Fluorinated tensides

Abstract

The present invention relates to novel compounds containing fluorinated end groups, to the use thereof as surface-active substances, and to compositions comprising these compounds.

Claims

1. A compound of formula ##STR00036## ##STR00037## where R.sup.1, R.sup.2 and R.sup.3, independently of one another, CF.sub.3—(CF.sub.2).sub.1-2—O—, o=1-30, X=—S.sub.3.sup.−, —OSO.sub.3.sup.−, —COO.sup.−, —PO.sub.3.sup.2−, —OP(O)(O.sup.−)O—, —OPO.sub.3.sup.2−, a polyethylene glycol, a poly-propylene glycol, —CH(OH)—CH.sub.2—NH-sach, —Y′—(CH.sub.2—CH.sub.2—O).sub.v-R.sup.4, a betaine, or a sulfobetaine, with counterions being H.sup.+, Na.sup.+, K.sup.+ or NH.sub.4.sup.+, sach being a sugar, X.sup.1 and X.sup.2, independently of one another, have the meaning of X, or, in the formulae (IIa), (IIb), (IIc) and (V) are also equal to H, Y′=S, O or NH, and L.sup.1, L.sup.2 and L.sup.3, independently of one another, are a linear or branched C1-C6-alkyl group, or ##STR00038## where R.sup.1 and R.sup.2 independently of one another are CF.sub.3—(CF.sub.2).sub.1-2—, X.sup.1=—SO.sub.3.sup.−, —OSO.sub.3.sup.−, —COO.sup.−, —PO.sub.3.sup.2−, —OP(O)(O.sup.−)O—, —OPO.sub.3.sup.2−, a polyethylene glycol, a polypropylene glycol, —CH(OH)—CH.sub.2—NH— sach, —Y′—(CH.sub.2—CH.sub.2—O).sub.v-R.sup.4, a betaine, or a sulfobetaine, with counterions being H.sup.+, Na.sup.+, K.sup.+ or NH.sub.4.sup.+, sach being a sugar, and Y′=S, O or NH.

2. A compound of formula: ##STR00039## where R.sup.1, R.sup.2 and R.sup.3 are independently 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—(CF2).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 or —CF.sub.3—(CF.sub.2).sub.0-3—O—(CF.sub.2—O).sub.1-8—CF.sub.2—, o is equal to 1-30 and R.sup.a, R.sup.b and R.sup.c=H or C1-4-alkyl.

3. The compound according to claim 1, of formula: ##STR00040##

4. A paint, coating, printing ink, protective coating, special coating in electronic or optical applications, photoresist, top antireflective coating or bottom antireflective coating, developer solution, wash solution or photoresist for photolithographic processes, cosmetic product, agrochemical, floor polish, photographic coating or coating of optical elements comprising an additive, wherein the additive is a compound according to claim 1.

5. A composition comprising paint, coating preparations, fire-extinguishing compositions, lubricants, washing or cleaning compositions, de-icers, developer solutions, wash solutions or photoresists for photolithographic processes, cosmetic products, agrochemicals, floor polishes or hydrophobicising compositions for textile finishing or glass treatment, and a compound according to claim 1.

6. The compound according to claim 1, wherein o=5-30.

7. The compound according to claim 1, wherein o=3, 5, 6, 10, 12, 15, 18, 20 or 24.

Description

EXAMPLES

(1) The NMR spectra are measured using a Bruker 400 MHz spectrometer with internal standard.

(2) The IR spectra are measured using a Brucker Alpha Platinum-ATR spectrometer.

(3) Determination of the Static Surface Tension

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

(5) Instrument: Dataphysics tensiometer (model DCAT 11)

(6) Temperature of the measurement solutions: 20°±0.2° C.

(7) Measurement method employed: measurement of the surface tension using the Wilhelmy plate method in accordance with DIN EN 14370.

(8) Plate: platinum, length=19.9 mm

(9) 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:

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

(11) 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°.

(12) The term cos θ therefore approximately reaches the value 1, so that only the measured force and the length of the plate have to be taken into account.

Abbreviations

(13) EO ethylene oxide units

(14) THF tetrahydrofuran

(15) MTBE tert-butyl methyl ether

(16) b.p. boiling point

(17) w % percent by weight

Example 1: Synthesis of Compounds of the Formula (XIX)

Example 1a

(18) ##STR00023##

(19) 77.3 g of 1,1,1,2,2,3,3-heptafluoro-3-trifluorovinyloxypropane, 52.2 g of 2-mercaptoethanol, 12.05 g of potassium carbonate and 50 ml of acetonitrile are combined in a pressure reactor. The reaction mixture is stirred at 100° C. for 20 h. 50 ml of water and 50 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. The combined organic phases are subsequently 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. The residue is then subjected to fractional vacuum distillation.

(20) The product here has a head temperature of 49° C. at a pressure of 0.058 mbar. Product weight: 63.47 g

(21) 1H-NMR: 7.2 ppm (dt, 1 H, —CFH); 5.1 ppm (t, 1 H, ═OH);

(22) 3.6 ppm (q, 2 H, —CH2-OH); 3.0 ppm (t, 2 H, S—CH2—CH2)

Example 1b

(23) ##STR00024##

(24) The alcohol prepared in Example 1a is reacted with ethylene oxide at 140° C. and max. 4 bar in a pressure reactor to give the corresponding fluorosurfactants. Various chain lengths can be achieved depending on the reaction time. The materials synthesised here have a statistical EO chain length of 3, 10 or 18 units.

Example 1c: n=3

(25) 1H-NMR: 7.2 ppm (dt, 1 H, —CFH); 3.6 ppm (q, 2 H, —CH2-OH); 3.55-3.40 (m, 12 H, —CH2CH2-O); 3.0 ppm (t, 2 H, S—CH2-CH2)

Example 1d: n=10

(26) 1H-NMR: 7.2 ppm (dt, 1 H, —CFH); 3.6 ppm (q, 2 H, —CH2-OH); 3.55-3.40 (m, 42 H, —CH2CH2-O); 3.0 ppm (t, 2 H, S—CH2-CH2)

Example 1e: n=18

(27) 1H-NMR: 7.2 ppm (dt, 1 H, —CFH); 3.6 ppm (q, 2 H, —CH2-OH); 3.55-3.40 (m, 74 H, —CH2CH2-O); 3.0 ppm (t, 2 H, S—CH2-CH2)

Example 1f

(28) ##STR00025##

(29) 11 g of the alcohol from Example 1a are initially introduced in 4 ml of toluene in a reaction flask and heated to 60° C. 2.00 g of phosphoryl chloride are slowly added over the course of 10 min. The reaction mixture is subsequently heated to 115° C. and stirred at this temperature for 5.5 h. The batch is subsequently cooled to 90° C. and carefully hydrolysed using 0.3 ml of water, and the mixture is stirred at this temperature for a further hour. The solvent is subsequently removed, leaving a brown residue.

(30) 20 ml of MTBE and 20 ml of water are added to the crude product, and the phases are separated. The aqueous phase is extracted with 2×30 ml of MTBE. The combined organic phases are subsequently neutralised using ammonia solution and separated off.

(31) Product weight: 11.18 g.

(32) 1H-NMR: 7.3-7.1 ppm (m, 2 H, —CFH); 4.0-3.2 ppm (m, S—CH2-CH2); 31 P-NMR: −0.7 ppm (t, 2 P); −1.8 ppm (quin, 1 P), i.e. mono- and diester are present in the ratio 2/1.

Example 1 g

(33) ##STR00026##

(34) 11 g of the alcohol from Example 1c are reacted with 1.5 g of POCl.sub.3 analogously to Example 1f.

(35) Yield 11.0 g

(36) 1H-NMR: 7.3-7.1 ppm (m, 2H, —CFH); 3.8-3.3 ppm (m, 4H, S—CH2-CH2) and (m, 24H, CH2-CH2-O);

(37) 31 P-NMR: −0.7 ppm (t, 3 P); −1.8 ppm (quin, 2 P), i.e. mono- and diester are present in the ratio 2/1.

Example 1h

(38) ##STR00027##

(39) 6.5 g of the alcohol prepared in Example 1a are initially introduced in 24 ml of acetonitrile in a round-bottomed flask, and 5.4 ml of 40% peracetic acid are slowly added dropwise with stirring. The reaction mixture is then heated to 80° C. and stirred at this temperature for 24 h. 30 ml of water and 30 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. The combined organic phases are subsequently 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: 6.69 g

(40) 1H-NMR: 8.2 and 7.2 ppm (m, 1 H, —CFH); 4.0 ppm (m, 4 H, SO2-CH2-CH2-OH)

Example 2: Synthesis of the Compound of the Formula (XX)

Example 2a: Preparation of the Fluorinated Maleic Acid Ester

(41) ##STR00028##

(42) 10.49 g of the alcohol prepared in Example 1a, 1.30 g of maleic anhydride and 0.68 g of p-toluenesulfonic acid monohydrate are combined in 30 ml of toluene in a round-bottomed flask. The reaction mixture is stirred under reflux on a water separator for 24 h. 30 ml of water and 30 ml of MTBE are added to the reaction mixture, and the phases are separated. The aqueous phase is extracted twice with 20 ml of MTBE. The combined organic phases are subsequently washed with 30 ml of water and 30 ml of saturated NaCl solution. The extract is dried over sodium sulfate, and the solvent is distilled off. Product weight: 10.68 g

(43) 1H-NMR: 7.2 ppm (dt, 2 H, —CFH); 6.5 ppm (m, 2 H, —CH═CH—);

(44) 4.3 ppm (t, 2 H, —CH2-CH2-O); 3.2 ppm (t, 2 H, —CH2-CH2-S—)

Example 2b: Preparation of the Fluorinated Sulfosuccinate

(45) ##STR00029##

(46) 10.00 g of the fluorine-containing maleic acid ester, 2.71 g of a 39% sodium hydrogensulfite solution and 30 ml of 2-propanol are initially introduced in a round-bottomed flask. The pH of the reaction mixture is then adjusted to pH 6.3 using sodium hydroxide solution. The reaction mixture is subsequently stirred at 95° C. for 96 h. 30 ml of MTBE and 30 ml of water are added to the reaction mixture, and the phases are separated. The aqueous phase is extracted twice with 20 ml of MTBE. The combined organic phases are subsequently washed with 30 ml of water and 30 ml of saturated NaCl solution.

(47) The extract is dried over sodium sulfate, and the solvent is distilled off.

(48) Yield: 6.64 g

(49) 1H-NMR: 7.2 ppm (dt, 2 H, —CFH); 4.2 ppm (m, 4 H, S—CH2-CH2);

(50) 3.7 ppm (dd, 1 H, —CH—SO3-); 3.2 ppm (t, 4 H, CH2-CH2-O);

(51) 2.8-3.0 ppm (m, 2 H, —CH2-CH);

Example 2c: Precursor for the Synthesis of the Compound of the Formula (XVIII)

(52) ##STR00030##

(53) 9.49 g of the alcohol prepared in Example 1a, 1.50 g of aconitic acid and 0.45 g of p-toluenesulfonic acid monohydrate are combined in 50 ml of toluene in a round-bottomed flask. The reaction mixture is stirred at 115° C. on a water separator for 72 h. 30 ml of water and 30 ml of MTBE are added to the reaction mixture, and the phases are separated. The aqueous phase is extracted twice with 20 ml of MTBE. The combined organic phases are subsequently washed with 30 ml of water and 30 ml of saturated NaCl solution. The extract is dried over sodium sulfate, and the solvent is removed. Product weight: 6.78 g

(54) 1H-NMR: 7.8-7.6 ppm (m, 2 H, —CFH); 6.8 ppm (s, H, —C═CH—); 4.4-4.0 ppm (t, 2 H, —CH2-CH2-S—); 3.7 ppm (s, H, CH2-C═CH—); 3.2-2.8 ppm (t, 2 H, —CH2-CH2-O)

Example 2d: Synthesis of the Compound of the Formula (XVIII)

(55) ##STR00031##

(56) 6.78 g of the fluorine-containing aconitic acid ester from Example 2c, 1.22 g of a 39% sodium hydrogensulfite solution and 24 ml of 2-propanol are initially introduced in a round-bottomed flask. The pH of the reaction mixture is then adjusted to pH 6.3 using sodium hydroxide solution. The reaction mixture is subsequently stirred at 95° C. for 96 h. 30 ml of MTBE and 30 ml of water are added to the reaction mixture, and the phases are separated. The aqueous phase is extracted twice with 20 ml of MTBE. The combined organic phases are subsequently washed with 30 ml of water and 30 ml of saturated NaCl solution. The extract is dried over sodium sulfate, and the solvent is removed. Yield: 6.26 g

(57) 1H-NMR: 7.0 ppm (dt, 3 H, —CFH); 4.2-3.8 ppm (m, 6 H, S—CH2-CH2); 3.5-2.5 ppm (m, 10 H, CH2-CH2-O) and CH2-RCH—CH—SO3H

Example 3: Synthesis of the Compound of the Formula (XXI) where n=5; 7.510

Example 3a: Preparation of the Fluorinated Diol

(58) ##STR00032##

(59) 8.63 g of 1,1,1,2,2,3,3-heptafluoro-3-trifluorovinyloxypropane, 2.50 g of 1,4-dimercaptobutane-2,3-diol, 0.67 g of potassium carbonate and 30 ml of acetonitrile are combined in a pressure reactor and stirred at 120° C. for 20 h. 30 ml of water and 30 ml of MTBE are added to the reaction mixture, and the phases are separated. The aqueous phase is extracted twice with 20 ml of MTBE. The combined organic phases are subsequently washed with 30 ml of water and 30 ml of saturated NaCl solution. The extract is then dried over sodium sulfate, and the solvent is distilled off. Product weight: 9.82 g

(60) 1H-NMR: 7.2 ppm (dt, 2H, —CFH); 5.3 ppm (m, 2 H, —OH);

(61) 3.7 ppm (dt, 2 H, CH2-CH—O—); 2.9-3.2 ppm (m, 4 H, CH2-S);

Example 3b: Preparation of the Ethoxylated Compound

(62) ##STR00033##

(63) The alcohol prepared is reacted with ethylene oxide at 140° C. and max. 4 bar in a pressure reactor to give the corresponding fluorosurfactant. Various chain lengths can be achieved depending on the reaction time. The material synthesised here has a statistical EO chain length of 5 units.

(64) 1H-NMR: 7.2 ppm (dt, 2 H, —CFH); 3.85-3.4 ppm (m, 44 H); 2.9-3.2 ppm (m, 4 H, CH2-S);

Examples 3c-e

(65) Carried out analogously to Example 3b, only with the ethoxylation being carried out longer until an average recurring number of 3c: EO=10; 3d: EO=15; 3e EO=20 has been reached.

Example 3f

(66) ##STR00034##

(67) 11 g of the compound from Example 3a are initially introduced in 4 ml of toluene in a reaction flask and heated to 60° C. 1.98 g of phosphoryl chloride are slowly added over the course of 10 min. The reaction mixture is subsequently heated to 115° C. and stirred at this temperature for 18 h. The batch is subsequently cooled to 90° C. and carefully hydrolysed using 0.3 ml of water, and the mixture is stirred at this temperature for a further hour. The solvent is subsequently removed, leaving a brown residue.

(68) 20 ml of MTBE and 20 ml of water are added to the crude product, and the phases are separated. The aqueous phase is extracted with 2×30 ml of MTBE. The combined organic phases are subsequently neutralised using ammonia solution and separated off.

(69) Product weight: 11.18 g

(70) 1H-NMR: 7.2 ppm (dt, 2 H, —CFH); 3.75 ppm (m, 2 H, ROCH—CHOR); 2.75 ppm (m, 4 H, S—CH.sub.2—CHR)

Example 4: Synthesis of Compounds of the Formula (XVII)

(71) ##STR00035##

(72) 7.53 g of 1,1,1,2,2,3,3-heptafluoro-3-trifluorovinyloxypropane, 3.58 g of the sodium salt of 2-mercaptoethanesulfonic acid, 0.90 g of potassium carbonate and 30 ml of acetonitrile are combined in a pressure reactor and stirred at 110° C. for 18 h.

(73) MTBE and water 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 phases are washed with 30 ml of water and 30 ml of saturated NaCl solution.

(74) The extract is dried over sodium sulfate, and the solvent is removed.

(75) Product weight: 6.53 g

(76) 1H-NMR: 7.2 ppm (dt, 1 H, —CFH); 3.2-2.7 ppm (m, 4 H, S—CH.sub.2—CH.sub.2—SO.sub.3Na);

(77) Table 1 shows the static surface tension and the CMC (critical micelle concentration) of compounds according to the invention.

(78) TABLE-US-00001 TABLE 1 Static surface tension measurement of the surfactants described above as 0.1% aqueous solution in dynes (mN/m) Ex. 1c 1d 1e 1f 1 g 2b 2d Dynes 20.4 20.5 27.0 20.0 17.0 16.0 20.2 Ex. 3b 3c 3d 3e 3f 4 Dynes 18.2 18.9 20.3 21.1 18.5 19.3 (1%)