US3326919A - Quaternary ammonium salts of phosphoric acid esters - Google Patents

Description

United States Patent 3,326,919 QUATERNARY AMMONIUM SALTS 0F PHUSPHORIC ACID ESTERS Reginald L. Wakeman, Philadelphia, Pa., and Joseph F.

Coates, Washington, D.C., assignors, by mesne assignments, to Millmaster Onyx Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed July 29, 1963, Ser. No. 298,472 4 Claims. (Cl. 260-286) The object of the present invention is the preparation of microbiologically active compounds by reaction of certain quaternary ammonium hydroxides or their salts of inorganic acids with acidic esters of phosphoric acid and oragnic hydroxyl-bearing compounds, specifically alcohols, phenols, alkyl phenols and their ethoxylated derivatives such as ethylene oxide adducts of higher aliphatic alcohols and ethylene oxide adducts of octyl phenol, nonyl phenol and the like. Acidic phosphoric acid esters of propoxylated alcohols and phenols are also included within the scope of this invention. The quaternary ammonium compounds used in the process of this invention contain at least one carbon chain having from 8 to 22 carbon atoms and the quaternary nitrogen atom may be a member of a hetero cyclic n'ng such as pyridine, isoquinoline, morpholine or pyrrolidine if desired.

Typical examples of these quaternary ammonium compounds are alkyl trimethyl ammonium chlorides, alkylbenzyl trimethyl ammonium chlorides, alkyl dimethyl benzyl ammonium chlorides, alkyl dimethyl menaphthyl ammonium chlorides, alkyl dimethyl substituted-benzyl ammonium chlorides in which the benzyl radical is substituted with one or more side chains containing from 1 to 4 carbon atoms such, for example, as methyl, dimethyl, ethyl and the like and in which the carbon atoms may all be in the same or different side chains or in which the benzyl radical bears one, two or more halo gen atoms such as chlorine or bromine, alkyl pyridinium chlorides, alkyl lower-alkyl pyrrolidinium chlorides, alkyl lower-alkyl morpholinium chlorides in all of which the alkyl group may have from 8 to 22 carbon atoms and the lower alkyl group may have from 1 to 4 carbon atoms and alkyl phenoxy ethyl dimethyl benzyl ammonium chloride in which the alkyl radical may be isooctyl or nonyl and in which the benzyl radical may, if desired, be substituted by a methyl radical. Various other analogs of these quaternaries may also be employed, such for example as cetyl dimethyl ethyl ammonium bromide or oleyl dimethyl ethyl ammonium bromide.

It has generally been thought that quaternary ammonium compounds such, for example, as those of the proceeding types which are microbiologically active are not compatible, that is to say, lose their microbiological activity in the presence of anionic materials, particularly anionic surface-active agents.

We have found, however, that contrary to general belief the reaction of microbiologically active watersoluble quaternary ammonium compounds with surfaceactive acidic esters of phosphoric acid and organic hydroxyl-bearing compounds such as alcohols, phenols, alkyl phenols, and ethoxylated and propoxylated derivatives thereof, or with water-soluble salts of such partial phosphoric acid esters, yields products which in many cases are equally as active microbiologically as the parent quaternary ammonium compounds from which they are derived. In some cases they are more active.

It is possible, if desired, to use condensed phosphoric acid esters, such as esters of pyro phosphoric acid, or mixtures of various phosphoric acid esters and acid esters of condensed phosphoric acid. In view of the complex chemistry of phosphoric acid and the ease of forming condensed acids and their derivatives, such for example,

as pyrophosphates and poly phosphates, it is often possible to obtain phosphate esters of the type herein employed only in the presence of varying proportions of polymeric, i.e., condensed esters.

As suitable phosphoric acid derivatives, we may employ any surface-active mono-acid ortho phosphate in the form of its free acid or its monoor di-alkali metal, ammonium, or other water-soluble salt, having the generic structure:

where X may be hydrogen or a water-soluble cation such as sodium, potassium, or ammonium, R is an alkyl, aryl, aralkyl, alkaryl, or alkaralkyl radical containing from 6 to 22 carbon atoms, R is hydrogen or methyl, n is an integer from 0 to 40, and a and b are either 1 or 2, the sum of a and b being 3. Typical compounds include the free acids and the monoand di-water-soluble salts of mono-hexyl-o-phosphoric acid, mono-octyl-ophosphoric acid, mono-decyl-o-phosphoric acid, monolauryl-o-phosphoric acid, mono-myristyl-o-phosphoric acid, mono-cetyl-o-phosphoric acid, mono-stearyl-o-phosphoric acid, mono-arachydyl-o-phosphoric acid, monobehenyl-o-phosphoric acid and their branched chain analogs and the corresponding acids obtained from the ethoxylated alcohols such, for example, as mono-lauryl poly ethoxylated-o-phosphoric acid, the corresponding di-aIkyLO-phosphoric acids such as dilauryl-o-phosphoric acid, for example, and the corresponding ethoxylated derivatives such as di(lauryl poly ethoxy ethyl)-o-phos phoric acid, monoand di-octyl-phenoxy ethyl and octyl phenoxy poly ethoxy ethyl-o-phosphoric acids, monoand di-nonyl phenoxy ethyl-o-phosphoric acid, monoand di-phenyl, cresyl, benzyl, or dodecyl benzyl-o-phosphoric acids, propylene oxide derivatives corresponding to the ethoxylation products herein enumerated and the like.

Numerous organic acid phosphates which are currently commercially available are suitable for making the products of this invention. Among such products are the isooctyl, stearyl, phenyl, and octyl phenyl organic acid phosphates described as phosphate esters containing varying amounts of poly phosphates and having acid numbers (mg. KOH per gm. of sample) of 305, 165, 360, and 200, respectively.

Other commercially available phosphoric acid esters suitable for the purposes of this invention are available both as free acids and as sodium salts and are believed to be phosphate esters of ethylene oxide adducts, of alkyl phenols or branched chain aliphatic alcohols such, for example, as those described in U.S. Patent No. 3,033,889.

Products suitable for the purposes of this invention also include dialkyl orthophosphates in which the alkyl radical is iso-octyl or Z-ethylhexyl and which are described as mixtures of approximately equal molar proportions of mono-esters and di-esters of orthophosphoric acid, 1

mono-alkyl orthophosphates in which the alkyl radical is iso-octyl, Z-ethylhexyl, decyl, tridecyl, or lauryl and described as mixtures of monoand di-esters containing larger proportions of mono-esters of orthophosphoric acid than do the dialkyl acid orthophosphates, dialkyl acid pyrophosphates in which the alkyl radical is isooctyl or 2-ethylhexyl and described as di-esters of pyrophosphoric acid (H P O and mixed alkyl acid orthophosphates in which the alkyl radicals are ethyl .and oleyl or ethyl and lauryl and which are described as esters of orthophosphoric acid with mixed alkyl groups.

The quaternary ammonium compounds useful in this invention are the higher alkyl quaternary ammonium hydroxides, halides (chlorides and bromides), sulfates,

mixed mono and dihydrogen methosulfates and the like possessing the following formula:

N RI RI! R/II wherein R is selected from the group consisting of an alkyl, an alkaralkyl radical containing from 8 to 22 carbon atoms, an alkyl benzyl phenoxy ethyl radical in which the alkyl radical contains from 8 to 9 carbon atoms, and in which the phenyl radical may be substituted by a methyl group; R and R" are selected from the group consisting of a methyl, ethyl, and radicals of members of a hetero cyclic ring system including pyridine, isoquinoline, pyrrolidine, and morpholine; R is selected from the group consisting of a methyl radical, a benzyl group, a substituted benzyl group including monochlorobenzyl radical, a dichlorobenzyl radical and mixtures thereof, a methyl benzyl, dirnethyl benzyl, ethyl benzyl, diethyl :benzyl, isopropyl benzyl, tertiary butyl benzyl or another benzyl radical containing from 1 to 4 carbon atoms as a single or multiple side chains, a menaphthyl group, a hydrogenated menaphthyl group, a methyl, ethyl, propyl or butyl group when R and R" are members of a morpholine and pyrro-lidine ring or R' is the same radical as R when R and R" are members of an unsaturated hetero cyclic ring including pyridine or isoquinoline; and X is selected from the group consisting of a chlorine, bromine, sulfate, and methosulfate radical.

The compounds of this invention may be prepared by mixing aqueous solutions of the quaternary ammonium salts or hydroxides with an aqueous solution of the acid in question or any of its water-soluble salts.

After thorough mixing, the organic product layer is separated from the aqueous layer (as with a separatory funnel) since two distinct phases are formed. Separation may be facilitated by the addition of an organic solvent immiscible with water. The product may be washed with water to remove any residual by-product salt or unreacted materials. The solvent, if any, may be evaporated and the product air or vacuum dried to a paste, wax, oil or solid.

It is not necessary to use an aqueous medium. Any solvent or solvent mixture in which the starting materials are soluble 'will be satisfactory. Non-aqueous solvents facilitate the separation of by-product inorganic salt and reduce the need for vacuum drying to get an anhydrous product. When a non-aqueous medium is employed, it is usually necessary to add a small amount of water to facilitate ionic reaction.

The product may be used, if desired, without drying since any entrapped water is irrelevant to the microbiological activity of the compounds. In other applications, removal of water may be essential for reasons not related to biological activity.

An alternative method for the preparation of compounds especially applicable to the treatment of fabric, ropes, net, woven and non-woven fabric and reticulated or convoluted materials, involves a two-step process. In the first step, the material is passed through a bath containing the anionic moiety. Excess solution is removed by methods well known to those skilled in the art. The treated material is then passed through a second bath wherein the concentration of quaternary ammonium compound is such that the material pickup will result in an equivalent amount of quaternary ammoniumcompound reacting with the anionic moiety, depositing the product in the most intimate way on the surface and in the interstices, convolutions and reticulations of the material.

The method of adjustment of solution concentration to achieve the required pickup is well known to those skilled in the art. The order of treatment may be reversed without affecting the biological activity or durability of the product on the material. The products of this invention may be formulated as water dispersions by dissolving them in a water-miscible organic solvent such as acetone or methanol and diluting with water or by dissolving them in emulsifiable oils such as, for example, sulfonated castor oil or pine oil and diluting With Water. In preparing aqueous dispersion, emulsifying agents such, for example, as ethylene oxide condensates of alkyl phenols may be used with or without organic solvents.

It is surprising that the compounds of this invention exhibit high microbiological activity despite their relative insolubility in water. Because of their unusual combination of physical and microbiological properties, they can be used to impart laundry-resistant anti-microbial characteristics to textiles. They can also be used as the active agent in anti-mildew finishes for textiles which are resistant to leaching with Water.

Although the compounds have loW water solubility, they are compatible with various organic solvents, plasticizers and high molecular weight compounds. Consequently, they may be incorporated as anti-microbial agents in synthetic resins and plastics. The compounds are compatible with natural and synthetic rubber latices. Therefore, they may be used to prepare bacteriostatic films and molded objects deposited from such latices.

The compounds can be incorporated intocutting and grinding fluids without precipitation. Also, they blend well with non-ionic and anionic surface-active agents. In such compositions they retain their microbiological activity.

It will be understood that the properties of the products described herein will vary depending upon the nature of the quaternary ammonium compound used in their preparation as well as the phosphoric acid derivative reacted therewith. It is also to be understood that we may react suitable mixtures of the quaternary ammonium compounds with a selected phosphoric acid derivative previously described or mixtures thereof.

The chemical, physical and biological properties of the products of our invention make them especially appropriate for the following applications when suitably incorporated in active amounts in an appropriate vehicle, binder, medium or substrate:

(1) Mildewproofing fabric, canvas, ropes, textiles, awnings, sails, tenting and other woven and non-woven reticulated materials.

(2) Paint mildewstats.

(3) Jet plane fuel additive to control growth of microorganisms.

(4) Odor preservative agents for clothes and shoes.

(5) Mildew retardant and odor suppressant for shoes and other leather products.

(6) Topical antiseptics.

(7) Antidandruff agents.

(8) Disinfection agents for hair and gut of man and beast.

(9) Bacteriostatic furniture dressing.

(10) Surface finishes for stone, plaster, tile, cement, brick and other inorganic building materials, to retard growth of microorganisms, fungi, mold and algae.

(11) Wool preservative.

(12) Plant and tree spray to combat fungi.

(13) Antimycotic agents for soap Wrappers.

Self-sanitizing brushes.

Mildewproofing agent in and on plastic and film.

(16) Mildewproofing of cellulosics, cardboard, fibreboard, paper and cordage.

17) Contact biostat for application to film, waxes and cloth to preserve cheese, meats and vegetables and other food products.

(18) Algal inhibition, especially on surfaces and in solution where low foaming is desirable.

( 19) Paper pulp slime control.

(20) Sanitizing agent for rug, carpet, curtains.

(21) Egg preservation.

(22) Adhesive preservation.

(23) Preservation of latex paints.

(24) Preservation of metal-working compounds.

The microbiological activity of our compounds has been evaluated for microbiological stasis by the Standard Tube Dilution Test, the technique for which is common knowledge to those skilled in the art. A Difco Bacto CSMA Broth #0826 was used in the study. This test is used to determine the lowest concentration of microbiologically active compounds which will inhibit the growth of the organism in question. For a wide range of applications, the inhibition of growth rather than outright kill is satisfactory.

Briefly put, the tube dilution test consists in placing 9 cc. of the CSMA Broth in a test tube which is then sterilized in an autoclave. One cc. solution of the microbiologically active compound at an appropriate concentration is added to the test tube which is then inoculated with 0.1 cc. of a twenty-four hour old culture of the organism under study. The test tube is then incubated at 37 C. for forty-eight hours and observed for bacterial growth.

The same procedure is followed for fungi. In such tests, however, the tubes are incubated for fourteen days at a temperature suitable for optimum fungal growth, usually 25 C.

The invention is illustrated by, but not restricted to, the following examples:

Example 1 To 60 g. of a 10% solution of the sodium salt of lauryl ortho phosphate in a separatory funnel was added 70 g. of a 10% solution of alkyl dimethyl ethyl-benzyl ammonium chloride (alkyl=50% C 30% C 17% C 3% C The separatory funnel was shaken for one minute and then allowed to stand to permit layer separation. The upper layer was separated and dried to give 12 g. (93 yield) of a yellow paste, alkyl dimethyl ethyl-benzyl ammonium lauryl ortho phosphate.

Example 2 As in Example 1, the sodium salt of lauryl ortho phosphate was reacted with a chemically equivalent amount of alkyl dimethyl benzyl ammonium chloride (alkyl C14, C16, C12, C13). A yellow paste, alkyl dimethyl benzyl ammonium lauryl ortho phosphate, was obtained in 92% yield.

Example 3 Using the same technique as in Example 1, the sodium salt of lauryl ortho phosphate was reacted with a chemically equivalent amount of alkyl isoquinolinium bromide (alkyl=50% C 30% C 17% C 3% C Areddishbrown paste, alkyl isoquinolinium lauryl ortho phosphate, was obtained in 89% yield.

Example 4 Example 5 Using the technique of Example 4 above an aqueous solution of disodium lauryl ortho phosphate was reacted with an aqueous solution of alkyl isoquinolinium bromide (identified in Example 3) to give 11 g. of a dark brown paste consisting mainly of mono sodium alkyl isoquinolinium lauryl ortho phosphate.

Example Using the technique of Example 4 above an aqueous solution of the mono sodium salt of dilauryl ortho phosphate was reacted with an equimolar amount of an aqueous solution of alkyl ethyl benzyl dimethyl ammonium chloride (identified in Example 1 above). The product, a yellow paste consisting mainly of alkyl ethyl-benzyl dimethyl ammonium dilauryl ortho phosphate, was obtained in yield.

Example 7 Using the technique of Example 4 above an aqueous solution of the mono sodium salt of dilauryl ortho phosphate was reacted with a chemically equivalent amount of alkyl dimethyl benzyl ammonium chloride (identified in Example 2 above). The product, a yellow paste consisting mainly of alkyl dimethyl benzyl ammonium dilauryl ortho phosphate, was obtained in 100% yield.

Alkyl isoquinolinium (identified in Example 3) dilauryl ortho phosphate, a dark brown paste, was prepared in a similar way.

Example 8 Three hundred grams of a 10% solution of the sodium salt of a phosphate derived from an alkyl phenol ethoxylate was prepared.

This solution was divided into three 100 g. portions and each of these portions placed in a 500 ml. separatory funnel. To the first portion was added 280 g. of a 10% solution of alkyl ethyl benzyl dimethyl ammonium chloride (identified in Example 1); to the second portion, 280 g. of a 10% solution of alkyl dimethyl benzyl ammonium chloride (identified in Example 2); to the third portion, 280 g. of a 10% solution of alkyl isoquinolinium bromide (identified in Example 3). Each of the funnels was well shaken and 50 ml. of benzene added to each to speed layer separation. The product layer from each funnel was separated and dried in a vacuum oven.

Approximately 38 g. of a yellow paste consisting principally of alkyl ethyl-benzyl dimethyl ammonium alkyl phenoxy ethyl phosphate was obtained from the first funnel. Approximately 42 g. of a yellow paste consisting mainly of alkyl dimethyl ammonium alkyl phenoxy ethyl phosphate was obtained from the second, and 20 g. of a dark brown paste consisting mainly of'alkyl isoquinolinium alkyl phenoxy ethyl phosphate from the third.

Products were also prepared in which equimolar quantities of quaternary ammonium compounds and phosphate esters were used.

Example 9 One hundred and twenty grams of a 5% solution of an alkyl phenol ethoxylate phosphate was prepared and divided into two 60 g. portion-s. To the first of these in a 250 ml. separatory funnel was added 100 g. of a 10% solution of alkyl ethyl-benzyl dimethyl ammonium chloride (identified in Example 1). To the second was added 100 g. of a 10% solution of alkyl isoquinolinium bromide (identified in Example 3).

The products were separated as described in Example 8. Alkyl ethyl-benzyl dimethyl ammonium alkyl phenoxy ethyl phosphate, a yellow paste, was obtained in approximately 100% yield (12.5 g.). Alkyl isoquinolinium alkyl phenoxy ethyl phosphate, a dark brown paste, was obtained in 70% yield ('8 g.).

Products were also prepared in which equimolar quantitles of quaternary ammonium compounds and phos phate esters were used.

Example 10 Ten grams of a 25% aqueous solution of sodium alpha nap'hthyl phosphate was prepared. In a 10 ml. separatory funnel were placed 4.83 g. of this solution and 1.77 g. of a 10% solution of alkyl ethyl-benzyl dimethyl ammonium chloride (identified in Example 1) added and the funnel well shaken. A colorless oil, alkyl ethyl-benzyl dimethyl ammonium alpha naphthyl phosphate, separated on standing. The dry weight of this oil was 0.288 g. (100% yield).

An additional 3.95 g. of the 2.5% solution of sodium alpha naphthyl phosphate was placed in a second 10 ml. separatory funnel and 1.35 g. of a 10% solution of alkyl isoquinolinium bromide (identified in Example 3) added. The solutions were well mixed by shaking the separatory funnel. On standing a yellow oil separated which had a dry weight of 0.216 g. The product here is alkyl isoquinolinium alpha naphthyl phosphate.

Example 11 Sixty grams of a 10% solution of sodium di(Z-ethylhexyl) phosphate were placed in a separatory funnel and 60 g. of a 10% solution of alkyl ethyl-benzyl dimethyl ammonium chloride (identified in Example 1) were added and the funnel well shaken, approximately 20 ml. of benzene and 10 ml. saturated salt solution were added to promote layer separation. The benzene layer was separated and dried in a vaccum oven to give 8 g. (70% yield) of alkyl ethyl-benzyl dimethyl ammonium di(2- ethyl-hexyl) phosphate, a light yellow paste.

In a similar way alkyl isoquinolinium bromide (identified in Example 3) was reacted with sodium di(2-ethylhexyl) phosphate to give alkyl isoquinolinium di(2-ethylhexyl) phosphate, a red paste, in 90% yield.

7 Example 12 One hundred grams of a 10% solution of the sodium salt of an alkoxy ethyl phosphate was placed in a separatory funnel and 1 g. of 10% solution of alkyl ethyl benzyl dimethyl ammonium chloride (identified in Example 1) added. The funnel was well shaken and when allowed to stand a clear oil separated. This oil was vacuum dried to give a 100% yield of principally alkyl ethyl benzyl dimethyl ammonium alkoxy ethyl phosphate, a pale yellow paste.

Products were also prepared in which equimolar quantities of quaternary ammonium compounds and phosphate esters were used.

Example 13 The results of static dilution tests performed upon the products of Examples 1 to 12 are shown in the following tables wherein S.a. indicates Staphylococcus aureus, St. is Salmonella typhosa, and An. is Aspergillus niger:

TABLE I.-BACTERIOSTATIC ACTIVITY OF VARIOUS QUATERNARY AMMONIUM SALTS OF ACIDIC ESTERS OF PHOSPHORIC ACID Reciprocal of Static Dilution of Product vs. Product S.a. St. A.n.

(A) Derivatives of Alkyl Ethyl-Benzyl Dimethyl Ammonium Chloride (see Example 1) with Lauryl Ortho Phosphate (mono sodium salt) 10 10 10 Dilaurly Ortho Phosphate (sodium salt) 10 10 Alkyl Phenoxy Ethyl Phosphate (Example 8) 10 10 10 Alkyl Phenoxy Ethyl Phosphate (Examp e 10 1O 10' Alpha Naphthyl Phosphate- 10 10 10 Di(2-ethylhexyl) Phosphate 10 10 10 Alkoxy Ethyl Phosphate (Example l2) 10 10 10 (B) Derivatives of Alkyl Benzyl Dimethyl Ar ralfinonium Chloride (see Example 2) W1 Lauryl Ortho Phosphate (mono sodium salt 10 10 10 Lauryl Ortho Phosphate (di sodium salt) 10 10 10 Dilauryl Ortho Phosphate (sodium salt). 10 10 10 Alkyl Phenoxy Ethyl Phosphate (Example 8) 10 10 10 (C) Derivatives of Alkyl Isoquinolinium Bromide (see Example 3) with- Lauryl Ortho Phosphate (mono sodium salt) 10 10 10 Lauryl Ortho Phosphate (di sodium salt) 10 10 10 Dilauryl Ortho Phosphate (sodium salt)- 10 10 10 Alkyl Phenoxy Ethyl Phosphate (Example 8) 10 10 10 Alkyl Phenoxy Ethyl Phosphate (Example 9) 10 10 10 Alpha Naphthyl Phosphate 10 10 10 Di(2-ethylhexyl) Phosphate 10 10 10 The fungistatic activity of the products of this invention is indicated by the following:

Table Il.Appr0ximately static dilution level of the product of Example 1 Aspergillus niger 1/75,000

Penicillium luteum 1/75,000

Pullularia pullulans 1/75,000

Example 14 A 25 weight percent solution of each of the compounds of Examples 1 to 12 was prepared in ethylene glycol mono butyl ether and mixed with a commercial grade of alkyd base paint containing no other fungicide in the ratio of 4 parts by weight of this solution to 96 parts by weight of paint. Strips of filter paper cut to 1" x 4" were coated with this paint and allowed to dry. They were then inoculated with a culture of Pullularia pullulans and held in an incubator at 25 C. and relative humidity for three weeks. At the end of this time, nofungus growth was visible.

Example 15 Four parts of each of the 25% solutions of the compounds of Examples 1 to 12 (see Example 14) were added to 96 parts of a latex acrylic type paint with thorough stirring and each of the latex emulsions thus prepared was inoculated with a culture of Pullularia pullulans and incubated as in Example 9. At the end of three weeks, no fungus growth was visible in the latex.

In the preceding examples, and in the appended claims, it is to be understood that where the term ethyl or ethoxy is employed it is intended to designate both single and polyethyl and polyethoxy groups.

We claim:

1. The compound:

wherein X is quaternary ammonium cation, hydrogen, sodium, potassium or ammonium, at least one X being a quaternary ammonium cation, wherein R is alkyl, aryl, aralkyl or alk-aralkyl having 6 to 22 carbon atoms, wherein R is hydrogen or methyl, wherein n is an integer from 0 to 40, wherein a and b are either 1 or 2, the sum of a and b being 3, and wherein the quaternary ammonium cation has attached to the quaternary nitrogen, at least one alkyl group of from 8 to 22 carbon atoms, one alkaralkyl group containing 8 to 22 carbon atoms, or one alkyl benzyl phenoxy ethyl group in which the alkyl radical has 8 to 9 carbon atoms and in which the phenyl group may be substituted by a methyl group.

2. The compound of claim 1 wherein the cation is alkyl ethyl-benzyl dimethyl ammonium and the phosphate anion is lauryl ortho phosphate, dilauryl ortho hosphate, alkyl phenoxy ethyl phosphate, alpha naphthyl phosphate, di(2-ethylhexyl) phosphate, or alkoxy ethyl phosphate.

3. The compound of claim 1, wherein the cation is alkyl benzyl dimethyl ammonium and the phosphate anion is lauryl ortho phosphate, dilauryl ortho phosphate -or alkyl phenoxy ethyl phosphate.

4. The compound of claim 1, wherein the cation is alkyl isoquinolinium and the phosphate anion is lauryl ortho phosphate, dilauryl ortho phosphate, alkyl phenoxy ethyl phosphate, alpha naphthyl phosphate, or di(2-ethylhexyl) phosphate.

References Cited UNITED STATES PATENTS 2,563,506 8/1951 Werntz 260-295 2,729,576 1/1956 Trusler.

2,824,113 2/1958 Zech 260924 X 2,904,416 9/1959 Clarke et a1. 260-924 X CHARLES B. PARKER, Primary Examiner. F. M. SIKORA, R. L. RAYMOND, Assistant Examiners.

Claims (1)

1. THE COMPOUND: