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))
Z.sub.nC.sub.cD.sub.dspacer.sub.mX.sub.x(I) where Z=R.sub.fO.sub.o1-A.sup.1.sub.a1-O.sub.o2-A.sup.2.sub.a2-O.sub.o3B.sub.b n=1, 2, 3, 4, 5 or 6, R.sub.f=fluorinated alkyl, linear or branched, A.sup.1 and A.sup.2=independently of one another (CF.sub.2) or (CF(CF.sub.3)CF.sub.2) or (CF.sub.2O) or (CF.sub.2CF.sub.2)O, a.sub.1 and a.sub.2=independently of one another 0-4, B=CHFCF.sub.2CR.sup.1R.sup.2O b=1 R.sup.1=H or alkyl, preferably C1-C4, in particular CH.sub.3 or CH.sub.2CH.sub.3 R.sup.2=H or alkyl, preferably C1-C4, in particular CH.sub.3, C=CR.sub.2CR.sub.2O, c=0 or an integer from the range from 1 to 100, R and R=independently of one another H or alkyl, D=CO d=0 or 1, spacer=a saturated or unsaturated, branched or unbranched hydrocarbon unit, optionally containing heteroatoms, m=0 or 1, X is a hydrophilic group, x=1, 2, 3 or 4, o1, o2 and o3=independently of one another 0 or 1, where all indices are selected so that no OO bonds are present and the following compound is excluded: ##STR00013##

2. Compounds according to claim 1, characterised in that they conform to the formula (I):
(ZC.sub.cD.sub.d)spacer.sub.mX.sub.x(I) where the variables have the meanings indicated for formula (I).

3. Compounds according to claim 1, characterised in that n is equal to 2-3.

4. Compounds according to claim 1, characterised in that R.sub.f=fluorinated C1-C6-alkyl, in particular fluorinated C1-C3-alkyl.

5. Compounds according to claim 1, characterised in that x=1.

6. Compounds according to claim 1, characterised in that Z is equal to: R.sub.fOCHFCF.sub.2CR.sup.1R.sup.2O or R.sub.fO(CF.sub.2).sub.1-4CHFCF.sub.2CR.sup.1R.sup.2O or R.sub.fO(CF.sub.2).sub.1-4OCHFCF.sub.2CR.sup.1R.sup.2O or R.sub.fO(CF(CF.sub.3)CF.sub.2).sub.1-4CHFCF.sub.2CR.sup.1R.sup.2O or R.sub.fO(CF(CF.sub.3)CF.sub.2).sub.1-4OCHFCF.sub.2CR.sup.1R.sup.2O or R.sub.fO(CF.sub.2O).sub.1-4CHFCF.sub.2CR.sup.1R.sup.2O or R.sub.fO(CF.sub.2CF.sub.2O).sub.1-4CHFCF.sub.2CR.sup.1R.sup.2O or R.sub.fO(CF.sub.2O).sub.1-4(CF.sub.2CF.sub.2O).sub.1-4CHFCF.sub.2CR.sup.1R.sup.2O.

7. Compounds one or more of claim 1, characterised in that Rf=CF.sub.3 or CF.sub.3CF.sub.2 or CF.sub.3CF.sub.2CF.sub.2.

8. Compounds according to claim 1, characterised in that they conform to the formulae (II) to (XI) where Y=(OCR.sub.2CR.sub.2)0/1-Z, X=Na.sup.+, K.sup.+, Li.sup.+, NH.sup.4+, N(CH.sub.3).sup.4+, Q=Cl, Br, I and R and R=independently of one another H or C1-C4 alkyl ##STR00014##

9. Compounds one or more of claim 8, characterised in that Y=(OCH.sub.2CHR.sub.2)0/1-Z, where R=H or C1-C2 alkyl.

10. Compounds according to claim 8, characterised in that they conform to the formulae (II-a), (II-b), (II-c) or (II-d): ##STR00015##

11. Compounds one or more of claim 1, characterised in that Rf=CF.sub.3, CF.sub.3CF.sub.2 or CF.sub.3CF.sub.2CF.sub.2, Z=R.sub.fOCHFCF.sub.2CR.sup.1R.sup.2O or R.sub.tO(CF.sub.2).sub.1-4CHFCF.sub.2CR.sup.1R.sup.2O, where R.sup.1 and R.sup.2 independently of one another=H, CH.sub.3 or CH.sub.2CH.sub.3 and X is one of the groups SO.sub.3.sup., OSO.sub.3.sup., PO.sub.3.sup.2 or OPO.sub.3.sup.2, polyethylene glycols or polypropylene glycols, CH(OH)CH.sub.2NHSach, Y(CH.sub.2CH.sub.2O).sub.vR.sup.4, betaines, or sulfobetaines.

12. A method comprising adding a compound according to claim 1 as an additive to a composition selected from: 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 or coatings of optical elements.

13. Composition comprising a compound 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 selected from: paint and coating preparations, fire-extinguishing compositions, lubricants, washing and cleaning compositions, de-icers, developer solutions and wash solutions and photoresists for photolithographic processes, cosmetic products, agrochemicals, floor polishes or hydrophobicising compositions for textile finishing or glass treatment.

Description

EXAMPLES

Abbreviations

[0091] MTBE tert-butyl methyl ether
b.p. boiling point
DM demineralised

Example 1

2-Sulfosuccinic acid bis-[2-(2,2,3-trifluoro-3-heptafluoropropyloxypropoxy)ethyl] ester sodium

[0092] ##STR00012##

[0093] 20.20 g of 2,2,3-trifluoro-3-heptafluoropropyloxypropan-1-ol, 6.56 g of ethylene carbonate and 0.95 g of potassium carbonate are reacted at 130 C. for 75 hours. 50 ml of semi-concentrated HCl are added to the reaction mixture, which is extracted by shaking with 325 ml of MTBE, the combined organic phases are dried over sodium sulfate, and the solvent is distilled off. Crude yield: 21.75 g

[0094] Distillative work-up gives 12.9 g of 96% product (b.p. 78 C./10 mbar). GC-MS and NMR investigations confirm the structure

[0095] 12.65 g of the alcohol, 1.72 g of maleic anhydride and 0.3 g of p-toluenesulfonic acid (catalyst) in 60 ml of toluene are boiled under reflux for 96 hours. The water liberated during the reaction is removed with the aid of the water separator. 30 ml of DM water are added to the reaction mixture, and the phases are separated. The aqueous phase is subsequently extracted with 325 ml of MTBE, the combined organic phases are washed with 130 ml of water and with 130 ml of sat. NaCl solution and dried over sodium sulfate, filtered off, and the solvent is distilled off.

[0096] Distillation in a high vacuum gives 8.22 g of the corresponding ester in 96% purity (b.p. 180/6.7*10.sup.2 mbar).

[0097] 6.6 g of diester are dissolved in 12 ml of 2-propanol, and 5.57 g of 39% aqueous sodium hydrogensulfite solution are added at 50 C. The pH is adjusted to 5-6 using 32% sodium hydroxide solution and stirred at 100 C. for 41 h.

[0098] 40 ml of DM water are added to the reaction mixture, and the phases are separated.

[0099] The aqueous phase is subsequently extracted with 325 ml of MTBE, the combined organic phases are washed with 130 ml of water and 130 ml of saturated NaCl solution and dried over sodium sulfate.

[0100] Removal of the solvent by distillation gives a yield of 3.90 g

[0101] The static surface tension .sub.stat is determined by the method indicated and is 17.69 mN/m for a solution comprising 0.1% by weight of the compound and 16.78 mN/m for a solution comprising 1% by weight of the compound.

[0102] The dynamic surface tension is shown in FIG. 1.

Example 2

Determination of the Static Surface Tension

[0103] The static surface tensions of aqueous surfactant solutions having various concentrations c (grams per litre) are determined.

[0104] Instrument: Dataphysics tensiometer (model DCAT 11)

[0105] Temperature of the measurement solutions: 200.2 C.

[0106] Measurement method employed: measurement of the surface tension using the Wilhelmy plate method in accordance with DIN EN 14370.

[0107] Plate: platinum, length=19.9 mm

[0108] 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]$=\frac{F}{L.Math.\cos .Math..Math.}=\frac{F}{L}$

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

Example 3

Determination of the Dynamic Surface Tension

[0109] The dynamic surface tension of a 0.1% (percent by weight) aqueous solution of the compound to be investigated is determined.

[0110] Measurement method employed: measurement of the surface tension using the bubble pressure method

[0111] Instrument: SITA tensiometer (model t 60)

[0112] Temperature of the measurement solutions: 20 C.0.2 C.

[0113] During measurement of the dynamic surface tension, air bubbles are forced at different speeds through a capillary into the surfactant solution. The surface tension can be determined from the resultant pressure change as a function of the bubble lifetime using the following equation:

[00002]$=\frac{r\left(p_{\max }-.Math.g.Math.h\right)}{2}$

p.sub.max=maximum pressure, =density of the liquid, h=immersion depth, r=radius of the capillary