 6.7 ppm (m, 2 H, —CFH); 4.0 ppm (m, 1H, —CH ); 3.6 ppm (m, 4H, CF2—CH2-13 O—); 3.5 ppm (m, 4 H, CH2);

Example 4b

[0089] ##STR00012##

[0090] 50 ml of toluene, 0.5 g of p-toluenesulfonic acid, 1.8 g of methacrylic anhydride and 15.0 g of fluoroalcohol are initially introduced in a two-necked flask. The mixture is subsequently stirred under reflux on a water separator for 6 h.

[0091] 35 ml of water are added to the mixture, the phases are separated, and the organic phase is washed in each case with 2×20 ml of MTBE. The combined organic phase is washed with sodium sulfate, and the solvent is distilled. The substance is purified by column chromatography, (silica gel: EA:hexane 1:5)

[0092] Yield 14.2 g

[0093] 1 H-NMR: 6.7 ppm (m, 2 H, —CFH); 6.5 ppm (d, 2H, ═CH2); 5.0 ppm (m, 1H, —CH ); 3.6-3.5 ppm (m, 8H, CF2—CH2—O- and —CH2—C); 2.0 ppm (d, 3 H, ═C—CH3)

Example 5

[0094] Synthesis of the compound of the formula (VIIa)

##STR00013##

Example 5a

[0095] ##STR00014##

[0096] 12.3 g of 2,2,3-trifluoro-3-heptafluoropropyloxypropan-1-ol are initially introduced with 2.41 g of sodium methoxide in 11 ml of methanol and heated at the boil for 1 h. 5.0 g of allyl bromide is subsequently added dropwise at RT, and the mixture is warmed under reflux for 24 h.

[0097] 10 ml of water and 20 ml of MTBE are added to the batch, and the phases are separated. The aqueous phase is extracted with 2×20 ml of MTBE, and the combined org. phases are washed with 25 ml of water.

[0098] The solvent is removed in vacuo.

[0099] Yield: 8.88 g 60%

[0100] 1 H-NMR: 6.8 ppm (dt, 1 H, —CFH); 5.9 ppm (m, 1 H, C═CH); 5.3 ppm (m, 2 H, C═CH2); 4.1 ppm (m,2 H, —OCH2); 3.8 ppm (m, 2H, —CH2-13 O)

Example 5b

[0101] ##STR00015##

[0102] 0.15 g of hexachloroplatinic(IV) acid hexahydrate (˜40% of Pt) for synthesis and 5 g of 3-(2,2,3-trifluoro-3-heptafluoropropyloxypropoxy)propene in 9.5 ml of dry THF are initially introduced in a 100 ml 4-necked flask with ice cooling and under protective gas. The 2.0 ml of trichlorosilane are slowly added dropwise via a syringe (IT<5° C.). The batch is heated to 56° C. and stirred at this temperature for 4 h. The batch is subsequently cooled to RT under protective gas. 5 ml of trimethyl orthoformate are added to the batch, and 2 ml of MeOH are additionally added. The mixture is heated to 50° C. and stirred at this temperature for 2 h. After cooling, the solvent is distilled and the residue is separated off via a microfilter.

[0103] Yield: m=6.60 g 95%

[0104] 1H-NMR: 6.8 ppm (dt, 1 H, —CFH); 3.8 ppm (m,2 H, —OCH2); 3.5 ppm (s, 9H, —OCH3); 3.4 ppm (m, 2H, —CH2O); 1.4 ppm (m, 2 H, —CH2); 0.6 ppm (m, 2 H, —SiCH2);

Example 6

Synthesis of the Compound of the Formula (VIIIa)

[0105] ##STR00016##

Example 6a

[0106] ##STR00017##

[0107] 15.3 g of 2,2,3-trifluoro-3-heptafluoropropyloxypropan-1-ol and 3.0 g 3-chloro-2-chloromethylpropene are heated at the boil with 4.0 g of potassium hydroxide and 20 ml of toluene for 24 h.

[0108] After cooling, the precipitate is filtered off with suction, 20 ml of water and 20 ml of MTBE are added to the filtrate, and the phases are separated. The aqueous phase is extracted with 2×20 ml of MTBE, and the combined organic phases are again washed with 20 ml of water and dried over sodium sulfate. The solvent is distilled in vacuo. Crude yield: m=7.1g

[0109] The product is purified in a high vacuum.

[0110] B.p.: 42-45° C. at 4.8 10-2 mbar m:6.5 g

[0111] 1 H-NMR: 6.8 ppm (dt, 2 H, —CFH); 5.15 ppm (d, 2 H, ═CH2); 4.05 ppm (s, 4H, —OCH2—C═); 3.75 ppm (m, 4H, —CF2—CH2O)

Example 6b

[0112] ##STR00018##

[0113] 0.15 g of hexachloroplatinic(IV) acid hexahydrate (˜40% of Pt) for synthesis and 6.5 g of bis 3-(2,2,3-trifluoro-3-heptafluoropropyloxypropoxy)propene in 9.5 ml of dry THF are initially introduced in a 100 ml 4-necked flask with ice cooling and under protective gas. The 1.2 ml of trichlorosilane are slowly added dropwise (IT<5° C.). The batch is heated to 56° C. and stirred at this temperature for 4 h. The batch is subsequently cooled to RT under protective gas. 3.5 ml of trimethyl orthoformate are added to the batch, and 1 ml of MeOH is additionally added. The mixture is heated to 50° C. and stirred at this temperature for 2 h. After cooling, the solvent is distilled and the residue is separated off via a microfilter. The yellowish oil is dried in a high vacuum Yield: m=5.2 g 75%

[0114] 1H-NMR: 6.8 ppm (dt, 2 H, —CFH); 3.8-4.1 ppm (m, 9H, —CH2-); 3.5 ppm (s, 9H, —OCH3); 0.6 ppm (m, 2 H, —SiCH2)