DE3035641A1 - Per:fluoro-alkyl-alkanol textile finish intermediate prepn. - by reacting per:fluoro-alkyl iodo-alkane with peroxido-carboxylic acid opt. using phase transfer catalyst - Google Patents

Abstract

Perfluoroalkyl-alkanols, (I), are prepd. by reacting perfluoroalkyl-iodoalkanes, (II), with a 1-20C peroxido-carboxylic acid, (III), at -20 to +80 deg.C.,opt. under pressure, and opt. in the presence of water, inert organic solvents and/or standard phase transfer catalysts. At least 3 (pref. 3.1-4) mol. equiv. peroxido-carboxylic acid gps. are used for each mol. of (II). (I), esp. perfluoroalkyl-ethanols, are used as intermediates for the prepn. of water-, oil- and/or dirt-repellent textile finishes. E.g. (I) are converted to their esters with unsatd. carboxylic acids, e.g. acrylic or methacrylic acid, and polymerised. (I) are prepd. from (II) under mild conditions with good selectivity. The reaction prod. of iodine is easily separated and allows an easy recovery of I2.

Description

Process for the preparation of Perfluoroalylyi-alkanols

The invention relates to a process for the preparation of perfluoroalkyl alkanols from the corresponding perfluoroalkyl-iodoalkanes by reaction with peroxidocarboxylic acids.

There are already various processes for the production of perfluoroalkyl alkanols known from the corresponding perfluoroalkyl-iodoalkanes. U.S. Patent 3,246,030 describes the reaction of perfluoropropyl ethyl halides, including iodides, with silver or mercury nitrate, whereby the perfluoropropylethyl nitrate is formed first in a second stage with reducing agents, for example ammonium hydrosulfite or lithium aluminum hydride is converted to the perfluoropropylethyl alcohol. The reaction with silver or mercury nitrate is carried out in a suitable solvent, for example acetonitrile, carried out in the absence of water. After this Processes should be possible in yields of perfluoropropylethanol of 70 to 80%. The total reaction time is considerable and the implementation of the process in two steps cumbersome.

According to a recently proposed procedure (P 30 16 571.0) Perfluoroalkyl-iodoalkanes in the presence of heavy metal cations, known phase transfer catalysts and / or perfluoroalkyl carboxylic acid anions rapidly and with very good yields Perfluoroalkylalkanols unset It is necessary here, however, the resulting, poorly soluble metal iodide in a second stage to work up to regenerate the heavy metal cations as quantitatively as possible.

According to the process of DE-OS 23 18 941 one obtains from the reaction of the perfluoroalkyl-ethyl iodides with amides of the general formula RCONR'R ", in which R, R 'and R "mean hydrogen atoms or lower alkyl radicals, in the presence of Water Mixtures of perfluoroalkyl ethyl esters, ethyl alcohols and ethylenes, the however, with respect to the perfluoroalkyl-ethyl alcohols, generally only low selectivity exhibit.

In DE-OS 28 34 794 a similar process is described in the perfluoroalkyl ethyl iodide with water and comparatively high amounts of N-methyl-2-pyrrolidone implemented. The selectivity of this reaction with respect to perfluoroalkylethanols is good, but despite considerable temperatures (preferably 120 to 160 OC), relatively long reaction times (about 8 to 14 hours) are used will.

According to DE-OS 23 18 677, perfluoroalkyl ethyl iodides are diluted in aqueous solutions of inorganic and / or organic non-oxidizing oxygen acids or hydrogen iodide is saponified and the perfluoroalkylethyl alcohols thus obtained are isolated. Despite the use of considerable reaction times and comparatively high temperatures (190 to about 250 OC) yields of 36 to 88% are obtained, with the Partly form considerable amounts of by-products.

Finally, after another, in DE-PS 12 14 660 described Process perfluoroalkyl ethyl iodide with oleum to give the corresponding sulfuric acid ester implemented and then saponified to the perfluoroalkylethanols. Likewise The process according to DE-OS 20 28 459 works in two stages, in which a perfluoroalkylethyl iodide in a first stage with about 70 to 98% nitric acid in the corresponding Nitric acid ester transformed and this in a second stage in the presence of the usual Hydrogenation catalysts is hydrogenated to the desired alcohols.

A process has now been found which makes it possible to use perfluoroalkyl alkanols from the corresponding perfluoroalkyl iodoalkanane under mild conditions with good Produce selectivity, the reaction product of the iodine being easily separable and enables easy recovery of elemental iodine.

This process for the preparation of perfluoroalkylalkanols from the corresponding perfluoroalkyl-iodoalkanes by reaction with an oxidizing acid, optionally at elevated temperature, is characterized in that the reaction at -20 to about +80 OC, optionally under pressure, in the presence of a peroxidocarboxylic acid, containing 1 to about 20 carbon atoms, and optionally in the presence of one or more of the following substances: water, inert, organic solvents, known Phase transfer catalyst ren, is carried out, per mole of perfluoroalkyliodalkane at least 3 molar equivalents of peroxidocarboxylic acid groups are used.

Peroxidocarboxylic acids are suitable for the process according to the invention, that is to say organic compounds which contain at least one, usually one or two of the following radicals: contain. Because of their easier accessibility, peroxidocarboxylic acids in which the carbon atom in the above formula is linked to an H atom or a straight-chain or branched alkyl radical or an aromatic radical, which can optionally also be substituted, are preferably used. An aliphatic peroxidocarboxylic acid with 1 to 4 carbon atoms, for example peroxidoformic acid, peroxidoacetic acid, peroxidopropionic acid or peroxidobutyric acid and their isomers, or a peroxidobenzoic acid, which is optionally substituted on the benzene nucleus, is particularly suitable. Examples of core substituents are lower aliphatic hydrocarbon radicals such as methyl, ethyl or tert-butyl, halogen such as fluorine or chlorine, the nitro group or the carboxylic acid group, optionally also a second peroxidocarboxylic acid group.

Aliphatic monoperoxido- and diperoxidodicarboxylic acids, which differ, for example, from the malonic, succinic, Glutar.

Adipic, pimelic, cork (or suberic), azelaic or sebacic acid derive.

The production of said peroxydocarboxylic acids respectively Peroxidodicarboxylic acids are carried out by known methods, for example by reaction of non-peroxo-containing carboxylic acids with hydrogen peroxide in acidic Solution; by reaction of the corresponding carboxylic acid chlorides with alkali peroxide or by oxidation of aldehydes, optionally under catalytic Influence actinic light, ozone or heavy metal salts. While the former is the Methods mainly for aliphatic peroxidocarboxylic and diperoxidodicarboxylic acids comes into question, the latter two methods are more suitable for aromatic peroxydocarboxylic acids used.

The preparation of peroxidocarboxylic acids is known and extensive described in the literature, for example by Daniel Swern in the 1st volume of the book "Organic Peroxides Wiley Interscience / New York 1970, pages 315 to 322 and 337 to 474.

Because of the decomposability of the free peroxydocarboxylic acids, they are mostly handled in inert solvents. Examples of such solvents are Hydrocarbons that are liquid at room temperature, such as n-heptane, cyclohexane or toluene as well as chlorinated or fluorinated hydrocarbons such as methylene chloride, chloroform, n-butyl chloride, trifluorotrichloroethane; Ethers such as diethyl ether or diisopropyl ether as well as esters such as ethyl acetate. Such solvents can be used simultaneously also for the solution of solid perfluoroalkyl-iodoalkanes, which with the peroxidocarboxylic acids are to be implemented, serve, especially in the case of higher molecular weight perfluoroalkyl-iodoalkanes and low reaction temperatures.

Another means of making perfluoroalkyl-iodoalkanes, which are among the chosen The reaction conditions are solid to liquefy, the addition of other perfluoroalkyl-iodoalkanes, which have a lower molecular weight.

In a preferred embodiment of the method according to the invention is a peroxidocarboxylic acid in a mixture with the analogous carboxylic acid, which is no Peroxo groups contains, used, for example peroxidoacetic acid along with acetic acid. Such mixtures arise in particular when a Carboxylic acid with hydrogen peroxide, whereby an equilibrium is established in which Peroxidocarboxylic acid in addition to the simple carboxylic acid used as the starting product is present. Such reaction mixtures contain water, which is partly through the reaction of the carboxylic acid with the hydrogen peroxide forms, in some cases already with the hydrogen peroxide as its diluent in the reaction mixture is introduced. A solution of hydrogen peroxide is advantageous for this reaction used in water containing 35 to about 75 wt% hydrogen peroxide and 65 to about Contains 25% by weight of water. Higher hydrogen peroxide contents are also effective, however, the risk of ignition or explosion of the reaction mixture increases.

Contents of less than 35% by weight of hydrogen peroxide generally lead to a deterioration in the yield due to excessive dilution.

The mixing ratio of peroxydocarboxylic acid and not peroxide groups analogous carboxylic acid containing is expediently about 1:10 to 1: 1.

Mixtures of several can also be used for the process according to the invention Peroxidocarboxylic acids and these in turn in a mixture with several analogous ones, not Carboxylic acids containing peroxide groups are used.

The implementation of the peroxidocarboxylic acids with the perfluoroalkyl-iodoalkanes takes place at -20 to +80 OC. The reaction time is generally below -20.degree too long and difficulties arise due to the transition of a liquid reaction line: £ hmr in the solid state. Above 80 ° C occurs increasingly Decomposition of the peroxidecarboxylic acid, the risk of explosion also increases.

Particularly good results are achieved in the temperature range from +10 to +60 ° C.

Usually the reaction takes place in air at normal atmospheric pressure carried out. However, overpressure up to about 1 MPa can also be applied will. The use of inert gases instead of air, for example nitrogen, Argon, or carbon dioxide, can be beneficial.

For the reaction according to the invention, perfluoroalkyl-iodoalkane are used per mole at least 3 molar equivalents of peroxidocarboxylic acid groups are used. Get less used as 3 molar equivalents of peroxidocarboxylic acid groups, the reaction proceeds incomplete, the yield of perfluoroalkyl alkanols decreases. Become useful also not more than 5 to 6 molar equivalents of peroxidocarboxylic acid groups per mole of perfluoroalkyl-iodoalkane used because the use of even larger amounts does not improve the yield but, on the contrary, undesirable mist reactions can occur. Advantageous 3.1 to 4 molar equivalents of peroxidocarboxylic acid groups are used per mole of perfluoroalkyliodoalkane.

A compound of the formula is preferably used as the perfluoroalkyl iodoalkane RfCH2 CIHX used. In the formula mentioned: Rf is a perfluoroalkyl radical, which is straight-chain or terminally branched with a CF3 group and 1 to 21 Contains carbon atoms and X contains a hydrogen or a CH3 group It Mixtures of different compounds of the above formula can also be used especially mixtures of compounds that vary in chain length (number of carbon atoms) of the RF remainder. The compounds or mixtures mentioned of connections are through. the well-known reaction of perfluoroalkyl iodides with Easily accessible ethylene or propylene.

Furthermore, compounds of the formula Rf (CfI2) 41 where can also be used Rf has the meaning defined above, convert it into the corresponding alcohols.

Particularly preferred starting compounds for the inventive Reactions are those of the general formula: R'f (C2F4) nCH2CH2I where: R1 Perfluoromethyl, perfluoro-n-propyl and especially perfluoroethyl or perfluoroisopropyl and n is an integer or, in the case of mixtures, a fractional number (as Mean) from 0 to 9.

If two liquid phases occur during the reaction, what if not already present, for example by adding water to the reaction mixture can be achieved or enhanced, the reaction can be achieved by using Accelerate at least one phase transfer catalyst known per se, whereby the conversion can usually also be increased.

Suitable phase transfer catalysts are described, for example in the journal Angewandte Chemie ", 86th year, 1974, pages 187 to 196 and 89th year, 1977, pages 521 to 533. for the present proceedings an ammonium or phosphonium catalyst is preferably used as the phase transfer catalyst EyesetæL that have at least one nitrogen or at least one phosphorus atom 3 or 4 bonds with carbon atoms and in the entire molecule per ammonium nitrogen or phosphonium phosphorus atom contains 4 to about 60 carbon atoms. The catalysts should not contain any chloride or bromide anions, as these are undesirable Can induce decomposition of the peroxidocarboxylic acids.

Based on 1 mol of perfluoroalkyl-iodoalkane, 0.001 to 0.1 mol of the phase transfer catalyst or catalyst mixture applied. Below 0.001 mol the effectiveness of the catalysts decreases significantly, above 0.1 mol will not have an improving, but rather a slightly worsening, effect of the catalyst established. Preferred amounts are from 0.005 to 0.05 mol of the phase transfer catalyst per mole of perfluorotalkyl iodoalkane.

Since the reaction according to the invention is slightly exothermic, it is expedient the perfluoroalkyl-iodoalkane placed in the reaction vessel and the peracid solution is metered in with vigorous mixing of the components by stirring or shaking, wherein the heat of reaction can optionally be removed by external cooling.

The peroxidocarboxylic acid can be in the form of a solution in at least one the inert solvents described above can be used. Using a peroxidocarboxylic acid, previously made from the corresponding carboxylic acid and hydrogen peroxide was produced, and the n (bubbles of the oxydocyclic acid still the unchanged carboxylic acid, residues of hydrogen peroxide and water and one Catalyst, for example sulfuric acid, contains, is the use of an additional Solvent for the peroxidocarboxylic acid is not normally required. at Longer-chain perfluoroalkyl-iodoalkanes, it is advantageous to add the peroxidocarboxylic acid the perfluoroalkyl iodoalkane with a to lower its fixed point to 30 to mix a sufficient amount of carboxylic acid up to 40 ° C.

In the reaction according to the invention, the reaction time increases with increasing Molecular weight of the perfluoroalkyliodalkane increases. In general, it is only a few Hours.

Perfluoroalkylalkanol carboxylic acid esters are formed as primary reaction products as well as small amounts of perfluoroalkyl olefins. Form in the presence of water even the free perfluoroalkyl alkanols. Leave the fluorine-containing products isolate themselves from the reaction mixture by customary methods. Unless in with water Immiscible organic solvent is worked, for example the iodic acid formed is filtered off, the remaining liquid organic phase with alkaline water atisgeschüttelt after separation from the aqueous phase over a conventional desiccant, such as sodium sulfate, and dried from it the organic solvent can be distilled off.

A particularly favorable form of work-up consists in adding of water to the reaction mixture, the fluorine-containing products or their Solution in the optionally used organic solvent as a separate Separate phase and the by-product Iodic acid in the aqueous phase remains. The advantage of this approach is that that the valuable iodine can be obtained very easily from the resulting aqueous iodic acid solution by reduction, for example by adding the required amount of a water-soluble one Sulfite, can be deposited.

The crude product phase containing the organic, fluorine-containing compounds is, if necessary after removing the solvent, in a manner known per se, for example by heating with aqueous and / or alcoholic alkali such as sodium hydroxide or potassium hydroxide, saponified to split the ester component. This is advantageous in the presence of phase mediators such as lower aliphatic alcohols, di-alkyl glycol ethers, Di-methylformamide or n-methylpyrrolidone worked.

The desired perfluoroalkyl-alkanol finally becomes the end product and obtained in a small amount the corresponding perfluoroalkyl olefin, which according to known methods can be separated and cleaned.

The perfluoroalkyl alkanols obtained according to the invention, in particular the perfluoroalkylethanols are used as intermediate products in the manufacture of hydrophobic, oleophobic and / or dirt-repellent textile finishing agents. For this purpose, the alkanols are converted into their esters with unsaturated carboxylic acids, for example such as acrylic or methacrylic acid, and the compounds thus obtained are polymerized. In this way, technically important products are obtained, which are in the field of textile finishing Find use.

The following examples are intended to explain the process according to the invention in more detail explain.

Precautions: When working with peracids there are impurities carefully to exclude heavy metals or their compounds. As material glass, polyethylene or enamel are suitable for storage and reaction vessels. the Peracid solutions should be stored out of light.

Example 1 Preparation of peroxido-acetic acid solution 1 1 glacial acetic acid and 10 ml of concentrated sulfuric acid are mixed in a 2.5 l polyethylene bottle, the mixture is cooled to 10 ° C. and 184.7 g of 70-term H 2 O 2 (3.8 mol) are added. After shaking, the mixture is left to stand in the dark at room temperature for 30 to 40 hours. The solution then contains approx. 3.3 mol of peracetic acid.

Reaction with perfluoroalkyl iodoalkane In a 4 l glass flask with stirrer, Internal thermometer and dropping funnel are placed 474 g (1.0 mol) of C6F13CH2CH2I. The peroxidoacetic acid solution described above is stirred vigorously added dropwise over 2 hours, the temperature being reduced by cooling with a water bath is kept at 30 ° C. The mixture is stirred for a further 4 hours and then 700 ml of H2O are added.

Two phases are obtained, which are separated in a separating funnel. The upper phase consists of iodic acid, acetic acid, water and a little sulfuric acid. The pink colored lower phase (420 g) contains fluorine compounds and some acetic acid and water. The distribution of the fluorine-containing products according to the 1H nuclear magnetic resonance spectrum is as follows (in mol%): C6F13CH2CH2-OCOCH3: 64.0; C6F13C112CH2O11: 23.6; C6F13Cll2CH2OSO3H : 6.0; C6F13CH = CH2: 2.5; C6F13CH2CH2I: 3.9. The turnover corresponds 96.1 t.

Work-up The lower phase is mixed with 300 ml of methanol and the pH is adjusted to 10 by adding 50 titer of NaOH. This mixture will Heated to boiling with stirring under reflux for 2 hours. Then it is with 1 liter of water diluted. The product phase is separated off, dried with Na2SO4 and distilled. 315 g of C6F13CH2CH2OH (boiling point 74-760C, yield 86.5%) and 21.8 g of C6F13CH-CH2 are obtained (Bp 730 104 OC, yield 6.3 t).

302.5 g (2.4 Mol) sodium sulfite slowly added in the form of an aqueous solution, whereby the Maintains the temperature of the mixture at 25 to 30 ° C. After standing for a short time you suck it up precipitated iodine and washed with 1 1 water.

121.8 g of moist iodine (water content: 6%) are obtained, corresponding to 114.4 g dry iodine (yield 90%, based on the C6F13CH2CH2I used).

Examples 2 to 11 Test results are summarized in Table 1, those with various peroxydocarboxylic acids made from aliphatic carboxylic acids and 70% hydrogen peroxide, and perfluoroalkyl-iodoalkanes.

The procedure was analogous to Example 1. The maximum initial temperature was 45 OC. The final temperature was room temperature in each case. With perfluoroalkyliodalkanes with a total of 10 or more carbon atoms (Examples 8, 10 and 11) became so many Carboxylic acid with submitted that the melting point of the starting material is at most 40 0C. For this were in Example 8: 0.4 moles, in example 10: 0.8 mol and in Example 11: 1.0 mol of acetic acid, each per 0.2 mol of perfluoroalkyl-iodoalkane, necessary.

Example 12 A 10% solution of 0.55 mol of peroxybenzoic acid in Ethyl acetate is added to 0.15 mol of C6F13CH2CH2I with stirring over the course of one hour. The reaction is allowed to continue for 3 hours, then 200 ml of water are added and the phases are separated. Sodium carbonate solution is added to the lower phase and extracted by shaking Remove benzoic acid. After the ethyl acetate has been distilled off, the procedure is as in Example 1 worked up. Yield 44 g of C6F13CH2CH2OH (81%) and 1.5 g of C6F13CH = CH2 (2.9%).

Examples 13 to 16 Production of perfluoroalkylethanols under Use of phase transfer catalysts 1 mole of perfluoroalkyl ethyl iodide in each case is presented together with the phase transfer catalyst listed in Table 2 and, as described in Example 1, reacted with peroxidoacetic acid at 32 "C. The Reaction conditions and results are given in Table 2.

TABLE I: Reactions of perfluoroalkyl-iodoalkanes with equilibrium percarboxylic acids Example: starting compound peroxidocarboxylic acid solution, initial reaction dmsetzungs- products and yields No. (Mol) manufactured as: temperature (0C) duration (b): rad (%) (%) 2 C6F130i2CH21 150 ml CH3C02H, 30 6 87 C6F13CH2CH20H C6F13 ERZ 0.2 34 g H2021 1.5 'II ";;'J;: = lc'j I = 73.6 14.2 3 C6F130H2CH2 1 200 ml Ci3C02h, 30 6 93.2 C6F13C2CH20H C6F13CHC '\. 2 0.2 34 o rr 2 q 81.5 7 ,: 4 06F13CH2CH2I 200 ml ", i 3: 41% F13CH2Cii20H C6F13CH-2; i'2 0.2 34 ohl; g; H202 34.1 5.6 L "200 drew Dzml cH3CH2c.:L., 6 90.4 C6F13CH2CH20H C6F13CH = C2 0.2 36.9 g H202.2 2S04 71.3 16.2 HN Or 'R - WN 6 fCH2 Oh2 1 ltr. CHCO2.3 1: 94.5 RfCH 2 2 2 to 40c1 {; 1 ?: '% c} 2F285) 17 15 H2,02, 1'.; 8 &, 6 7.2 1.0 C2F5CH2OH2 1 2: 0 m CHC2 6 9.5 O2F5c2cH2: H C2F5Chh2 SO 49 8 08 F17CH2CH2 1; r ml OH "4 10 75.4 C8F17CH20H20H c8F17c \" -: - :. 2 0.2 36.9 g 2 65.7 27.2 H202, 3 i 'St) 9 C6F13CH2.CHI 10: ml CH3CO2, 3:20 96 C6F13CH-CHOH 0.1 C'3 17 g of ore CH2 10 C6F13 (H2) 4I 2t) C m CH3C02 24; 2.6 26F1 3 (CH2) LOH R yr \ -I), t), 2 3 ;. g H202, 3: 2S '65.6 2.3 11 C10F (CH2) 4I 320 nl CH3CC2-, 4, 24 70.2 C10F V> rl Ci F (r,% CH2 0.2 39 gz <C.1 TABLE II Preparation of RfCH2CH2OH with Phase Transfer Catalysts Example perfluoroalkyl phase transfer catalyst reaction conversion product yield (%) No. iodoalkane (1 mol) (mol) duration (h) (%) Rf-alkanol Rf-alkene 13 C6F13CH2CH2 I [(C10H21) 2N (CH3) 2] + O2CCH3 + 6 98.0 87.0 4.2 (0.005) 14 C6F13CH2CH2 I [(C10H21) 2N (CH3) 2] + OSO3CH3- 6 98.5 87.5 3.9 (0.01) 15 RfCH2CH2 I +) [(C10H21) 2N (CH3) 2] + OSO3CH3-10 96.5 86.0 7.2 (0.01) 16 C6F13CH2CH2 I [(C8H17) 3PC2H5] + O2CCH3- 6 97.5 85.5 4.6 (0.008) +) Rf (distribution in mol%): C6F13 40, C8F17 34.5, C10F22 17.5, C12F25 8.

Claims (9)

Claims 1. Process for the preparation of perfluoroalkyl alkanols from the corresponding perfluoroalkyl-iodoalkanes by reaction with an oxidizing one Acid, optionally at elevated temperature, characterized in that the reaction at -20 to about +80 OC, optionally under pressure, in the presence of a peroxidocarboxylic acid, containing 1 to about 20 carbon atoms, and optionally in the presence of one or more of the following substances: water, inert, organic solvents, known Phase transfer catalyst is carried out, with per mole of Pcrfluorallcyl-iodalkan at least 3 molar equivalents of peroxidocarboxylic acid green are used. 2. The method according to claim 1, characterized in that a peroxidocarboxylic acid used in a mixture with the analogous carboxylic acid, which does not contain any peroxido groups will. 3. The method according to any one of claims 1 or 2, characterized in that that an aliphatic peroxidocarboxylic acid having 1 to b carbon atoms is used. 4. The method according to any one of claims 1 or 2, characterized in that that peroxidobenzoic acid is used, which is optionally substituted on the benzene nucleus is. 5. The method according to any one of claims 1 to 4, characterized gekennzeichneb, that the reaction is carried out at 10 to 60 ° C 6. Procedure according to one of claims 1 to 5, characterized in that per mole of perfluoroalkyl iodoalkane 3.1 to 4 molar equivalents of peroxidocarboxylic acid groups are used. 7. The method according to any one of claims 1 to 6, characterized in that that a perfluoroalkyl-iodoalkane or a mixture of several perfluoroalkyl-iodoalkanes the following formula can be used: RfCH2 CIH-X where: Rf is a perfluoroalkyl radical, which is straight-chain or trifluoromethyl branched and has 1 to 21 carbon atoms and X contains a hydrogen atom or a methyl group. 8. The method according to any one of claims 1 to 7, characterized in that that the reaction in the presence of water and per mole of perfluoroalkyl-iodoalkane 0.001 to 0.1 mol of a known phase transfer catalyst is carried out. 9. The method according to claim 8, characterized in that the phase transfer catalyst an ammonium or phosphonium compound is used, which is at least one Nitrogen or phosphorus atom 3 or 4 bonds with carbon atoms and each ammonium-nitrogen or phosphonium-phosphorus atom contains 4 to 60 olefin atoms.