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. Compounds of the formula (I), ##STR00020## where R is equal to H, alkyl, —OH or —CH.sub.2—O-A′″.sub.a′″—Rf′, Rf, Rf′ and Rf″ are, independently of one another, equal to CF.sub.3—CF.sub.2—CF.sub.2—O—CF(CF.sub.3)—CH.sub.2— or CF.sub.3—(CF.sub.2).sub.n—(CH.sub.2).sub.m—, where n=1-7 and m=1-10, R.sup.1-R.sup.4 are, independently of one another, equal to hydrogen or a C1-C4 alkyl group, o and p are, independently of one another, 0-4, o+p≧2 and q≧1, A, A′ and A″ are, independently of one another, equal to (O—(CR.sup.5R.sup.6).sub.r—(CR.sup.7R.sup.8).sub.s).sub.t, where R.sup.5-R.sup.8 are, independently of one another, equal to hydrogen or a C1-C4 alkyl group, r and s are, independently of one another, 0-4 and t=0 or 1, B is equal to (CH.sub.2).sub.0-1—O or (CH.sub.2).sub.0-1—NR′, where R′═H or linear or branched alkyl, and X is equal to H or linear or branched alkyl.

2. Compounds according to claim 1, characterised in that n=1-5, m=1-3, R═H or —OH, B is equal to O, CH.sub.2—O or CH.sub.2—NR′, where R′ is equal to H or CH.sub.3, o and p are equal to 1-4, in particular 1-2, q is 1-100, in particular 1-40, particularly preferably 1-20, the group ((CR.sup.1R.sup.2).sub.o(CR.sup.3R.sup.4).sub.pO).sub.q is equal to polyethylene glycol, polypropylene glycol and/or polybutylene glycol units, t=0 or A, A′ and A″ are equal to —O—CH.sub.2—CHR″—, where R″ is equal to H or CH.sub.3, and X is equal to H or CH.sub.3.

3. Compounds according to claim 1, characterised in that Rf, Rf′ and Rf″ are identical and/or A, A′ and A″ are identical.

4. Compounds according to claim 1, characterised in that Rf and Rf′═CF.sub.3—CF.sub.2—CF.sub.2—O—CF(CF.sub.3)—CH.sub.2—, C.sub.2F.sub.5—CH.sub.2— or C.sub.3F.sub.7—CH.sub.2—, R is equal to H or —OH, B is equal to O or CH.sub.2—NR′, where R′ is equal to H or CH.sub.3, the group ((CR.sup.1R.sup.2).sub.o(CR.sup.3R.sup.4).sub.pO).sub.q is equal to a polyethylene glycol or polypropylene glycol unit, q is equal to 1-40, t is equal to 0, and X is equal to H.

5. Compounds according to claim 1, characterised in that they conform to the formula (I′), ##STR00021##

6. Compounds according to claim 1, characterised in that they conform to the formulae (II), (IIIa), (IIIb), (IVa) or (IVb), ##STR00022##

7. Compounds according to claim 1, characterised in that they conform to the formulae (IIa) to (IId), (IIIa-1) or (IVa-1), ##STR00023##

8. Process for the preparation of compounds of the formula (I) according to claim 1, comprising the steps: a) conversion of the alcohols of the formula (Va) or (Vb), which may optionally also be chain-extended, ##STR00024## into compounds of the formula (VI) ##STR00025## where R is equal to H, alkyl, —OH or —CH.sub.2—O-A′″-Rf″, Rf, Rf′ and Rf″ are, independently of one another, equal to CF.sub.3—CF.sub.2—CF.sub.2—O—CF(CF.sub.3)—CH.sub.2— or CF.sub.3—(CF.sub.2).sub.n—(CH.sub.2).sub.m—, where n=1-7 and m=1-10, A, A′ and A″ are, independently of one another, equal to (O—(CR.sup.5R.sup.6).sub.r—(CR.sup.7R.sup.8).sub.s).sub.t, where R.sup.5-R.sup.8 are, independently of one another, equal to hydrogen or a C1-C4 alkyl group, r and s, independently of one another, are 0-4 and t=0 or 1, preferably 0, and b) polymerisation of the compounds of the formula (VI) with alkylene oxide, preferably ethylene oxide, butylene oxide or propylene oxide.

9. Process for the preparation of compounds of the formula (I′) according to claim 5 where Rf′═Rf, comprising the steps: a) reaction of the alcohols of the formula (Va) or (Vb), ##STR00026## with 1,3-dichloropropan-2-ol or epichlorohydrin to give compounds of the formula (VI′), ##STR00027## where R is equal to H and Rf is equal to CF.sub.3—CF.sub.2—CF.sub.2—O—CF(CF.sub.3)—CH.sub.2— or CF.sub.3—(CF.sub.2).sub.n—(CH.sub.2).sub.m—, where n=1-5 and m=1-3, and b) polymerisation of the compounds of the formula (VI′) with alkylene oxide, preferably ethylene oxide, butylene oxide or propylene oxide.

10. Process for the preparation of compounds of the formula (I) according to claim 1, comprising the steps: a) conversion of the alcohols of the formula (Va) or (Vb), which may optionally also be chain-extended, ##STR00028## into compounds of the formula (VII), ##STR00029## where Rf, Rf′ and Rf″ are, independently of one another, equal to CF.sub.3—CF.sub.2—CF.sub.2—O—CF(CF.sub.3)—CH.sub.2— or CF.sub.3—(CF.sub.2).sub.n—(CH.sub.2).sub.m—, where n=1-7 and m=1-10, A, A′ and A″ are, independently of one another, equal to (O—(CR.sup.5R.sup.6).sub.r—(CR.sup.7R.sup.8).sub.s).sub.t, where R.sup.5-R.sup.8 are, independently of one another, equal to hydrogen or a C1-C4 alkyl group, r and s are, independently of one another, 0-4 and t=0 or 1, preferably 0, b) epoxidation of the compounds of the formula (VII), and c) reaction of the epoxides from step b) with polyethylene glycols or aminopolyethylene glycols.

11. Process for the preparation of compounds of the formula (I′) according to claim 5 where Rf′═Rf, comprising the steps: a) reaction of the alcohols of the formula (Va) or (Vb), ##STR00030## with 3-chloro-2-chloromethyl-1-propene to give compounds of the formula (VII′), ##STR00031## where Rf is equal to CF.sub.3—CF.sub.2—CF.sub.2—O—CF(CF.sub.3)—CH.sub.2— or CF.sub.3—(CF.sub.2).sub.n—(CH.sub.2).sub.m—, where n=1-5 and m=1-3, b) epoxidation of the compounds of the formula (VII′), and c) reaction of the epoxides from step b) with polyethylene glycols or aminopolyethylene glycols.

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

13. Composition comprising a compounds according to claim 1 and a vehicle which is suitable for the respective application, and optionally further specific active substances.

14. Composition according to claim 13, characterised in that the composition is paint and coating preparations, fire-extinguishing compositions, lubricants, washing compositions and detergents, de-icers, developer solutions and washing solutions and photoresists for photolithographic processes, cosmetic products, agrochemicals, floor polishes or hydrophobicising compositions for textile finishing or glass treatment.

15. Compounds of the formula (VI) or (VI′), ##STR00032## where R is equal to H, alkyl, —OH or —CH.sub.2—O-A′″.sub.a′″-Rf″, Rf, Rf′ and Rf″ are, independently of one another, equal to CF.sub.3—CF.sub.2—CF.sub.2—O—CF(CF.sub.3)—CH.sub.2— or CF.sub.3—(CF.sub.2).sub.n—(CH.sub.2).sub.m—, where n=1-7 and m=1-10, A, A′ and A″ are, independently of one another, equal to (O—(CR.sup.5R.sup.6).sub.r—(CR.sup.7R.sup.8).sub.s).sub.t, where R.sup.5-R.sup.8 are, independently of one another, equal to hydrogen or a C1-C4 alkyl group, r and s are, independently of one another, 0-4 and t=0 or 1.

16. Compounds of the formula (VII) or (VII′), ##STR00033## where Rf and Rf′ are, independently of one another, equal to CF.sub.3—CF.sub.2—CF.sub.2—O—CF(CF.sub.3)—CH.sub.2— or CF.sub.3—(CF.sub.2).sub.n—(CH.sub.2).sub.m—, where n=1-7 and m=1-10, A and A′ are, independently of one another, equal to (O—(CR.sup.5R.sup.6).sub.r—(CR.sup.7R.sup.8).sub.s).sub.t, where R.sup.5-R.sup.8 are, independently of one another, equal to hydrogen or a C1-C4 alkyl group, r and s are, independently of one another, 0-4 and t=0 or 1.

Description

EXAMPLES

Abbreviations

[0052] Et.sub.2O diethyl ether [0053] EtOAc ethyl acetate [0054] MTBE tert-butyl methyl ether [0055] HFPO alcohol 1H,1H-perfluoro(2-methyl-3-oxahexan-1-ol) [0056] RT room temperature [0057] DBTL dibutyltin dilaurate

Example 1: Synthesis of 1H,1H-perfluoro(2-methyl-3-oxahexan-1-ol) (CAS 2101-3-71)

[0058] ##STR00012##

[0059] 30 ml of absol. Et.sub.2O are initially introduced in a dry 500 ml four-necked flask with metal condenser, CaCl.sub.2 drying tube, dropping funnel and thermometer, and 70 ml of 1M LiAlH.sub.4 solution (0.07 mol) in Et.sub.2O are introduced via a septum. 44.30 g (0.12 mol) of methyl perfluoro(2-methyl-3-oxahexanoate) (ABCR, Karlsruhe Germany) in 50 ml of abs. Et.sub.2O are introduced into the dropping funnel.

[0060] The ester is added dropwise with stirring at such a rate that the exothermicity of the reaction maintains the diethyl ether at the boil. When the addition is complete, the reaction mixture is stirred under reflux for a further 1.5 hours. A cloudy dispersion forms in the course of the reaction. The batch is cooled in an ice bath. The excess LiAlH.sub.4 is decomposed by addition of 10 ml of EtOAc with slight evolution of heat. 10 g of H.sub.2O are subsequently added, after which a flocculent aluminium hydroxide precipitate forms. 78 g of 25% sulfuric acid is added dropwise to the suspension over the course of 30 minutes, during which a clear two-phase mixture forms. The organic phase is separated off, and the aqueous phase is washed with 3×40 ml of Et.sub.2O. The organic phases are combined, washed with 3×40 ml of H.sub.2O and dried over Na.sub.2SO.sub.4. The ether is distilled off, and the residue is subjected to fractional distillation. Product: 31.8 g (b.p. 57° C./100 mbar); purity 91% (GC-MS); yield 73% of theory

Example 2

[0061] ##STR00013##

[0062] 37.9 g of the HFPO alcohol from Example 1 and 5.0 g of 1,3-dichloropropan-2-ol are initially introduced in a 250 ml 3-necked flask. 6.52 g of powdered KOH are added with ice-cooling. During this addition, the temperature is kept below 10° C. When the addition is complete, the batch is warmed to 110° C. and stirred at this temperature for 16 hours.

[0063] The mixture is subsequently cooled to RT, and 50 ml of water are added. The organic phase is separated off, and the aqueous phase is extracted again with 3×50 ml of dichloromethane. The combined organic phases are then washed with 50 ml of water and dried over sodium sulfate.

[0064] After the solvent has been distilled off, the material is distilled in vacuo. B.p. 80-83° C./0.1 mbar; yield 17.56 g.

[0065] The branched alcohol is reacted with ethylene oxide in a pressure reactor in accordance with the prior art. (Conditions: 140° C.; maximum pressure 4 bar). The reaction is terminated when the polyethylene oxide chain statistically contains 8, 12 and 17 units. The static surface tension of the compounds and the critical micelle concentration (CMC) are reproduced in FIG. 1 as measurement values B2-8EO, B2-12EO and B2-17EO.

Example 3

[0066] ##STR00014##

[0067] 17.5 g of HFPO alcohol and 3 ml of 3-chloro-2-chloromethyl-1-propene are initially introduced in 30 ml of toluene. Powdered KOH is added with ice-cooling (temp. 0-10° C.). The mixture is subsequently heated to 110° C. and stirred at this temperature for 65 h. 50 ml of water are added to the batch, which is then extracted 3 times with 25 ml of MTBE. The combined organic phases are washed with 25 ml of water and dried over sodium sulfate. The batch is distilled in vacuo. B.p. 110-118° C./5 mbar; yield: 10 g.

Example 4: Epoxidation

[0068] 6 g of 3-chloroperoxybenzoic acid are dissolved in 25 ml of dichloromethane at room temperature and subsequently cooled to 10° C. 7 g of product from Example 3 are dissolved in 5 ml of dichloromethane and added to the batch, and the mixture is stirred at room temperature for 24 hours. The batch is filtered, and the filtrate is washed by shaking with 50 ml of 10% NaHSO.sub.3. The organic phase is separated off, dried and evaporated. Yield 5.59 g.

Example 5

[0069] ##STR00015##

[0070] 5 g of material from Example 4 are combined with 4 g of aminopolyethylene glycol (MW 560) and one drop of DBTL and warmed to 120° C. After 5 hours, the batch is a single phase. The batch is cooled to RT and passed through a short silica-gel column (10 g) with dichloromethane until the filtrate is colourless. The product is subsequently washed from the column using ethanol, the solvent is distilled off, and the residue is dried in vacuo (pale-yellow oil, yield: 8 g).

[0071] The static surface tension is γ=20.3 mN/m (0.1 g/l of H.sub.2O).

Example 6

[0072] ##STR00016##

[0073] 265.5 g of pentafluoropropanol and 217 g of DI water are initially introduced in a reactor with internal thermometer and reflux condenser and heated to a temperature of 30° C. 74.8 g of epichlorohydrin are added with stirring, and 56.11 g of a 47% KOH solution are subsequently slowly added dropwise. The metering rate here is selected so that the temperature of the reaction solution does not rise above 32° C. Towards the end of the addition, the batch becomes noticeably cloudy, with the viscosity increasing. When the addition is complete, the mixture is stirred at 70° C. for a further 15 h. The batch is cooled to room temperature, adjusted to pH 7 using dil. HCl, the organic phase is separated off and distilled in vacuo: yield 83%, 285 g. Purity 98% (GC).

Example 7

[0074] ##STR00017##

[0075] The alcohol prepared in Example 6 is reacted with ethylene oxide in a pressure reactor at 140° C. and a maximum pressure of 4 bar to give the corresponding fluorosurfactant. Different chain lengths can be achieved corresponding to the reaction time. Three materials having a statistically distributed recurring unit of 8, 12 and 17 are obtained. The material is freed from low-boiling impurities by vacuum distillation. The static surface tension of the compounds and the CMC are reproduced in FIG. 1 as measurement values B7-8EO, B7-12EO and B7-17EO.

Example 8

[0076] ##STR00018##

[0077] 180.7 g of heptafluorobutanol and 230 g of DI water are initially introduced in a reactor with internal thermometer and reflux condenser and heated to a temperature of 30° C. 40 g of epichlorohydrin are added with stirring, and 61.31 g of a 47% KOH solution are subsequently slowly added dropwise. The metering rate here is selected so that the temperature of the reaction solution does not rise above 32° C. Towards the end of the addition, the batch becomes noticeably cloudy, with the viscosity increasing. When the addition is complete, the mixture is stirred at 70° C. for a further 15 h. The batch is cooled to room temperature, adjusted to pH 7 using dil. HCl, the organic phase is separated off and distilled in vacuo. Yield 86%, 195 g. Purity 98% (GC).

Example 9

[0078] ##STR00019##

[0079] The alcohol prepared in Example 8 is reacted with ethylene oxide in a pressure reactor at 140° C. and a maximum pressure of 4 bar to give the corresponding fluorosurfactant. Different chain lengths can be achieved corresponding to the reaction time.

[0080] Three materials having a statistically distributed recurring unit of 8, 12 and 17 are obtained. The material is freed from low-boiling impurities by vacuum distillation. The static surface tension of the compounds and the CMC are reproduced in FIG. 1 as measurement values B9-8EO, B9-12EO and B9-17EO.

Determination of the Static Surface Tension

[0081] The static surface tensions γ of aqueous surfactant solutions having various concentrations c (grams per litre) are determined.

[0082] Instrument: Dataphysics tensiometer (model DCAT 11)

[0083] Temperature of the measurement solutions: 20°±0.2° C.

[0084] Measurement method employed: measurement of the surface tension using the Wilhelmy plate method in accordance with DIN EN 14370.

[0085] Plate: platinum, length=19.9 mm

[0086] 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]$\gamma =\frac{F}{L.Math.\cos .Math..Math.\theta }=\frac{F}{L}$

[0087] γ=interfacial or surface tension; F=force acting on the balance; L=wetted length (19.9 mm); θ=contact angle.

[0088] 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 approximately reaches the value 1, so that only the measured force and the length of the plate have to be taken into account.

FIGURES

[0089] FIG. 1 shows a comparison of the static surface tensions and CMCs of the synthesised short-chain fluorosurfactants with commercially available C6 (Capstone™) and C8 (Zonyl™) samples. Measurement values (denoted by *) above the bars are the CMCs determined in g/l. In the case of B7-12EO and B7-17EO, no CMC could be determined.

[0090] It can be seen from FIG. 1 that, in particular, the materials from Examples 3 and 10 cause a very good reduction in surface tension. Compared with commercially available C6 compounds, these materials in some cases do better and thus achieve the technical properties of C8 fluorosurfactants, which have been banned in the meantime.