FLUORINE COMPOUNDS

Abstract

The present invention relates to novel compounds containing fluorinated end groups and to the use thereof in, for example, dirt-repellent coatings.

Claims

1. Compounds of the formulae (I) or (I′)
(Rf-CHF—CF.sub.2—O—CHR).sub.m-L-(X).sub.n  (I)
(Rf-CHF—CF.sub.2—S—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—(CF.sub.2).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 R.sub.f 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.1-3—, 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—.

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 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 one of the formulae (Ia) to (Ih) or (I′a) to (I′h) ##STR00029## ##STR00030## ##STR00031## where Rf=a perfluorinated alkyl group, optionally containing heteroatoms, R″=C1-C4-alkyl and R′″=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.1-3— or CF.sub.3—O—(CF.sub.2).sub.1-2—O—.

15. A method of providing a dirt-repellent surface to a substrate comprising applying to said substrate at least one compound according to claim 1.

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, 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 to claim 1.

19. Process for the preparation of compounds of the formula (I′) according to claim 1 comprising a) the reaction of perfluoroalkyl vinyl ethers of the formula Rf-CF═CF.sub.2 with mercaptoalcohols of the formula (HS)x-alkyl-(OH)y to give compounds of the formula (Rf-CHF—CF.sub.2—S).sub.x-alkyl-(OH).sub.y and b) the reaction of the compounds prepared in a) with unsaturated acids or acid anhydrides, where Rf=a perfluorinated alkyl group, optionally containing heteroatoms, and x and y are, independently of one another, ≧1.

20. Compounds of the formulae (II), (III) or (IV) ##STR00032## where Rf=a perfluorinated alkyl group, optionally containing heteroatoms, and R.sup.1=H or C1-C4-alkyl.

Description

EXAMPLES

Abbreviations

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

Example 1: Synthesis of a Compound of the Formula (Id) where R.SUP.1.=H, R′″=CH.SUB.3 .and Rf=C.SUB.3.F.SUB.7.—O

[0064] ##STR00009##

Example 1a

[0065] ##STR00010##

[0066] 100 g of 2,3-dihydroxypropyl acetate, 595 g of perfluoropropyl vinyl ether, 134 g of potassium carbonate and 460 g of acetonitrile are stirred at 80° C. in a pressure container for 70 hours. The internal pressure increases to 4 bar during the reaction. The reaction product is washed out of the reactor with 100 ml of acetonitrile, the mixture is filtered, and the solvent is separated off in a rotary evaporator, and the crude product is distilled under reduced pressure (b.p. 75° C. at 0.3 mbar). Yield: 533 g=80%. 1H-NMR: 6.8 ppm (m, 2H, —CFH); 4.8 ppm (m, 1H, —OCH); 4.3 ppm (m, 4H, —CH2); 2.1 ppm (s, 3H, O═CCH3)

Example 1b

[0067] ##STR00011##

[0068] 30 g of ester are hydrogenated with 20 ml of methanol, 0.5 g of sodium methoxide, 27 mg of Ru-MACHO (Takasago International, JP) using hydrogen in a pressure reactor at 50 bar and 40° C. for 12 hours. 50 ml of methyl tert-butyl ether and 50 ml of water are added to the reaction mixture, the organic phase is separated off and dried over NaSO4. The product is freed from the solvent and distilled in vacuo (b.p.: 74° C. at 0.4 mbar).

[0069] Yield: 20 g=70%).

[0070] 1H-NMR: 6.8 ppm (m, 2H, —CFH); 4.8-4.3 ppm (m, 5H, —CH2);

Example 1c

[0071] ##STR00012##

[0072] 10 g of fluoroalcohol alcohol are dissolved in 35 ml of toluene with 0.5 g of toluene-4-sulfonic acid monohydrate. 2.7 g of methacrylic anhydride are then slowly added with stirring, and the reaction mixture is stirred at 110° C. for 24 h. 25 ml of water and 25 ml of MTBE are added to the batch, which has been cooled to room temperature, and separated off in a separating funnel. The aqueous phase is subsequently washed twice with 25 ml of MTBE. The combined organic phase is dried sodium sulfate and filtered. The solvent is subsequently distilled in a rotary evaporator. Yield: 9.98 g 1H-NMR: 6.8 ppm (m, 2H, —CFH); 6.0 ppm (d, 1H, ═CH); 5.6 ppm (d, 1H, ═CH); 4.8-4.3 ppm (m, 5H, —CH2); 1.7 ppm (s, 3H, —CH3)

Example 2: Synthesis of a Compound of the Formula (I′e) where R′″=CH.SUB.3 .and Rf=C.SUB.3.F.SUB.7.—O

[0073] ##STR00013##

Example 2a

[0074] ##STR00014##

[0075] 8.63 g of perfluoropropyl vinyl ether are heated at 120° C. in a pressure reactor for 18 hours with 2.5 g of 1,4-dimercaptobutane-2,3-diol, 25 ml of acetonitrile and 0.67 g of potassium carbonate. 25 ml of water and 25 ml of MTBE are added to the reaction mixture, and the phases are separated. The aqueous phase is extracted with 2×25 ml of MTBE, and the combined organic phase washed with 70 ml of water and 70 ml of saturated NaCl solution. The extract is dried over sodium sulfate, and the solvent is distilled.

[0076] Yield: 9.82 g=88%

[0077] 1H-NMR: 6.8 ppm (d, 2H, —CFH); 3.6 ppm (m, 2H, —CHOH); 3.0 ppm (m, 4H, —SCH2);

Example 2b

[0078] ##STR00015##

[0079] 10 g of fluoroalcohol alcohol are dissolved in 35 ml of toluene with 0.5 g of toluene-4-sulfonic acid monohydrate. 4.5 g of methacrylic anhydride are then slowly added with stirring, and the reaction mixture is stirred at 110° C. for 24 h. 25 ml of water and 25 ml of MTBE are added to the batch, which has been cooled to room temperature, and separated off in a separating funnel. The aqueous phase is subsequently washed twice with 25 ml of MTBE. The combined organic phase is dried sodium sulfate and filtered. The solvent is subsequently removed in a rotary evaporator. Yield: 14.5 g

[0080] 1H-NMR: 6.8 ppm (m, 2H, —CFH); 6.0 ppm (d, 2H, ═CH); 5.6 ppm (d, 2H, ═CH); 3.6 ppm (m, 2H, —OCH—); 3.0 ppm (m, 4H, —SCH2); 1.6 ppm (s, 6H, —CH3)

Example 3: Synthesis of a Compound of the Formula (I′c) where R′″=CH.SUB.3 .and Rf=C.SUB.3.F.SUB.7.—O

[0081] ##STR00016##

Example 3a

[0082] ##STR00017##

[0083] 77.30 g of perfluoropropyl vinyl ether are heated at 100° C. in a pressure reactor for 18 hours with 52.21 g of 2-mercaptoethanol 40 ml of acetonitrile and 12 g of potassium carbonate. 25 ml of water and 25 ml of MTBE are added to the reaction mixture, and the phases are separated. The aqueous phase is extracted with 2×25 ml of MTBE, and the combined organic phase washed with 70 ml of water and 70 ml of saturated NaCl solution. The extract is dried over sodium sulfate, the solvent is removed, and the crude material is distilled (b.p. 45-49° C. at 0.1 mbar). Yield: 63.40 g=63%

[0084] 1H-NMR: 6.8 ppm (dt, 1H, —CFH); 3.6 ppm (t, 2H, —CH2O—); 3.1 ppm (t, 2H, —SCH2);

Example 3b

[0085] ##STR00018##

[0086] 10 g of fluoroalcohol alcohol are dissolved in 60 ml of toluene with 0.5 g of toluene-4-sulfonic acid monohydrate. 4.5 g of methacrylic anhydride are then slowly added with stirring, and the reaction mixture is stirred at 110° C. for 24 h. 25 ml of water and 25 ml of MTBE are added to the batch, which has been cooled to room temperature, and separated off in a separating funnel. The aqueous phase is subsequently washed twice with 25 ml of MTBE. The combined organic phase is dried sodium sulfate, filtered, and the solvent is removed in a rotary evaporator.

[0087] Yield: 11.30 g=94%

[0088] 1H-NMR: 7.1 ppm (m, 1H, —CFH); 6.1 ppm (m, 1H, ═CH); 5.7 ppm (m, 1H, ═CH); 4.3 ppm (t, 2H, —CH2O—); 3.2 ppm (t, 2H, —SCH2); 1.9 ppm (s, 3H, —CH3)

Example 4: Synthesis of a Compound of the Formula (Id) where R′″=CH.SUB.3., R.SUP.1.=CH.SUB.3 .and Rf=CF.SUB.3.—O—C.SUB.3.F.SUB.6.—O

[0089] ##STR00019##

Example 4a

[0090] ##STR00020##

[0091] 5 g of methyl 3-hydroxy-2-hydroxymethyl-2-methylpropionate, 20 ml of 1,1,2,2,3,3-hexafluoro-1-trifluoromethoxy-3-trifluorovinyloxypropane 60 ml of acetonitrile and 6 g of potassium carbonate are stirred at 80° C. in a pressure reactor for 20 h. A pressure of 1.5 bar became established. 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 2×50 ml of MTBE. The combined organic phase is subsequently washed with 70 ml of water and 70 ml of NaCl solution. The extract is dried over sodium sulfate, and the solvent is distilled.

[0092] Product weight: 20.58 g 75%

[0093] 1H-NMR: 6.6 ppm (m, 2H, —CFH); 4.2 ppm (dd, 4H, —CH2O); 3.7 ppm (s, 3H, —OCH3); 1.25 ppm (s, 3H CCH3)

Example 4b

[0094] ##STR00021##

[0095] 20 g of ester are hydrogenated with 15 ml of methanol, 0.3 g of sodium methoxide, 15 mg of catalyst using hydrogen in a pressure reactor at 50 bar and 40° C. for 12 hours. 50 ml of methyl tert-butyl ether and 50 ml of water are added to the reaction mixture, the organic phase is separated off and dried over NaSO4. The product is freed from the solvent and distilled in vacuo (b.p.: 95° C. at 0.1 mbar).

[0096] Yield: 16 g=82%).

[0097] 1H-NMR: 6.6 ppm (m, 2H, —CFH); 6.1 ppm (m, 1H, ═CH); 5.7 ppm (m, 1H, ═CH); 4.3-4.1 ppm (m, 6H, —CH2O); 1.3 ppm (s, 3H CCH3)

Example 4c

[0098] ##STR00022##

[0099] 10 g of fluoroalcohol alcohol are dissolved in 35 ml of toluene with 0.5 g of toluene-4-sulfonic acid monohydrate. 2 g of methacrylic anhydride are then slowly added with stirring, and the reaction mixture is stirred at 110° C. for 24 h. 25 ml of water and 25 ml of MTBE are added to the batch, which has been cooled to room temperature, and separated off in a separating funnel. The aqueous phase is subsequently washed twice with 25 ml of MTBE, and the combined organic phase is dried using sodium sulfate and filtered. The solvent is removed in a rotary evaporator. Yield: 10.5 g=96%

[0100] 1H-NMR: 6.6 ppm (m, 2H, —CFH); 6.2 ppm (m, 1H, ═CH); 5.7 ppm (m, 1H, ═CH); 4.3-4.1 ppm (m, 6H, —CH2O); 1.9 ppm (s, 3H, —CH3); 1.25 ppm (s, 3H CCH3)

Example 5: Synthesis of a Compound of the Formula (Ih) where R″=CH.SUB.3 .and Rf=C.SUB.3.F.SUB.7.—O

[0101] ##STR00023##

Example 5a

[0102] ##STR00024##

[0103] 3.56 g of but-2-en1,4-diol and 26.87 g of perfluorovinyloxypropane are heated to 80° C. in an autoclave with 2.84 g of KOH and 27.5 g of acetonitrile and brought to reaction at this temperature for 24 h. During this time, the internal pressure drops from initially 2.6 bar to 1 bar. After cooling to room temperature, the batch is filtered and the solvent is distilled. The solvent is removed in vacuo. Crude yield: m=30.28 g

[0104] The crude product is dissolved in 30 ml of acetonitrile, 20 ml of toluene are added, causing a white gel to precipitate out. The precipitate is filtered off via a little silica gel and rinsed with 20 ml of acetonitrile. After removal of the solvent, the residue is dried.

[0105] Yield: m=24.8 g

[0106] 1H-NMR: 6.7 ppm (m, 2H, —CFH); 6.0 ppm (s, 2H, ═CH); 4.6 ppm (s, 4H, —CH2O);

Example 5b

[0107] ##STR00025##

[0108] 0.15 g of hexachloroplatinic(IV) acid hexahydrate (40% of Pt) and 10 g of perfluoroolefin in 12 ml of abs. THF are initially introduced in a 100 ml four-necked flask with ice-cooling and under argon. 1.84 ml of trichlorosilane are added to the batch via a syringe with stirring and ice-cooling at such a rate that the IT does not exceed 5° C. The batch is heated to 60° C. and brought to reaction at this temperature for 4 h. The mixture is subsequently cooled to RT under argon overnight. 5 ml of trimethyl orthoformate are added, and 2 ml of MeOH are subsequently added. During this addition, the temperature rises by 5K to 33° C. The mixture is warmed to 50° C. and stirred at this temperature for 2 h. The batch is cooled, the solvent is removed, and the residue is dried in vacuo. Crude yield: m=18.95 g

[0109] The batch is purified at 120° C. in a bulb-tube distillation apparatus in a high vacuum.

[0110] 1H-NMR: 6.7 ppm (dt, 2H, —CFH); 3.8 ppm (m, 4H, —OCH2); 3.5 ppm (s, 9H, —OCH3); 1.4 ppm (m, 2H, —CH2); 0.6 ppm (m, 1H, —SiCH);

Example 6: Synthesis of a Compound of the Formula (Ig) where R″=CH.SUB.3 .and Rf=C.SUB.3.F.SUB.7.—O

[0111] ##STR00026##

Example 6a

[0112] ##STR00027##

[0113] 10.0 g of allyloxy-1,2-propanediol are brought to reaction with 60.4 g of perfluorovinyloxypropane, 13.6 g of potassium carbonate and 46.5 g of acetonitrile at 80° C. in an autoclave for 48 h. After completion, the batch is filtered, and the solvent is removed in vacuo. Yield: m=50.2 g

[0114] The product is distilled in vacuo (64-65° C. at 3 mbar)

[0115] 1H-NMR: 6.8 ppm (d, 2H, —CFH); 5.9 ppm (m, 1H, CH); 5.3 ppm (d, 1H, ═CH.sub.2), 5.2 ppm (d, 1H, ═CH.sub.2), 4.8 ppm (d, 1H, ═CH) 4.2 ppm (m, 2H, —OCH.sub.2); 4.0 ppm (m, 2H, —OCH.sub.2); 3.8 ppm (m, 2H, —OCH.sub.2)

Example 6b

[0116] ##STR00028##

[0117] 0.15 g of hexachloroplatinic (IV) acid hexahydrate (40% of Pt) and 10 g of perfluoroolefin in 12 ml of abs. THF are initially introduced in a 100 ml four-necked flask with ice-cooling and under argon. 1.84 ml of trichlorosilane are added to the batch via a syringe with stirring and ice-cooling at such a rate that the IT does not exceed 5° C. The batch is heated to 60° C. and brought to reaction at this temperature for 4 h. The mixture is subsequently cooled to RT under argon overnight. 5 ml of trimethyl orthoformate are added, and 2 ml of MeOH are subsequently added. The batch is warmed to 50° C. and stirred at this temperature for 6 h. The batch is cooled, the solvent is removed, and the residue is dried in vacuo. Crude yield: m=15.2 g

[0118] The product is purified in a bulb-tube distillation apparatus. 115° @ C. 0.01 mbar

[0119] 1H-NMR: 6.8 ppm (d, 2H, —CFH); 5.9 ppm (m, 1H, CH); 4.2 ppm (m, 2H, —OCH.sub.2); 4.0 ppm (m, 2H, —OCH.sub.2); 3.5 ppm (s, 9H, —OCH.sub.3); 3.4 ppm (m, 2H, —OCH.sub.2) 1.5-0.6 ppm (m, 4H, CH.sub.2—CH.sub.2—Si—)