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.nspacerX.sub.x (I) where ZR.sub.fO.sub.o1-A.sup.l.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, BCHFCF.sub.2Y(CH.sub.2).sub.m YO or S, b=1 m=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.

2. Compounds according to claim 1, characterised in that Z is equal to: R.sub.fCHFCF.sub.2Y(CH.sub.2).sub.m or R.sub.fOCHFCF.sub.2Y(CH.sub.2).sub.m or R.sub.fO(CF.sub.2).sub.1-4CHFCF.sub.2Y(CH.sub.2).sub.m or R.sub.fO(CF.sub.2).sub.1-4OCHFCF.sub.2Y(CH.sub.2).sub.m or R.sub.fO(CF(CF.sub.3)CF.sub.2).sub.1-4CHFCF.sub.2Y(CH.sub.2).sub.m or R.sub.fO(CF(CF.sub.3)CF.sub.2).sub.1-4OCHFCF.sub.2Y(CH.sub.2).sub.m or R.sub.fO(CF.sub.2O).sub.1-4CHFCF.sub.2Y(CH.sub.2).sub.m or R.sub.fO(CF.sub.2CF.sub.2O).sub.1-4CHFCF.sub.2Y(CH.sub.2).sub.m or R.sub.fO(CF.sub.2O).sub.1-4(CF.sub.2CF.sub.2O).sub.1-4CHFCF.sub.2Y(CH.sub.2).sub.m where m=0 or 1.

3. Compounds according to claim 1, characterised in that Z is equal to: R.sub.fCHFCF.sub.2Y(CH.sub.2).sub.m or R.sub.fOCHFCF.sub.2Y(CH.sub.2).sub.m or R.sub.fO(CF.sub.2).sub.1-4CHFCF.sub.2Y(CH.sub.2).sub.m or R.sub.fO(CF.sub.2).sub.1-4OCHFCF.sub.2Y(CH.sub.2)m where m=0 or 1.

4. Compounds according to claim 1, characterised in that Z is equal to: R.sub.fOCHFCF.sub.2Y(CH.sub.2).sub.m or R.sub.fO(CF.sub.2).sub.1-4OCHFCF.sub.2Y(CH.sub.2)m where m=0 or 1.

5. Compounds according to claim 1, characterised in that RfCF.sub.3 or CF.sub.3CF.sub.2 or CF.sub.3CF.sub.2CF.sub.2.

6. Compounds according to claim 1, characterised in that the group (spacer-X) has one of the following meanings: CR.sup.5(CH.sub.2).sub.nOH, CR.sup.5(CH.sub.2).sub.nSH, CR.sup.5(CH.sub.2).sub.nCOOH, CR.sup.5(CH.sub.2).sub.nSO.sub.3H, CR.sup.5(CH.sub.2).sub.nNH.sub.2, CR.sup.5(CH.sub.2).sub.nNR.sub.2, CR.sup.5(CH.sub.2).sub.nN.sup.+(CH.sub.3).sub.3 Cl.sup., CR.sup.5(CH.sub.2).sub.nNR.sub.2CH.sub.2COO.sup., CR.sup.5(CH.sub.2).sub.nO(CHR.sup.aCHR.sup.bO).sub.nR, CR.sup.5(CH.sub.2).sub.nS(CHR.sup.aCHR.sup.bO).sub.nR or CR.sup.5(CH.sub.2).sub.nNH(CHR.sup.aCHR.sup.bO).sub.nR, where n=1-30 and R.sup.5, R, R, R.sup.a and R.sup.b independently of one another=H or alkyl.

7. Compounds according to claim 1, characterised in that they conform to the formula (IIa) or (IIb):
[F(CF.sub.2).sub.n(O).sub.oCHFCF.sub.2Y(CH.sub.2).sub.m].sub.2spacer-X formula (IIa)
[F(CF.sub.2).sub.n(O).sub.o(CF.sub.2).sub.1-4OCHFCF.sub.2Y(CH.sub.2).sub.m].sub.2spacer-X formula (IIb) where n=1-6, m=0 or 1, o=0 or 1, YO or S, and the group (spacer-X)=CR.sup.5(CH.sub.2).sub.nOH, CR.sup.5(CH.sub.2).sub.nSH, CR.sup.5(CH.sub.2).sub.nCOOH, CR.sup.5(CH.sub.2).sub.nSO.sub.3H, CR.sup.5(CH.sub.2).sub.nNH.sub.2, CR.sup.5(CH.sub.2).sub.nNR.sub.2, CR.sup.5(CH.sub.2).sub.nN.sup.+(CH.sub.3).sub.3 Cl.sup., CR.sup.5(CH.sub.2).sub.nNR.sub.2CH.sub.2COO.sup., CR.sup.5(CH.sub.2).sub.nO(CHR.sup.aCHR.sup.bO).sub.nR, CR.sup.5(CH.sub.2).sub.nS(CHR.sup.aCHR.sup.bO).sub.nR or CR.sup.5(CH.sub.2).sub.nNH(CHR.sup.aCHR.sup.bO).sub.nR, n=0 or 1, n=1-30, and R.sup.5, R, R, R.sup.a and R.sup.b independently of one another=H or alkyl.

8. Compounds according to claim 1, characterised in that n=1-3, m=0 or 1, o=1, YO, and R, R, R.sup.a and R.sup.b independently of one another=H or C1-C4 alkyl.

9. Compounds according to claim 1, characterised in that they conform to the formula (III), (III), (IV) or (IV): ##STR00028## where R.sub.f=fluorinated alkyl, linear or branched, preferably perfluorinated C1-C4-alkyl, and X is a hydrophilic group.

10. Compounds according to claim 1, characterised in that they conform to the formulae (IIIa), (IIIa), (IIIb) (IIIb), (IVa), (IVa), (IVb) (IVba), (IVc) or (IVc): ##STR00029## ##STR00030## where R.sub.f=fluorinated alkyl, linear or branched, preferably perfluorinated C1-C4-alkyl, and PEG stands for polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether or polypropylene glycol alkyl ether.

11. Compounds according to claim 1, characterised in that they conform to one of the formulae (V) to (XII): ##STR00031## ##STR00032##

12. (canceled)

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 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.

15. Composition according to claim 13, which is 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.

Description

EXAMPLES

[0160] The NMR spectra are measured using a Bruker 400 MHz spectrometer with internal standard.

[0161] The IR spectra are measured using a Brucker Alpha Platinum-ATR spectrometer.

[0162] Determination of the Static Surface Tension

[0163] The static surface tensions of aqueous surfactant solutions having various concentrations c (grams per litre) are determined.

[0164] Instrument: Dataphysics tensiometer (model DCAT 11)

[0165] Temperature of the measurement solutions: 200.2 C.

[0166] Measurement method employed: measurement of the surface tension using the Wilhelmy plate method in accordance with DIN EN 14370.

[0167] Plate: platinum, length=19.9 mm

[0168] 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]$=\frac{F}{L.Math.\cos .Math..Math.}=\frac{F}{L}$

[0169] =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.

[0170] Abbreviations

[0171] EO ethylene oxide units

[0172] THF tetrahydrofuran

[0173] MTBE tert-butyl methyl ether

[0174] b.p. boiling point

[0175] w % percent by weight

Example 1

General Ethoxylation Procedure

[0176] For the ethoxylation, the corresponding alcohol in accordance with the prior art is introduced into a pressure reactor with a catalyst (for example potassium hydroxide) under inert gas, and a corresponding amount of ethylene oxide is condensed in (b.p.: 10.5 C.). The reactor is sealed and heated to 80-150 C. at about 5 bar. After completion of the reaction, the mixture is decompressed and any by-products are removed from the product under reduced pressure.

Example 2

[0177] 6 EO are adducted onto isopropylideneglycerol (Sigma-Aldrich) as described under Example 1.

##STR00015##

[0178] NMR analysis:

[0179] .sup.1H-NMR (DMSO): 4.13CH (m), 3.93CH (dd), 3.7-3.3 14CH.sub.2 (m), 1.26CH.sub.3 (s), 1.21CH.sub.3 (s)

[0180] .sup.13C-NMR (DMSO): 108. 8 quart. C; 74.7, 72.8, 72.0, 70.6, 70.2, 66.5, 60.7 sec. C; 27.0, 25.8 prim. C

[0181] 25 g of this compound are dissolved in 125 ml of THF and initially introduced in a three-necked flask with reflux condenser, thermometer, stirring device and septum. Under a protective-gas atmosphere, 9 g of potassium tert-butoxide (Sigma-Aldrich) are added, during which a slight increase in temperature (to 32 C.) is observed. After 20 min, 10 g of dimethyl sulfate (Sigma-Aldrich) is slowly added. It must be ensured that the temperature does not exceed 37 C. during the addition. After stirring for one hour at room temperature, the reaction mixture is heated to the boiling temperature for 2 hours.

[0182] After cooling to room temperature, 50 ml of 10% NH.sub.3 solution we added to the batch, which is then stirred for a further 1 hour in order to decompose residual dimethyl sulfate.

[0183] 20 ml of 2 N HCl are added to the batch (pH=1), and the mixture is warmed under reflux for 6 hours in order to remove the isopropylidene protecting group.

[0184] The solvent is removed completely, and the residue is dispersed in 50 ml of acetone.

[0185] Salt residues are separated off via a frit, and the solvent is distilled off under reduced pressure.

##STR00016##

[0186] NMR analysis:

[0187] .sup.1H-NMR (DMSO): 3.8-3.3 14CH.sub.2 (m), 3.2OCH.sub.3 (s)

[0188] 11 g of 1,1,1,2,2,3,3 heptafluoro-3-trifluorovinyloxypropane (ABCR) are added to 5 g of this compound in an autoclave, 10 ml of acetonitrile and 2.4 g of potassium carbonate are mixed and warmed at 80 C. for 66 hours (internal pressure 3.7 bar). 100 ml of water and 100 ml of MTBE are added to the reaction mixture the phases are separated, and the aqueous phase is washed by shaking with 250 ml of MTBE. The combined organic phases are washed firstly with 50 ml of water and then with 50 ml of saturated NaCl solution, dried over Na.sub.2SO.sub.4, and the solvent is separated off under reduced pressure.

[0189] The yield is 6 g of a viscous, amber-coloured substance. The following structure arises from the spectroscopic data determined (NMR):

##STR00017##

[0190] NMR analysis

[0191] .sup.1H-NMR (DMSO): 5.9CHF (d), 3.8-3.4 14CH.sub.2 (m), 3.3OCH.sub.3 (s)

[0192] Static surface tension:

[0193] 18.9 mN/m (0.1 w %); CMC [g/l] 0.01

Example 3

[0194] 12 EO are adducted onto isopropylideneglycerol as described under Example 1.

##STR00018##

[0195] NMR analysis

[0196] .sup.1H-NMR (DMSO): 4.13CH (1 m), 3.93CH (1 dd), 3.7-3.3CH.sub.2 (26, m), 1.26CH.sub.3 (3, s), 1.21CH.sub.3 (3, s)

[0197] The further reaction is carried out analogously to Example 2

##STR00019##

[0198] NMR analysis:

[0199] .sup.1H-NMR (DMSO): 3.8-3.3CH.sub.2 (26, m), 3.2OCH.sub.3 (3, s)

[0200] The yield is 7.6 g of a viscous, amber-coloured substance. The following structure arises from the spectroscopic data determined (NMR):

##STR00020##

[0201] NMR analysis:

[0202] .sup.1H-NMR (DMSO): 5.9CHF (2, d), 3.8-3.4CH (26, m), 3.3OCH.sub.3 (3, s)

[0203] Static surface tension:

[0204] 18.0 mN/m (0.1 w %)

Example 4

[0205] 3,700 g of 1,1,2,2,3,3 hexafluoro-1-trifluoromethoxy-3-trifluorovinyloxy-propane are warmed in an autoclave with 500 g of glycerol 1-acetate, 670 g of potassium carbonate and 2,300 g of acetonitrile and at 80 C. for 68 hours (internal pressure 2.3 bar).

[0206] The batch is washed with water, and the organic phase is separated off. 500 ml of 32% sodium hydroxide solution and 500 ml of water are added to the batch, and the mixture is stirred at the boiling temperature for 72 hours.

[0207] The product is extracted with MTBE, washed again with water, dried over Na.sub.2SO.sub.4 and subjected to fractional distillation in vacuo main fraction (b.p. 82 C. at 0.37 mbar).

##STR00021##

[0208] NMR analysis

[0209] .sup.1H-NMR (DMSO): 6.6CHF (2, m), 5.2-3.7CH (5, m)

[0210] The partially fluorinated alcohol is ethoxylated analogously to Example 1 where 12 EO are adducted. The following structure arises from the spectroscopic data determined (NMR:

##STR00022##

[0211] NMR analysis

[0212] .sup.1H-NMR (DMSO): 6.8CHF (2, d), 4.9-4.0 CH (5, m), 3.8-3.2CH.sub.2CH.sub.2O (48, m)

[0213] Static surface tension:

[0214] 18.62 mN/m (0.1 w %)

Example 5

[0215] A surfactants having 24 EO units is synthesised analogously to Example 5. The following structure arises from the spectroscopic data determined (NMR):

##STR00023##

[0216] NMR analysis

[0217] .sup.1H-NMR (DMSO): 6.8CHF (2, d), 4.9-4.0CH (5, m), 3.8-3.2CH.sub.2CH.sub.2O (96, m)

[0218] Static surface tension:

[0219] 17.58 mN/m (0.1 w %)

Example 6

[0220] 3.12 g (0.056 mol) of potassium hydroxide are combined with 15 ml of acetonitrile and 2.83 g (0.024 mol) of 3-dimethylaminopropane-1,2-diol (ABCR) in a pressure reactor. 13.90 g (0.052 mol) of 1,1,1,2,2,3,3-heptafluoro-3-trifluorovinyloxypropane are subsequently added. The pressure reactor is sealed, and the mixture is heated to 80 C. Stirring is continued in this reaction for 18 hours.

[0221] After completion of the reaction, the reaction mixture is allowed to cool, filtered, and the solvent is removed in vacuo.

[0222] For further work-up, the product is subjected to fractional distillation in vacuo, giving 9.66 g (63%) of pale-yellow oil.

##STR00024##

[0223] NMR analysis:

[0224] .sup.1H-NMR (DMSO): 6.89-6.65CHF (2, dt), 5.20CH (1, tt), 4.34-4.16CH.sub.2 (2m), 3.56-3.37CH.sub.2 (2m), 2.88CH.sub.3 (6, s)

[0225] 7.4 g (0.011 mol) of [2,3-bis-(1,1,2-trifluoro-2-heptafluoropropyloxyethoxy)-propyl]dimethylamine, 1.41 g (0.012 mol) of chloroacetic acid sodium salt (VWR) and 10 ml of 90% ethanol are introduced into a round-bottomed flask and stirred under reflux for 96 h.

[0226] The reaction mixture is filtered, and the solvent is removed in vacuo.

[0227] The crude product is transferred onto silica gel and separated from the starting material using toluene/ethyl acetate 2/1.

[0228] The product is washed off the silica gel using acetone. Yield 4.4 g.

##STR00025##

[0229] NMR analysis:

[0230] .sup.1H-NMR (DMSO): 6.89-6.65CHF (2, dd), 5.5CH (1, s), 4.54-4.16CH.sub.2 (4m), 4.0CH.sub.2 (2, s), 3.40CH.sub.3 (6, ds)

[0231] Static surface tension:

[0232] 15.89 mN/m (1.0 w %)

Example 7

[0233] 5.0 g (0.034 mol) of methyl 3-hydroxy-2-hydroxymethyl-2-methylpropionate (VWR), 15 ml (0.084 mol) of 1,1,1,2,2,3,3-heptafluoro-3-trifluorovinyloxy-propane, 6.1 g (0.044 mol) of potassium carbonate and 25 ml of acetonitrile are combined in a pressure reactor and heated to 80 C. Stirring is continued at this temperature for 48 hours.

[0234] The mixture is subsequently allowed to cool, filtered, and the solvent is removed in vacuo.

[0235] The crude product is fritted through silica gel, giving 17.1 g (0.025 mol) of methyl 2-methyl-3-(1,1,2-trifluoro-2-heptafluoropropyloxyethoxy)-2-(1,1,2-trifluoro-2-heptafluoropropyloxyethoxymethyl)propionate.

##STR00026##

[0236] 10.00 g (0.015 mol) of methyl 2-methyl-3-(1,1,2-trifluoro-2-heptafluoro-propyloxyethoxy)-2-(1,1,2-trifluoro-2-heptafluoropropyloxyethoxymethyl)-propionate are combined with 1.47 g (0.037 mol) of NaOH in 15 ml (0.257 mol) of ethanol and stirred under reflux for 18 hours.

[0237] The solvent is subsequently removed in vacuo, the residue is suspended in acetone and filtered to remove the sodium hydroxide.

[0238] The acetone is removed by vacuum distillation, giving 9.4 g (0.014 mol) of the corresponding fluorosurfactant as sodium salt.

##STR00027##

[0239] Characterisation by IR: COO.sup. st as 1607 cm.sup.1

[0240] Static surface tension:

[0241] 16.45 mN/m (1.0 w %)