NO845276L - FLUORATED QUATERNARY AMMONIUM COMPOUNDS, PROCEDURES FOR THEIR PREPARATION AND THEIR USE AS FLOW ACCELATORS - Google Patents

Description

It is generally known that turbulent flowing fluids at the walls that limit them, experience a frictional resistance. It is also known that this frictional resistance can be reduced by adding smaller amounts of certain substances. Substances that show this effect are known in English as "Drag reducing agents". In German, the term "Stromungsbeschleuniger" (hereinafter abbreviated SB) is used for these substances. According to this, a flow accelerator is understood as a substance.

that added in smaller quantities to a turbulent or pulsating flowing liquid, allows this liquid to flow faster under otherwise equal conditions. The flow accelerator makes it possible to transport more liquid with a given pump through a given pipeline.

In many cases, this fact alone is already a technical gain when, for example, a pipeline in normal operation is fully loaded and at certain times a peak consumption should be transported. As more liquid can be transported with a given pump performance when using flow accelerators, the associated energy savings also bring a technical advantage in many cases. Finally, when you do not want to increase the production quantity by using SB, you can reduce the pressure loss or use pipes with a smaller cross-section. Both are precautions that can improve the economics of operating a pipeline.

As a flow accelerator for water or aqueous solutions,

is it next to, of high molecular weight compounds such as polyethylene-

oxide and polyacrylamide known solutions of some surfactants. However, the addition of high molecular weight compounds has only a limited practical applicability as flow accelerators as in the area of high shear and expansion stress, e.g.

in pumps or to a lesser extent in the turbulent boundary layer near the pipe wall due to mechanical breakdown irreversibly lose their effect as flow accelerators. For closed water circuits in which the same aqueous solution is constantly pumped around through a pipeline system, high molecular weight additives are consequently unsuitable, as the irreversible mechanical degradation necessary

make a continuous re-dosing with effective high-molecular substance.

Additions of surfactants to water do not, as is known, have the disadvantage

by the irreversible mechanical breakdown (US patent 3 961 693). Admittedly, it is also possible here in areas with very high expansion and shear stresses, e.g. in the pump observe a mechanical breakdown which is, however, completely irreversible as soon as the solution has passed this range. Thus, the flow-accelerating effect of an aqueous solution of Na-oleate upon addition of KC1 + KOH or NaCl+NaOH is discussed

by Savins (Reol. Acta 6, 323 (1967)). Asslanow et al. Acad. Nauk. SSSr. Mech. Zhidk. Gaza 1, 36-43 (1980) examined, among other things, aqueous solutions of Na-laurate, -myristate, -palmi-

tat and - stearate at pH = 11 as SB.

Chang et al. (US patent 3,961,639) discusses the flow-accelerating effect of aqueous solutions of some nonionic surfactants with foreign electrolyte additives at temperatures in the region of the cloud point.

Substantial disadvantages of the aforementioned surfactant solutions are their relatively high application concentrations of at least 0.25% by weight, the formation of insoluble soaps with Ca 2+ and other cations, the formation of two phases which separate after a longer period of time and can lead to clogging. Necessity of adding corrosion-promoting foreign electrolytes as well as a very narrow temperature range of a few degrees Celsius, in which the SB effect occurs. Likewise, it is known that aqueous solutions of some cationic surfactants such as e.g. cetylpyridinium bromide (Inzh. Fizh. Zh, 38, No. 6, 1031-1037 (1980) or cetyltrimethylammonium bromide (Nature 214, 585-586 (1967)) in resp. 1:1 molar mixture with α-naphthol are effective as SB. Next to the poor water solubility of a-naphthol, it is here as a decisive disadvantage to mention that such mixtures lose their effectiveness as SB

within a few days due to chemical degradation (US Patent 3,961,639, Conference Proceding: Intern. Conference on Drag Reduction, 4-6.9.1974 Rolla Missouri, USA).

The use of cetyltrimethylammonium salicylate and tetradecyltrimethylammonium salicylate as SB (WO 83/01583)' is also known. The disadvantage of these surfactant salts as well as all previously known surfactant solutions is that they over approx. 80°C lose their effectiveness as SB, and are thus unsuitable for district heating networks. Further disadvantages of the known surfactant solutions are that in the presence of hydrocarbons such as e.g. lubricating oil or motor oils or generally fatty lubricants that can easily enter pipelines through pumps and valves lose their effect as SB to a small residue or even completely.

Surprisingly, it was now found that, in contrast to all surfactants previously known as SB, the compounds listed below in their pure form, even without any additives, are effective in aqueous solution already in the smallest concentrations, and also in the presence of hydrocarbons such as lubricating and motor oils as flow accelerators. Furthermore, it was found that the compounds, even under permanent stress over weeks, do not show a decrease in their effectiveness as SB, and that some compounds which are then effective above 100°C as SB.

The object of the invention is new quaternary ammonium compounds of formula

where R means n-fluoroalkyl, n-fluoroalkenyl, n-alkyl, n-alkenyl or a group of formula

or

Rf-(CH2)yB(CH2)x-

Rf means n-fluoroalkyl or n-fluoroalkenyl, R1 means hydrogen, methyl or ethyl, X means a number from 2 to 6, y means 0, 1

. or 2, B means an oxygen or sulfur atom,

K<+>means a cation with the formulas

R» means hydrogen, C 1 -C hydroxyalkyl, C 1 -C 6 alkyl, benzyl or phenyl, R 1 means hydrogen, ethyl or ethyl, R 2 resp. may be the same or different and mean hydrogen or C^-C^-alkyl and A~ in the case that fluorinated groups under the meaning of R, mean an n-alkyl-, n-alkenyl- or n-fluoroalkylsulfonate anion, a n -alkyl, n-alkenyl or n-fluoroalkenylcarboxylate anion, a benzoate, phenylsulfonate, naphthoate, iodide, rhodanide anion or an anion of the formula C Cl_ ,,C00-J n zn+i with n = 1, 2 or 3, and A in the case of non-fluorinated groups under the meaning of R means an n-alkyl, n-alkenylcarboxylate anion, n-fluoroalkyl or n-fluoroalkenylcarboxylate anion or n-fluoroalkylsulfonate or n-fluoroalkenylsulfonate anion, the compounds are excepted for the cases R = fluoroalkyl and K<+>trialkylammonium and A iodide, R = alkyl and K<+>= N+H3 and A~ = fluoroalkylcarboxylate and R-K+ = (C^-C^)-trialkylammonium, A - = fluoroalkyl sulfonate and fluoroalkyl carboxylate, likewise the salts of the formulas / C._H__N(CH~)~/+

for n = 12-14

and x = 1-3.

Preference is hereby given to such compounds with the formula R-K+A~, where R means C8-C8-n-fluoroalkyl,

C 8 -C 10 -n-fluoralkenyl, C 1 -C 2 -n alkyl or

C-^H^^-n-alkenyl, or a group of the formulas

or

Rf-(CH2)yB(CH2)x-

Rf means C8-C-4-fluoroalkyl or C8-C14-n-fluoroalkenyl, R means methyl or ethyl, X means an integer from 2 to 6,

y means 0, 1 or 2, B means an oxygen or sulfur atom, K<+>means a cation of formula

?4

+N-R 2 , R 2 means hydrogen, C 1 -C 4 -hydroxyalkyl, methyl or

R4ethyl,

R^ means hydrogen, R^ means hydrogen or methyl or ethyl, and A in the case of fluorinated groups under the meaning of R means a C 1 -C 8 -n-alkyl or n-alkenyl sulfonate anion, a trifluoromethyl or pentachloroethyl sulfonate anion, a Cg-Cg-n-alkyl or n-alkenylcarboxylate anion, a C-^-C^-n-perfluoroalkyl or C^-C^-n-perfluoroalkenylcarboxylate anion, an anion of formula

R 5 -COO or -SO 3 , R 8 means C 1 -C 4 -alkyl, C 2 -C 5 -alkenyl or C, -C 1 - - alkoxy, in positions 3, 4 or 5 to R 3 , or R

lb b g

means hydrogen when R7 means hydroxy, R^ means hydrogen or hydroxy, positions 2 or 3 to R5, or R^ means NO2~,

F-, Cl", Br" or J~ in position 3 to R^, Rg means hydrogen or methyl, or A means an iodide, rhodanide anion or an anion of the formula C2Cl2n+1COO- with n = 1, 2 or 3 . C atoms in the carboxylate anion and n means the number of C atoms in the group R, an n-fluoroalkyl or n-fluoroalkenyl sulfonate anion, the sum of (2y + n) must amount to 17 or 18, when y means the number of C atoms in the sulfonate anion and n the number of C atoms in the group R, or A means an n-alkyl or n-alkenylcarboxylate anion, the sum (z + n) must be a whole number greater than 23 except n = 16 when z means the number of C -atoms in the carboxylate anion and n the number of C atoms in the group R.

Particularly preferred are the compounds of formula R-K<+>A, where R-K<+>means a cation of formula

R means a group with the formula

<C>n<F>2n+l<-C>a<H>2a<->' C n^n^a-l"'<C>n<F>2n+l<-C>ONRl<C>kH2k - or<C>n<F>2n+l<-C>2<H>4SCkH2k<->'<C>n<F>2n+l<S>°2<NR>l<C>k<H >2k<->'

n means a number from 2 to 10, a means a number from 2 to 20,

k means a number from 2 to 16, the sum of (2n+a) and (2n+k) being a number from 12 to 24, R4 means methyl or ethyl, R4 means methyl, ethyl, hydroxymethyl or hydroxyethyl, R^ means methyl or ethyl ,

A~ means a 2-hydroxyphenylsulfonate, m-halobenzoate or salicylate anion, an anion of formula

wherein Rc means COO- or SO,- and R means C H0 or C H_ - 5 3 6 n 2n+l n 2n or C H„ ,,-O- with n equal to a number from 1 to 4 in the positions

n 2n+l

3, 4 or 5 to R5, or A- means a 2-hydroxy-1-naphthoate-, 3- or 4-hydroxy-2-naphthoate-, 2-hydroxy-naphthalene-1-sulfonate-,

3- or 4-hydroxy-naphthalene-2-sulfonate anion, or A- means an anion of formula CF^SO^-, or n-cxH2x+1-SO3-'-^et x means 6, for the case that (2n+a) at least means 18, x is 7, in which case (2n+a) is at least 16, or x is 8, in which case (2n+a) is a number from 14 to 18, or A- is an anion of the formula n-CxF2x+1-COO-, where x means 2 or 3, when (2n+a) is a number from 16 to 22, or x is 4 or 5 when (2n+a) is a number from 14 to 20, or x is a number from 6 to 9 when (2n+1) is a number from 14 to 22, or A- means an anion with the formula SCN~, J~ or CCl3COO~ in which case n is at least 6 and (2n+a) at least is 16.

Particularly preferred are also the compounds of formula R-K<+>A—, where R-K<+>means a cation of formula

n means a number from 1 to 22, R4 means methyl or ethyl, R2 means hydrogen, methyl, ethyl, hydroxymethyl or hydroxyethyl, A- means an anion of the formula n-C2F2x+^-COO-, where x is 2 or 3, when n+ 2x is a number from 20 to 28, or x is 4 or 5, when n+2x is a number from 20 to 26, or x is a number from 6 to 9, when (n+2x) is a number from 19 to 22, or A- is an anion with the formula n-CxH2x+^COO-, where x is a number from 7 to 9, when (n+x) is a number from 23 to 31 except in the case n = 16 or A- is a anion with formula n_cxF2X+i-SO3-'where x is a number chosen so that the sum (2x+n) amounts to 17 or 18.

Of particular interest are the compounds of formula (<CgF>17SO3~)(R4-N(R1, R2, R3)), where Rx means methyl or ethyl, R2 means methyl or ethyl, R3 means hydrogen, ethyl or methyl and R4 means hydrogen, methyl or ethyl, as well as of the formula (<C>n<H>2n+1<+>NH3) ( cxF2x+ lC00~)' where n is a number from 14 to L1 18 and x means a number from 1 to 3, especially 1 .

The Eor compounds according to the invention can be prepared as follows: In the case of ammonium iodides containing perfluoroalkyl groups, the appropriate starting point is the corresponding dimethylamines, resp. amide amines, med-dimethylamine structures and quaternizers; with methyl iodide. The reaction can take place in lower alcohols, such as methanol, ethanol, isopropanol and the like as a solvent. The formed trimethylammonium iodides are in this case soluble in the mentioned alcohols. However, the quaternization can also be carried out in an aprotic solvent such as Cl 2 , CHCl 2 , CH 2 Cl 2 or 1,1,2-trichloro-1,2,2-trifluoroethane. The reaction proceeds below the reflux temperature of the respective solvent. In order to increase the reaction rate, however, it is appropriate to carry out the temperatures at 100 or 120°C, since, however, due to methyl iodide's low boiling point, work must be done under pressure.

Hexahydro- or octahydrop erfluoroalkyltrimethylammonium iodide of the general formula

<ffi>e

^"RF (CH2)n<N>(<CH>3)3)<J9>n<=>3,4

can also be prepared by direct alkylation of trimethylamine with the corresponding iodides containing perfluoroalkyl groups.

If the desired perfluoroalkyltrimethylammonium carboxylates are to be prepared, it is appropriate to first prepare the silver salts of the relevant carboxylic acids. To this end, the carboxylic acids are mixed with a stoichiometric amount of alkali. Since it is a water-soluble alkali salt, silver nitrate solution is used. The silver core carboxylate that forms is poorly water-soluble, precipitates and can be sucked off and dried.

The production of the perfluoroalkyltrimethylammonium carboxylates takes place best in an aqueous solvent, such as methanol, ethanol or isopropanol, by combining stoichiometric amounts of silver carboxylate and perfluoroalkyltrimethylammonium halide at temperatures of 50-60°C. After cooling, the silver halide formed is sucked off and by evaporation of the filtrate the desired trimethylammonium carboxylate containing perfluoroalkyl groups is obtained. A further purification can take place by recrystallization from solvents, such as acetic acid ethyl ester, acetone, acetonitrile.

In an analogous way, it is possible from the perfluoroalkyltrialkylammonium halides by reaction with corresponding silver salts in

lead the others under the meaning of A listed anions.

A further manufacturing possibility for the desired perfluoroalkyl group-containing trimethylammonium carboxylates also exists

in the preparation of alkyltrimethylammonium hydroxide solution by treating alkyltrimethylammonium halide or other salts a strong basic anion exchanger, which is to be carried out in an anhydrous solvent such as methanol or ethanol. It is then neutralized with the desired carboxylic acid, and salts are recovered from the solution by evaporation.

The quaternary ammonium compounds where K<+> denotes a pyridinium ion can be prepared by reacting compounds of formula R-J with pyridine b to substituted pyridines.

The aforementioned compounds are suitable for reducing the frictional resistance of aqueous media. They are added in concentrations of 0.01 to 5% by weight, preferably 0.05 to 1% by weight, particularly preferably 0.1 to 0.5% by weight. For each surfactant, however, depending on the temperature, there exists a different lower critical concentration limit, for a sufficient effect as SB

which, however, as described below, can be determined by a simple preliminary test. The effect as SB depends on the temperature. Said compounds work together in a temperature range from 0°C to 145°C. A single surfactant shows an effect like SB, however only over a temperature interval of approx. 45°C

(-20°C). The lower temperature limit for all surfactants is the dissolution temperature (isotropic dissolution) or better Krafft

the point. However, if the surfactant is in solution, the solubility temperature can in most cases be lowered for a few hours to weeks around 5 to 25°C, without loss of the effect as SB occurring. An application of the surfactants such as SB

which remains in solution until the melting point is formed is possible at temperatures below 0°C when the water's melting point is lowered by the addition of an organic solvent, such as e.g. ethylene glycol or isopropanol. A lowering of the melting temperature of the water by electrolyte addition such as NaCl without loss of effect as SB is only conditionally possible. In particular, as example 2 9 shows, a number of the mentioned surfactants are also effective as SB at temperatures above 100°C.

The effect of the aforementioned compounds such as SB was not only investigated in deionized water, (E-water) at a pH value of 5 to 7,

but different salts (foreign electrolytes) such as e.g. NaCl, CaCl2, A1C13, Na2C03, CaCC>3, Na3PC>4 and others and also the solutions' pH value varied by adding NaOH or HCl. It turned out that the addition of foreign electrolytes led to no effect (see examples 8, 9,

10 and 11) until an improvement (see examples 14, 15) of the effect as SB, an analogous relationship occurs when changing the pH value. The amount of foreign electrolyte that can be added to the aqueous surfactant solution is limited upwards by the concentration where a salting-out effect occurs for surfactants associated with a decrease or complete disappearance of the effect of SB (compare examples 8, 9, 10, 14, 15, 16) . The highest concentration is also determined by the foreign electrolytes and is the lower the higher the value (charge) of the anion or cation. Instead of adding the surfactants mentioned according to the invention, it is also possible to proceed in such a way that one mixes the halogen salt of the cation R,-K<+>Hal , which e.g. x (<C>n<P>2n+l<C>l<H>21<N>(CH3)3)<Hal>' (<C>n<H>2n+l

<V,2n+lClH21N(CH3,3)<Hal>'

CnF2n+l<C>0NHC2H21N(CH3)3) Hal'

<C>n<F>2n+lS02N(C2H5) C^NfCI^ Hal or

(CnF2n+1CH2CH2SCH2CH2N(CH3)3)A

with A = Hal" of CH-SO ~

3 4

or the corresponding pyridinium compounds with Hal = Cl or Br with molar ratio 1:1 with an alkali salt of the anion NaA,

like for example. sodium salicylate or other sodium hydroxybenzoates or sodium 3-hydroxy-2-naphthoate or sodium hydroxynaphthoates, or use the sodium salts of the aforementioned carboxylic and sulfonic acids as flow accelerators. The effect is then similar to the effect achieved in the pure surfactant salts with the addition of alkali halides. Also mixtures that deviate from the molar ratio, e.g. 1:1 shows the effect as SB.

The maximum effect of the flow accelerators also depends on the time that has passed since the preparation of the aqueous surfactant solutions. It is true that the surfactant solutions immediately after the formation of the solution show an effect as a flow accelerator, however, this effect can change clearly within a week. The time required to achieve constant action can easily be determined for this case by simple experiments. In most cases, a constant effect is achieved after 1 to 3 days, in some cases after a week. A change, i.e. an improvement or decrease in the effect as SB, then no longer occurs.

Of some surfactants such as e.g. hexadecylpyridinium salicylate is known (H. Hoffmann et al., Ber. Bunsenges. Phys. Chem. 85,

(1981) 255), of a completely determined for each surfactant characteristic concentration with CMC^, large, not build up. spherical,

mostly rod-shaped micelles of the individual surfactants.

Surprisingly, it was now found that surfactants in aqueous solutions are always effective as flow accelerators when, for concentrations greater than CMC, they form non-spherical, preferably rod-shaped micelles. The spherical, preferably rod-shaped micelles, are present when, in the investigation of the isotropic tension resolution using the methods of electric birefringence with a pulsed, square electric field (E. Fredericq and C. Houssier, Electric Dichroism and Electric Birefringence, Claredon Press, Oxford 1973 and H . Hoffmann et al, Ber. Bunsenges, Phys. Chem. 84 (1981) 255) there is a measurement signal from the fall of which it is possible to determine a relation time of numbers greater than 0.5 ys. The lower concentration limit from a surfactant in aqueous solution acts as a flow accelerator, and is therefore always determined by means of CMC-^, preferably at 1.3 to 2 times the concentration value of CMC^. The determination of CMCjjer e.g. possible by measuring the electrical conductivity of the surfactant solution in dependence on the surfactant concentration as described by H. Hoffmann et al., (Ber. Bunsenges. Phys. Chem. 85 (1981) 255). It turned out that the value of CMCjj is temperature dependent, and shifts with increasing temperature to higher surfactant concentrations.

For determining surfactant concentrations that are minimally necessary to achieve a sufficient effect as SB in a specific temperature range, the determination of CMCjj at the application temperature by means of electrical conductivity is a suitable test.

The investigation of the aforementioned surfactants on their effect as SB, in most cases, took place in the usual way, as for the respective aqueous solution of the surfactant, the pressure drop A P over the section L was measured through a pipe with cross-section d for different flow rates u.

from these values, it is possible to calculate dimensionless large friction coefficients A and Reynolds number Re.

where 6 means the density and v the kinematic viscosity. Usually used for 6 and resp. the corresponding values of the pure solvent, water. The thus formed values A , Re, for the investigated tensin solutions, were compared to the usual double logarithmic plot A versus Re with the corresponding values for pure water, reproduced by

An effect such as SB or also friction reduction exists when it concerns: ^H2°~^SB >0'resP*the size of the friction reduction in % is calculated according to:

As can be seen from fig. 1, the aforementioned tension solutions act as SB so that the percentage reduction in friction increases with increasing Reynolds number, then, however, after having

exceeded a certain Reynolds number Re , again quickly off-

J max 3J r

takes at maximum percentage friction reduction. In the following text, the degree of the effect of a surfactant solution - such as SB, shall be characterized by the size of Re , according to this

max

does a tension resolution with R^max= 20,000 have a better effect as SB, than a tension resolution with Re at 10,000:.' It

ITlclX

associated a-value must be characterized with a . The of-

max

However, the determining factor for the maximum effect is not the Reynolds number but the wall shear stress T^:

that Re for the same SB takes on different values when

max x

different pipe diameters (comp. ex. 7 and 28 and ex. 17 and 29). However, if all SBs are examined with the same apparatus with the same pipe diameter, Remax is a suitable size for comparing the effect of SBs with each other. The examination of the surfactant solutions often only gave reproducible results when the aqueous solutions of the surfactant salt before the measurements or

was stored for approx. 1 week at measuring temperature. Admittedly, the solutions also show an effect as a flow accelerator immediately after formation, which, however, can also clearly change within a week.

The surfactants treated in this way were subjected to numerous tests. Thus, permanent tests over several days, as shown in example 28, show that with the listed surfactants, no decrease in their flow-accelerating effect occurs due to mechanical or chemical degradation. Furthermore, it turns out that the effect as Se of the mentioned surfactants increases with increasing concentration, although the viscosity of the solution also increases, so that the percentage reduction in friction at lower Reynolds number becomes worse as can be seen from fig. 1.

The investigations carried out show that the aforementioned surfactant salts are suitable as flow accelerators everywhere where water is pumped through the pipeline, especially where water is pumped around in a pipeline system constantly in the circuit, such as e.g.

in cooling and heating circuits, as a high long-term stability of SB, which the aforementioned surfactant salts have, is absolutely necessary here. In addition, some of the surfactants mentioned show a property especially for district heating networks, as these surfactants also above 90°C under stress over weeks (ex. 28 and 29) retain their effect, as a flow accelerator.

The dosing of surfactant salts in the water flowing through the pipelines can take place both in the form of a concentrated surfactant solution (1-10% by weight) and also by adding the pure crystalline surfactant salts. Due to the good mixing effect, an addition in the pipeline system shortly before a pump is the most favorable place.

Example 1

1,1,2,2,3,3,4,4-octahydroperfluorododecyl trimethyl ammonium salicylate. a) Preparation of 1,1,2,2,3,3,4,4-octahydroperfluorododecyl-trimethylammonium iodide.

100 g of CgF17(CH2)4J and 30 g of trimethylamine condensed at -20°C were filled into a 250 ml stainless steel autoclave and stirred under pressure for 10 hours at 80°C. After the autoclave had cooled, excess trimethylamine was degassed with formed quaternary ammonium salts precipitated with hot methanol and filtered. The filtrate was evaporated to dryness on a rotary evaporator. Yield is crude product: 103.5 g = 96.9% of the theoretical of a pale yellow powder. For further processing, the product was recrystallized from acetone.

b) Preparation of the salicylate.

48.4 g of salicylic acid and 14.0 g of NaPH were dissolved in 100 ml of water.

This solution was added to a solution of 59.5 g of silver nitrate in 100 ml of water, and stirred well for half an hour. The secreted silver salicylate is suctioned off over a filter nutch and washed with 50 ml each time of water, methanol and acetone. It is then dried in a desiccator with water. Yield 79 g = 92.1% of the theoretical.

In a solution of 13.2 g of that according to ex. la manufactured product with formula

(CgF17(CH2)4N®(CH3)3) j"

4.9 g of silver salicylate are added to 100 ml of methanol. The mixture is heated to approx. 50°C and then aspirate from precipitated silver iodide. The clear, colorless filtrate is evaporated on a rotary evaporator. 11.8 g of crude product is obtained as a colorless powder which is recrystallized from acetone. Melting point 153°C. Titration with perchloric acid in glacial acetic acid with a molecular weight of 650 (calculated 671).

The conductivity measurement shows that CMC-j. and CMC^ coincide

for this compound, the values are for 55°C 270 ppm (0.42 mmol/1) and for 70°C 375 ppm (0.58 mmol/1).

Example 2

1,1,3-trihydroperfluorododecenyl trimethylammonium salicylate

a) Preparation of 1,1,2-trihydroperfluorododecenyltrimethylammonium iodide.

100 g of CgF19CF=CHCH2N(CH3)2

(manufactured according to US patent 3,535,381) is dissolved in 100 ml of di-isopropyl ether and mixed in a one liter glass autoclave with 24.9 g of methyl iodide. After 10 hours of stirring at 80°C under intrinsic pressure, it was cooled, the mixture was evaporated on a rotary evaporator, the precipitated quaternary salt was sucked off and dried. Yield 118.5 g = 94.5% of the theoretical. For the further reaction, the product was recrystallized from acetone.

b) The preparation of the salicylate.

To a solution of 14.3 g (CgFlgCF=CHCH2<N>(CH )3) J

4.9 g of silver salicylate was added to 50 ml of methanol and the mixture was heated with stirring at 50°C. After 30 minutes, the clear filtrate is evaporated from the precipitated AgJ and evaporated to dryness on a rotary evaporator. 12.8 g of crude product is obtained, corresponding to 89.7% of the theoretical amount as light yellow powder.

The product can be recrystallized from acetone. Sm.p. 173°C

(under cleavage). Titration with perchloric acid in glacial acetic acid gives a molar mass of 739 (calculated 723).

The CMC values, determined by conductivity measurements, amount to:

25°C 124 ppm (0.17 mmol/1), 55°C 225 ppm (0.31 mmol/1) and 70°C 645 ppm (0.87 mmol/1). Example 3 1,1,2-trihydroperfluorodecenyl-trimethylammonium 3-hydroxy-2-naphthoate. a) Preparation of 1,1,2-trihydroxyperfluorodecenyltrimethylammonium iodide.

80 g of C7F15CF=CHCH2N(CH3)2

was dissolved in 250 ml of diethyl ether, mixed with 24.1 g of methyl iodide and then heated in a 1-liter glass autoclave for 8 hours at 80°C. After cooling, half of the used solvent was distilled off on a rotary evaporator, the precipitated quaternary salt was filtered off and washed twice with 50 ml of diethyl ether each time. Yield 97.3 g, corresponding to 93.3% of the theoretical. The further processing is recrystallized from acetone.

b) Preparation of the 3-hydroxy-2-naphthoate.

65.9 g of 2-hydroxy-2-naphthoic acid dissolved in 100 ml of methanol and added 14.0 g of NaOH, dissolved in 50 ml of water. While stirring, a solution prepared from 59.5 g of silver nitrate and 100 ml of water is slowly added. The poorly soluble silver naphthoate is formed which is suctioned off and washed each time with 100 ml of water, methanol and acetone.

After drying in vacuum, 98 g = 94.9% of the theoretical amount of an approximately colorless salt is obtained.

To a solution of 9.2 g (C7F15CF=CHCH2N(CH3)3) J~

in 200 ml of methanol, add 4.4 g of the above-mentioned silver 3-hydroxy-2-naphthoate. It is briefly heated to approx. 60°C and suction after cooling from precipitated silver iodide.

The clear filtrate is evaporated to dryness on a rotary evaporator, the residue is then recrystallized from acetone. Yield 8/4 g corresponding to 83% of the theoretical.

This compound was filtered with perchloric acid in glacial acetic acid. From the consumption, a molar mass of 653 (calculated 673) is calculated.

Example 4

1,1,2-trihydroperfluorododecenyl-trimethylammonium perfluoro-propionate.

In a solution of 4.3 g of the (CgPlgCE=CHCH28(CH3)3) prepared according to example 2a) J"

5.4 g of Ag propionate were stirred into 100 ml of methanol. After brief heating of the mixture, the precipitated Ag J is sucked off. The clear filtrate is evaporated on a reaction evaporator. Crude yield 14.2 g of an approximately colorless powder, which could be recrystallized from a mixture of acetone/1,1,2-trichloro-1,2,2-trifluoroethane in a 1:1 volume ratio. Sm.p. 14 8°C.

The titration with perchloric acid in glacial acetic acid gave a molar mass of 759 (calculated 749). The CMC values determined by conductivity measurements are: 55°C CMCZ179 ppm (0.23 mmol/1), CMC^700 ppm (0.92 mmol/1), 70°C CMC.,. 250 ppm (0.33 mmol/1), CMCX11100 ppm (1.5 mmol/1).

Example 5

Cetyltrimethylammonium perfluorobutyrate.

To a solution of 6.4 g of cetyltrimethylammonium chloride (commercial product) in 50 ml of methanol was added 6.4 g of silver perfluorobutyrate (prepared analogously to example 1b from perfluorobutyric acid and AgNO 2 ) dissolved in 50 ml of methanol. It is heated for 10 minutes at approx. 60 C, cools and extracts from precipitated dry chloride. The filtrate is freed of solvent on a rotary evaporator, the residue, a yellow powder, (14.2 g) was recrystallized from acetone/1,1,2-trichloro-1,2,2-trifluoroethane. Sm.p. 152°C.

The titration with perchloric acid in acetic acid gives a molar mass of

506 (calculated 497).

The CMC values determined by conductivity measurements amount to:

25°C CMCj= CMX1120 ppm (0.24 mmol/1), 55.5°C CMCj126

ppm (0.25 mmol/1), CMCX1370 ppm (0.73 mmol/1), 69.5°C

CMCj2 07 ppm (0.41 mmol/1), CMCXX 97 0 ppm (1.9 mmol/1).

Example 6

Tetramethylammonium perfluorooctyl sulfonate.

a) Preparation of tetramethylammonium iodide.

29.1 g of trimethylamine cooled to -20°C was filled into a cooled

250 ml stainless steel autoclave, mixed with 70 g methyl iodide dissolved in 70 ml methanol. After closing the autoclave, it is shaken for 10 hours at 80°C. After cooling, the autoclave is de-energized, the contents taken up with hot methanol and filtered. The filtrate is evaporated to dryness on a rotary evaporator. It is recrystallized from a mixture of water/methanol.

b) Preparation of perfluorooctyl sulphonate.

In a solution of 6.0 g of tetramethylammonium iodide in 50 ml

methanol/water in a volume ratio of 1:1, 18.2 g of the silver perfluorooctylsulphonate prepared analogously to example 1b is dissolved in 100 ml of water/methanol (volume ratio 1:1).

After brief heating (10 minutes) at 60°C, cool, filter off precipitated silver iodide and dry. 16.6 g of a powdery, yellowish salt is obtained which is recrystallized from a mixture of acetone/methanol/1,1,2-trichloro-1,2,2-trifluoroethane (in a volume ratio of 1:1).

After titration with perchloric acid in glacial acetic acid, the product has a molar mass of 586 (calculated 573).

From conductivity measurement it comes at 4 0°C CMC-j. = CMC^ 118 0 ppm (1.1 mmol/1).

Example 7

Of the compound characterized in example 1

(abbreviated: (CF)Q(CH)4Ta-Sal) a concentration range of 200, 500, 750, 1000, 1500 and 2000 ppm by weight was set in deionized water, with corresponding weight amounts of 0.2, 0, 5, 0.75, 1, 1.5 and 2 g of the (CF)g (CH)4Ta salt were weighed with deionized water to 1000 g. During the solution (solubility temperature approx. 40°C) the solution was briefly heated to approx. 90°C, and after cooling to 55°C stored for 1 week without stirring at this temperature.

Research on friction reduction was then carried out in a turbulence rheometer (Polymer Letter 9, 851 (1971)), as analogously in a syringe, a quantity of liquid of 1.5 liters is pressed by means of a piston through the measuring tube. The movement of the piston is accelerated during the measurement, so that the overall flow curve as shown in fig. 1 is obtained in one measurement. The diameter of the measuring tube was 3 mm, the measuring distance < for AP 300 mm and the inlet distance 12 00 mm.

In this apparatus, the same concentration range was measured at 70°C and 90°C after the solution had also previously been heated for a week at 70°C and 90°C. Then the solutions at 200, 500, 750 and 1000 wt ppm of (CF)g (CH)4TA salt were cooled to room temperature (25°C), i.e. to 15°C below the solubility temperature, stored for 1 week at this temperature, and finally also measured in a turbulence rheometer.

Table 1 includes the results of all measurements of 25, 55,

70 and 90°C when reproducing Re and a .1 the figure is max max

the X versus Re flow curves at 55°C for 500, 1000 and 2000 ppm solutions of (CF)g(CH)4TA-sal in E-water are listed in double logarithmic notation. As can be seen from table 1, the effect of the reduction in friction is also present when the solubility temperature is undershot at around approx. 15°C even after a week.

Example 8

Different amounts of NaCl were combined..with (CF)o 0(CH)4. TA-sal, discussed in Example 7, was added to aqueous solutions whose concentrations of (CF)g(CH)4TA-sal each time 75 0 ppm (1.15 mmol/1) and NaCl (1 mmol/1) were chosen as follows : 0.1, 0.5, 1.14, 5, 10, 100, 1000.

The results of the investigations for friction reduction at 40°C in the turbulence rheometer are listed in table 2. As can be seen from

table, the NaCl addition only has a small effect up to 10 mmol/1 NaCl, the maximum concentration of NaCl is between 100 and 1000 mmol/1. Table 2 also includes some measurements at 25°C, i.e. 15°C below the solubility temperature.

Example 9

Different amounts of Na 2 CO 3 together with (CF)g(CH) 4 TA-Sal, as discussed in Example 7, were added to an aqueous solution, the concentrations of (CF)g(CH) 4 TA-Sal each time 400 ppm (0, 62 mmol/1) and Na2C03 (in mmol/1) chosen as follows: 0.1,

0.6, 5, Table 3 reproduces the results of the investigations on the friction reductions in the turbulence rheometer at 4 0°C. As can be seen from table 3, the presence of Na2C03 affects the effect of SB only slightly, the maximum concentration of Na2S03 is 5 mmol/1 at pH = 11.2,

Example 10

Different amounts of Na^PC^ together with (CF)g(CH)4 TA-Sal, as indicated in Example 7, were added to aqueous solutions, the concentrations of (CF)g(CH)4TA-Sal each time being selected 400 ppm (0.62 mmol/1) and of Na^PC^ (in mmol/1) as follows: 0.1, 0.6, 5. Table 4 reproduces the results of the investigations on friction reduction in turbulence rheometer.

Example 11

Two solutions of (CF)g(CH)4TA-Sal with a concentration of 400 ppm in E-water were mixed with HCl resp. NaOH adjusted to the pH values 3 or 10.5, pretreated as described in example 7, and examined at 40°C in a turbulence rheometer. At pH = 3, Remax = 14900 (- 1500) and amax = 63 {- 3) appeared and at pH = 10.5 at Rem of 16200 (- 1600) and an a v of 69 (- 3).

max max

Compared to pure compounds in E-water at pH 7.4,

Re max = 15500 and a max = 65, the different ^pH values cause only a small change of the SB effect which is within the range of the measurement accuracy.

Example 12

As discussed in example 7, solutions were placed in E-water with different concentrations of salicylates listed below and examined at different temperatures in turbulence

rheometer on friction reduction.

1) (<CgF>13C4<Hg>N(CH3)3)+ Sal"

at 25°C: CMCJ= CMC^ 1110 ppm

at 55°C: CMCj = 1600, CMC^ = 2560.

<2>) (<c>ioF21C4H8N(CH3}3 )+ Sal~

at 69.2°C CMCj= 85 ppm, CMC = 581 ppm

at 25°C CMCj= CMCjj= 48 0 ppm,

at 55°C CMC]. = 720 ppm, CMC^ = 2740 ppm.

Sal means each time the salicylate anion. Table 5 reproduces the results.

Example 13

As discussed in example 7, solutions were placed in E-water with different concentrations of salicylates (Sal) listed below and examined at different temperatures in a turbulence rheometer for friction reduction.

<1.>(<C>7F15CF = CHCH2N(CH3)3)+ Sal"

at 25°C: CMCj= CTAC^= 880 ppm

at 4Q°C: CMCj= CMC^ = 1200 ppm.

<2.>(<C>gFigCF = CHCH2N(CH3))<+>Sal", comp. ex. 2.

3. (<C>7F15CF = CHCH2N(C<H>3)2CH2CH2OH)<+>Sal"

at 55°C: CRCX= 1390 ppm and CMC1X= 1700 ppm {- 250)

at 2 5°C* CMCj= CKC^= 96 0 ppm.

4. (C9FlgCF = CHCH2N(CH3)2CH2CH2OH) Sal

at 4Q°C: CMCj= 300 ppm, CMC^ = 600 ppm (- 200 ppm).

Table 6 reproduces all results.

Example 14

Different amounts of NaCl became the same with (C_F,_CF = CHCH N

y i y2(CH^)^) Sal as mentioned in ex-* .7, added to aqueous solutions whose concentrations of (CQF, QCF=CHCH„N (CH-.) 0) Sal each

y x y2.5 in

time was chosen to be 750 ppm (1 mmol/1) and of NaCl (in mmol/1) chosen as follows: 0.1, 0.5, 1.0, 5, 10, 100, 500. The results of the investigations on friction reduction in the turbulence rheometer at 55°C are listed in table 7. As can be seen from the table, the addition of NaCl up to a concentration of 10 mmol/1 causes a clear improvement in the effect as SB. Thereafter, a decrease in the SB effect takes place. High concentration of NaCl is greater than 500 mmol/1 or 2.9% by weight

NaCl.

Example 15

Different amounts of CaCl 2 „ were added together with (C y F i yCF = CHCH2N (CH3)3) Sal, as mentioned in example 7, to an aqueous solution in concentrations of (Cny F i y CF = CHCH z N(CH.j ) 3) Sal each time was chosen at 750 ppm (1 mmol/1) and CaCl2( in mmol/1) was chosen as follows: 0.1, 0.5, 1, 5, 10, 100, 500. The results of the investigations on friction reduction1 see in turbulence rheometer at 55°C are listed in table 8. As results in table 8 show, the addition of CaCl^ up to a concentration of 10 mmol/1 causes an improvement then a reduction of the effect as SB. The maximum concentration of CaCl^ is greater than 500 mmOl/1, resp. 5.5% by weight.

Example 16

Different amounts of A1C1 3 , together with (C 9 F 19CF=CHCH^N(CH^)^) Sal, as indicated in example 7, were added to an aqueous solution, the concentration of (C 9 F 19 CF= CHCH 2 N (CH 3 ) 3) Sal, each time 750 ppm (1 mmol/1) and AlCl3 (in mmol/1) were chosen

were chosen as follows: 0.1, 0.5, 1, 5. The result of the investigations on friction reduction in turbulence rheometer at

55°C is listed in table 9. As the results show at which additions of AlCl^ no improvement of the SB effect, and from 1 mmol/l even a complete suppression of friction slants1 sen.

Example 17

As discussed in example 7, solutions were placed in E-water with different concentrations of the following listed compounds, and examined at different temperatures in a turbulence rheometer on friction reducers1 see. 1) ' (C6<F>13C4H8N(CH3)3)+ Naph"

2) (<C>8<F>17C4<H>8 N(CH3)3+ NaPh~

3) (C10F21 C4H8 N(CH3)3^+ Naph" 4) (<C>8<F>17<C>2<H>4N(0) )+ Naph"

Naph means 3-hydroxy-2-naphthoate anion.

Table 10 indicates the results. Substances 2) and 3) were also

as discussed in example 29 investigated on another flow apparatus at temperatures above 100°C on friction reducers1 see.

Example 18

As discussed in example 7, a solution was placed in E-water with different concentrations of the following listed compounds and examined at different temperatures in a turbulence rheometer on a friction reducer1 see:

1. (CgFigCF = CHCH2N(CH3)3+ CF3 COO~

at 55°C: CMC = CMC^ = 1940 ppm

2. CgFigCF = CHCH2N (CH3) 3) + C F COO~

at 55°C CMCI= 175 ppm, CMC = 700 ppm (- 150)

3. (CgFlgCF = CHCH2N(CH3) 3) C F? COO"

at 70°C CMCI= CMC = 2630 ppm,

4. CgF CF = CHCH2N(CH3) 3) + C^^OO"

5*(C10F21 C4H8 N(CH3)3)+ C2F5COO"

Table 11 reproduces the result.

Example 19

As discussed in Example 7, solutions were placed in E-

water with different concentrations of the following listed perfluorocarbonates, of the n-hexadecyltrimethylammonium cation (C;LgH3 3N (CH3) ) +, abbreviated to C^ TA<+>, and examined at different temperatures a turbulence rheometer on a friction down set1 se.

1. C, r TA<+>C„FrCOO<->

16 2 5

at 25°C: CMC;[= CMC.^ = 1050 ppm

at 55°C: CMCI= CMC = 500 ppm.

2. C_,.TA + c,F_COO~

16 il coll. example.5.

3. C,rTA+ C.F^COO-

16 4 9

at 70°C: CMC]. = 240 ppm, CMC = 952 ppm.

4. C. r TA+CrF,.COO-.

16 5 11

Table 12 reproduces the results.

The substance 3) was examined with another flow apparatus, comp. e.g. 29 also at 107°C on friction reducer1 see.

Example 20

As indicated in example 7, solutions were placed in E-water with different concentrations of the following listed compounds and examined at different temperatures in turbulence rheometer, on friction down set1 see.

1. (N(CH.).<+>Co<F>.<_S>0<->comp. ex. 6

2. (H(C2H5)4+ C8F17S03-

at 25°C: CMC^= CMC = 650 ppm

at 40°C: CMC; [ = CMC = 850 ppm.

Table 13 reproduces the result.

Example 21

As indicated in Example 7, solutions were placed in E-water with different concentrations of the iodides of the compounds listed below and examined at different temperatures in a turbulence rheometer for friction reduction.

<1>'(CaP17 C4H8 N<CH3>3+ J_

at 40°C CMCI= CMC = 450 ppm (- 50)

at 40°C CMCI= CMC = 380 ppm (-■ 50)

3. (C9FigCF = CHCH2N(CH ) )+ J_

4. CF = CHCH.N (CH., ) + J_

r2 3

as R„ consists of chain sections C_F.. to C,.F__.

F J 511 1123

Table 14 reproduces the results.

Example 22

As indicated in Example 7, solutions were set in E-water

of various n-fluoroalkylpyridinium and n-fluoroalkyltrimethylammonium salicylates, the corresponding n-fluoroalkylpyridinium and n-fluoroalkyltrimethylammonium chlorides resp. was weighed in 1:1 molar sodium salicylate, so that the solutions contain equimolar amounts of NaCl in addition to the active surfactants. Table 15 reproduces the results of the investigations on friction reduction in turbulence rheometer. The

equimolar amounts of NaCl are not listed in the table. The abbreviations Sal means salicylate.

Example 23

As indicated in Example 7, solutions were set in E-water

of (C F (CH_) . N(CH,).+ with different motion ions, resp.

ol/Å4 33

as in example 22 the chloride of the n-fluoroacyltrimethylammonium compounds weighed 1:1-molar medii the Na salt of the corresponding anion. Table 16 reproduces the results of the investigations on friction reduction in turbulence rheometer. The equimolar amounts of NaCl are not listed in the table of numbers. Analogously, a solution of (CrF.. (CH.) , N(CH.)_,+ C_F_COO_,

613 24 33 3/

examined in a turbulence rheometer, and the results are listed in table 16.

Example 24

As discussed in example 7, solutions were put in E-water consisting of n-alkyltrimethylammonium cations and perfluorocarbonate anions, the resp. corresponding n-alkyltrimethylammonium chlorides were weighed with the sodium salts of the perfluorocarbonates molar 1:1. Table 17 reproduces the results of the investigations on friction reduction1 see in turbulence rheometer. The equimolar amounts of NaCl are not listed in the table.

Example 25

As indicated in example 7, solutions were placed in E-water consisting of n-alkyltrimethylammonium cations (cnH2n+iN^CH3^3^<+>'and n-alkylcarbonate anions, (cxH2x + lC°°^ ~~' ■ i-(3et resP« the corresponding n-alkyltrimethylammonium chlorides are weighed with sodium salts of n-alkylcarboxylic acids molar 1:1. Table 18

reproduces the results of the research on friction reduction1 see. The equimolar amounts of NaCl are not listed in the table.

Example 26

Solutions of the compound<e>(<c>n<H>2n+iNH3^+ C^COO- were added in E-water at 60°C, respectively, the corresponding primary amines C H„ , NH„ were weighed in with perfluoroacetic acid molar in pre-

n 2n+l 2ri

hold 1:1. After a storage time of approx. 7 days at 60 Cj, the solutions were examined in a turbulence rheometer on a friction slant see. Table 19 reproduces the results.

To achieve an optimal effect as SB, the compounds of the type (C H. NH_)+ A should not be heated above 70°C.

n 2ni 3

Example 27

As indicated in Example 7, a solution was placed in E-water with a concentration of 1000 wt-ppm of the following listed compounds and examined at the different temperatures in the turbulence rheometer for friction reduction.

1. (C8F17S02 N(C2H5) (CH2)3N(CH3)3+ J~

(abbreviated: SC>2TA<+>J<->).

Analogously, it was employed to investigate solutions of salicylates (Sal) of the following compounds:

3. (C8F1^,SO2N (C2H5) (CH2) 3 N(CH3)3<+>Sal" (abbreviated<*>.

S02TA -Sal")

4. (R CH„CH0SCH„CH„N(CH.)-+Sal" (abbreviated: STA<+->Sal<_>)

r 2 2 2 23 3

R_ stands for chain mixture C^F_. to C,_F-_.

r b 3 U 1225

Table 20 reproduces the results.

Example 28

For the investigation of friction reduction1 see in a permanent test at 70°C, a closed flow apparatus was used consisting of a 30 liter storage vessel, a circular pump (type CPK50-250 from the company KSB with mechanical regulation de1), an inductive flow meter and a pipeline of 2x10 m length, with an inner diameter of 29.75 mm.- The determination of the pressure drop AP took place after an associated inlet section over a measuring section of 2 m. For thermostatization, a diving boiler served as electrically heated liquid in the storage container.

During the permanent test, the liquid is constantly pumped off at the bottom

of the storage tank, and is supplied again via the pipeline into the storage tank. For water at 70°C, the pump's transport performance can be varied using a mechanical regulation drive from 3.25 to 14.3 m 3 per hour, corresponding to a pipe diameter of 29.75 mm, the flow rates of 1.3 to 5.7 m/sec. respectively Reynolds numbers from 9,400 to 411,000.

A 1000 ppm solution of (C 0 b F 17 (CH 2 )' 4 N(CH 3 ) 3_) Sal (Sal means the salicylic acid anion) was tested in this apparatus for persistence as a flow accelerator at 70°C. The preparation of the solution took place in such a way that the apparatus (absorption capacity approx. 40 litres) was filled up to a small residue with water, then 40 g of the powdered flow accelerator was added and then the apparatus was filled with the remaining water. After a run-in time of 3 days and 70°C, a Remax of

332,000 (- 30,000 and a = 76% - 4.

max

The permanent test was then carried out at a flow rate of 10.26 m 3/hour, corresponding to a flow rate of 4.1 m/sec. respectively Re = 295,000, over a period of 19 days. Under the specified conditions, the same volume of liquid passed approx.

4.3 times per minute the circulation pump. After 19 days of permanent stress, re-recording of the liquid curve after Re max = 329,000 (- 30,000) and 3 et a max = 77%- 4, ' thus

that no decrease in the effect could be determined by decommissioning.

Example 29

For the investigation of friction reduction1 see in the temperature range from 70 to 135°C, a closed flow apparatus was used, in which a liquid volume of approx. 1*5 liters were pumped into the circuit. With two parallel-connected Netzsch mono-pumps type 3 NU 06, with a production surface1 see from 10 to 150 l/hour and type 2 Ne 15A with a production surface 1 see from 80 to 1500 1/ hour, it is possible in measuring pipes easily with a diameter 6 mm set flow speeds of a total of 0.2 to 14 m/sec. The determination of the flow rate took place in an inductive flow meter, the pressure drop P is determined after an inlet section of 1.83 over a length of 1 m using Ziegler differential pressure measuring boxes (type D 248). Measuring pipe and return pipe are arranged parallel, and arranged vertically due to faster venting. While a combined pressure equalization and deaeration container is placed on the upper cross connection of the two parallel pipes, both pipelines are connected at the lower end above the parallel connected pumps. The entire pipeline, expansion tank and parts of the pumps are sheathed, and are tempered by a thermostat with bath liquid. Measured value and record and assessment of the measurements, pre-

goes over a HP 1000 rain.

The dissolution of the compounds listed below in E-water with different concentrations was investigated in this apparatus at different temperatures. 1. (<c>8<F>i9 (<C>H2)4N(CH3)3+ NaPh" 2. (C1QF21(CH2)4 N(CH3)3+ Sal"

3. (cioF21(CH2)4N(CH3)3)+ Naph-

4. (C16<H>33 N(CH3)3)+ C4Fg COO".

(Sal means the salicylate anion and Naph means the anion of 3-hydroxy-2-naphthoic acid).

After the preparation of the solutions as stated in example 7, further tempering of the solutions took place before a new measurement with a different temperature in the flow apparatus itself, as the solutions resp. for a few hours, resp. overnight circulates at the new measuring temperature in the circuit. The tempering of the samples is sufficient for some at temperatures above 90°C, as the system's equilibrium setting (or the time required to maintain the constant final value for friction slant tte 1 se ) is very short in this temperature range, which was established in some test measurements.

Table 21 shows the results in the form of Re max and amax

Claims (5)

1. Quaternary ammonium compounds with formula where R means n-fluoroalkyl, n-fluoroalkenyl, n-alkyl, n-alkenyl or a group of the formulas Rf-(CH2 )yB(CH2 )x -, Rj means n-fluoroalkyl or n-fluoroalkenyl, R^ means hydrogen, methyl or ethyl, X means an integer from 2 to 6, y means 0, 1 or 2, B means an oxygen or sulfur atom, K+ means a cation with formula R 2 means hydrogen, C 1 -C 4 -hydroxyalkyl, C 1 -C 4 -alkyl, benzyl or phenyl, R 4 means hydrogen, methyl or ethyl, R 4 which can each be the same or different means hydrogen, or C± -C 3 - alkyl and A- means in the case of fluorinated groups under the meaning of R an n-alkyl-, n-alkenyl- or n-fluoroalkyl-sulphon anion, an n-alkyl-, n-alkenyl or n-fluoroalkenylcarboxylate anion, a benzoate- , phenylsulfonate-, naphthoate-, iodide, rhodanide anion or an anion of formula C Cl„ ^,COO~ J _ n 2n+l with n = 1, 2 or 3 and A~ for the case of non?-fluorinated groups under the meaning of R et n- alkyl, n-alkenylcarboxylate anion, an n-fluoroalkyl or n-fluoroalkenylcarboxylate anion, or an n-fluoroalkylsulfonate or n-fluoroalkenylsulfonate anion, the compound being selected for the cases R=fluoroalkyl and K <+> trialkylammonium and A~ : iodide, R = alkyl and K = N+H + and A = fluoroalkylcarboxylate and R-K = (C±- C2)-trialkylammonium, A- = fluoroalkylsulfonate and fluoroalkylcarboxylate, likewise the salts of the formulas for n = 12-14 and z = 1-3. 2. Quaternary ammonium compounds with the formula R-K+A, where R means Cg-C2 -n-fluoroalkyl, Cg-C14-n-fluoroalkenyl, C1-C24-n-alkyl, or C2-C24-n-alkenyl or a group with formula Rf-(CH2 )yB(CH2 )x - Rf means Cg-C-^-n-fluoroalkyl or Cg-C-^-n-fluoroalkenyl, R^ means methyl or ethyl, X means a number from 2 to 6, y means 0, 1 or 2, B means an oxygen or sulfur atom , K <+> means a cation of formula ?4+N-R 4 R 2 means hydrogen, C 1 -C 8 -hydroxyalkyl, methyl or ethyl, R 3 means hydrogen, R 4 means hydrogen or methyl, or ethyl, and A~ in the case of fluorinated groups under the meaning of R a C 1 -C 8 -n-alkyl- or n-alkenylsulfonate anion, a trifluoromethyl cells pentafluoroethylsulfonate anion , a Cg-Cg-n-alkyl or n-alkenylcarboxylate anion, a C-^-C^-n-perfluoroalkyl or C^-C^-n-perfluoroalkenylcarboxylate anion, a R 5 -COO- or -SO 3 -, R 8 means C 2 -C 3 -alkyl, C 2 -C 5 -alkenyl or C 1 -C 6 -Alkoxy in position 3, 4 or 5 to RK , or R means 15 O O hydrogen when R^ is hydroxy, R^ means hydrogen or hydroxy in positions 2 or 3 to R 5 , or R 7 means NO 2~ , F~ , Cl", Br- or J-, in position 3 to Rj., Rg means hydrogen or methyl or A means an iodide, rhodanide anion or an anion of formula C2 Cl2n+l COO <_> with n = 1' 2 or 3' and A~ in the case of non-fluorinated groups under the meaning of R means et n-fluoroalkyl or n-fluoroalkenyl carboxylate anion, the sum of (2 x + n) being an integer from 19 to 24, when x is the number of C atoms in the carboxylate anion and n is the number of the C atom in the group R, n-fluoroalkyl or n-fluoroalkenyl sulfonate anion, the sum of (2y + n) must amount to 17 or 18, when y is the number of C atoms in the sulfonate anion, and n the number of C atoms in the group R, or A means n-alkyl or n-alkenyl carboxylate anion, the sum (z + n) must be a whole number greater than 23, except for n = 16, when z is the number of C atoms in the carboxylate anion and n the number of C atoms in the group R. 3. Quaternary ammonium compounds with formula R-K <+> A according to claim 1, wherein R-K <+> means a cation with formula R means a group of formula C F_ ,,-C H_ -, C F_ - Co 1 ^ * e n 2n+l a 2a n 2n za-l ' <C> n <F> 2n+l -CONRl Ck H2k - or Cn F2n+l -C2 H4 SCk H2k -' Cn F2n+l S02 NRl Ck H2k -' n means a number from 2 to 10, a a number from 2 to 20, k a number from 2 to 6, the sum of (2n+a) and (2n+k) must be a number from 12 to 25, R4 means methyl or ethyl, R4' means methyl, ethyl, hydroxymethyl or hydroxyethyl, R means methyl or ethyl, A means a 2-hydroxyphenylsulfonate, m-halobenzoate or salicylate anion, an anion of formula wherein R5 means COO or SO3 ~ and Rg means cn H2n+i~ or CH_ -or CH_, ,,-0- with n being a number from 1 to 4 in position n 2n n 2b+l _ 3,4 or 5 to Rbr , or A~ means a 2-hydroxyl-naphthoate-, 3- or 4-hydroxy-2-naphthoate-, 2-hydroxynaphthalene-1-sulfonate-, 3- or 4-hydroxy-naphthalene- 2-sulfonate anion, or A means an anion with the formula CF-SO-,- or n-C H_ ,,-SO ~, where x 3 3 x 2x+l 3 is 6, for the case (2n+a) is at least 18 , x is 7 for the case (2n+a) is at least 16 or X is 8, for the case (2n+a) is a number from 14 to 18, or A~ is an anion of formula n-C F _,-C00~, where x is 1 or 2, when (2n+a) is a number from 16 to 22, or x is 4 or 5, when (2n+a) is a number from 14 to 20, or x is a number from 14 to 20, or x is a number from 6 to 9, when (2n+a) is a number from 14 to 22, or A~ means an anion of the formulas SCN~, J~ or CCl-j COO <-> , for the case n at least 6 and (2n+l) at least 16. 4. Quaternary ammonium compounds with formula R-K+A, where R-K <+> means a cation with formula n means a number from 1 to 22, R4 means methyl or ethyl, R2 means hydrogen, methyl, ethyl, hydroxymethyl or hydroxyethyl, A~ means an anion with the formula n-C2 F2x+1 -COO , where x is 2 or 3, when n+2x means a number from 20 to 28, or x is 4 or 5 when n+2x is a number from 20 to 26, or x is a number from 6 to 9, when (n+x) is a number from 14 to 22, or A is an anion with formula n-C H„ ,,COO~, where x is a number from 7 to 9, when x 2x+l (n+2x) is a number from 23 to 31, except in the case of n = 16, or A~ an anion with the formula n-CxF2x+1-S03, where x is a number chosen so that the sum (2x+n) makes 17 or 18. 5. Use of quaternary ammonium compounds according to claim 1 as a flow accelerator.