US2702774A - Process of preparation of free flowing composition containing quaternary ammonium compound - Google Patents

Description

United States Patent Office 2,702,774 Patented Feb. 22, 1955 PROCESS OF PREPARATION OF FREE FLOWING COMPOSITION CONTAINING QUATERNARY AMMONIUM COMPOUND Richard D. Stayner, Albany, Calif., assignor to California Research Corporation, San Francisco, Calif., a corporation of Delaware No Drawing. Application June 16, 1950, Serial No. 168,650

4 Claims. (Cl. 167-42) This invention relates to germicidal compositions and methods for their preparation and is particularly directed to the preparation of dry free-flowing particulate materials containing a quaternary ammonium alkyl sulfate having germicidal and fungicidal properties.

Quaternary ammonium salts are widely used for germicidal, fungicidal and disinfectant purposes. Such compounds, however, are generally noted for their instability to heat and alkaline builders or bulking agents, and are therefore not well adapted to commercial production in the form of dry, free-flowing compositions.

This invention has as an object the provision of quaternary ammonium compositions which are more stable to heat and alkaline builders or bulking agents.

Another object of this invention is to provide compositions containing quaternary ammonium compounds in the form of a dry free-flowing composition.

Still another object of this invention is the provision of a method for producing dry free-flowing quaternary ammonium germicidal and fungicidal compositions in large quantities.

Further objects of this invention will be apparent from the disclosure which follows.

These objects are accomplished by my invention through the combination of a builder or bulking agent and a quaternary ammonium alkyl sulfate of the formula wherein R1 is an alkyl radical of from about 6 to 18 carbon atoms, R2 is a methyl radical or hydrogen, the radicals R3, R4 and R5 are aliphatic, unsaturated aliphatic,

araliphatic, haloalkyl, haloarylalkyl, hydroxyalkyl, etc.

types of substituted or unsubstituted hydrocarbon radicals containing not more than '7 carbon atoms each and together totaling no more than 12 carbon atoms, and preferably 3 to carbon atoms, Ar is an aryl nucleus such as benzene or naphthalene and R is a short-chain alkyl radical such as methyl, ethyl, etc.

I have found that quaternary ammonium compounds of this type are more stable to heat and alkaline builders or bulking agents and, therefore, can be compounded with builders or bulking agents to produce dry, freefiowing quaternary ammonium germicidal and fungicidal compositions. The higher stability of this particular class of quaternary ammonium compounds to heat and alkaline builders or bulking agents makes them readily adaptable to any of the known methods for preparing dry, free-flowing compositions.

The dry, free-flowing quaternary ammonium germicide compositions of my invention are suitably prepared by drum-drying an aqueous solution or a similar uniform or homogeneous suspension comprising a quaternary ammonium alkyl sulfate of the above-described type and a builder or bulking agent such as are hereinafter more particularly described. The free-flowing compositions according to this invention can also be produced using still other methods of drying within the knowledge of the art, such as spray-drying, rotary drying, filter drying, etc.

Another method of preparation which has been found suitable for the purposes of my invention utilizes the hydration properties that certain builders and bulking agents are known to possess. In this process, the quaternary ammonium alkyl sulfates described above are blended with an alkaline builder such as tetrasodium pyrophosphate or any other known builder or bulking agent. The builder or bulking agent should be capable of taking up water at temperatures below about 50 to 60 C. to form its corresponding hydrate and of losing its hydrate characteristics at temperatures above about 50 to 60 C. The blending is desirably carried out by first heating the tetrasodium pyrophosphate or other builder or bulking agent, such as are hereinafter more fully described, to a temperature substantially exceeding the temperature at which hydration is known to occur, as, for example, about C. in the case of tetrasodium pyrophosphate. At this point the above-described quaternary ammonium alkyl sulfate is added along with any other agents it may be desirable to use in the composition such as non-ionic surface active agents, abrasives, etc. The blehded materials are then mixed and water is added to form a slurry. The slurry is stirred by suitable stirring means until cool. Upon cooling, the water of the slurry is automatically taken up by the hydratable builder or bulking agent to produce a dry, free-flowing powder composition. If desired, the stirring operation whereby the free-flowing powder is produced may be omitted and the slurry instead pressed through a fine mesh screen or other similar device to give a granular free-flowing product.

By the use of various proportions of the quaternary ammonium salt and the builders or bulking agents, as well as other suitable agents such as non-ionic surface active agents, abrasives, etc., a wide variety of highly desirable dry, free-flowing, comminuted germicidal compositions are obtained. The quaternary ammonium alkyl sulfates in the dry, free-flowing compositions according to my invention may be present in various proportions ranging from only a small amount, just sufiicient to impart germicidal or fungicidal properties to the composition, up to l00% of active ingredient. Proportions of from about 5 to 20% of the quaternary ammonium compounds, based on the total dry weight of the composition, are particularly suitable for blending with hydratable builders or bulking agents in the above-described hydration process. For processes such as drum drying, spray drying, etc., blends containing from about 5 to 10% by dry weight of quaternary ammonium alkyl sulfate with the builder or bulking agent are preferred, although other pgfPOI'tiOHS ranging from about 1 to 20% are very suita e.

The water or other slurrifying agent used in the uniform or homogeneous suspension according to these processes may be present in any amount at least sufficient to produce such a slurry. In the hydration process it is desirable to avoid using quantities of water in excess of those which may be taken up by the hydratable builders or bulking agents utilized. In the other processes, such as drum drying, spray drying, etc., any amounts of slurrifying agent are permissible since they are ultimately evaporated. However, here again large excesses are preferably avoided since they make the drying process more costly.

The quaternary ammonium compounds which constitute the active germicidal ingredient of my compositions may be prepared by various methods such as will be apparent to one skilled in the art from the following disclosure; for the purpose of this invention, they are preferably produced from alkyl aromatic hydrocarbons by a sequence of steps involving nitration to the alkyl-aryl nitro derivatives, reduction to the corresponding alkyl-aryl amines and then quaternization with a short-chain dialkyl sulfate. They may also be prepared by the alkylation of aniline as noted, for example, in U. S. Patent No. 2,113,493 to Coffey et al. followed by quaternization with dialkyl sulfate.

The alkyl aromatic hydrocarbon utilized may contain a benzene or a naphthalene nucleus which may be substituted by a methyl radical. Benzene and toluene aryl groups are preferred. The alkyl portion of the alkyl aromatic hydrocarbon may be any alkyl group of from 6 to 18 carbon atoms. Although 6 to 10 carbon atoms in the alkyl radical are very satisfactory, in the case of atoms are desirable when branched-chain structures predominate. Long-chain olefins of from 6 to 18 carbon atoms obtained from cracked olefinic petroleum fractions or from Fischer-Tropsch synthesis are suitable as a source for such alkyl radicals. A particularly suitable type of alkyl group is that derived from acyclic polypropylene having from 9 to 15 carbon atoms with those of from 12 to 15 carbon atoms being even more preferred. Other sources of long-chain hydrocarbon mixtures such as those derived from mixtures of alcohols by catalytic dehydration are also suitable, although they are somewhat costlier than the more desirable petroleum sources.

The nitration process may be carried out using var1ous nitrating agents known to the art such as nitric acid, concentrated and dilute, liquid and vapor, or mixtures of nitric acid and sulfuric acid or fuming sulfuric acid and acetic acid, etc. However, due to the highly refractory nature of the alkyl aromatic hydrocarbons, certain agents and conditions are preferred. A 10% molar excess of concentrated nitric acid over the alkyl aromat1c hydrocarbons with a mixture of 70% fuming sulfuric acid (containing 20% S03) and 30% concentrated sulfuric acid is particularly suitable since it is found to give essentially complete conversions of the alkyl aromatic. A lthrough the proportions of the nitric acid to the sulfuric acid mixture may vary over a considerable range, from about 25 to 30% by weight is usually preferred. In the nitration of the long-chain alkyl aromatics according to this process, it is desirable that the temperatures utilized be below about 50 C. and preferably below about 30 C. in order to avoid the formation of alkyl aryl sulfonates which tend to produce undesirable mixtures such as emulsions, etc. Temperatures below about -l C. are 1mpractical to maintain. The nitration mixture is agitated during the reaction by suitable means such as mechanical stirrers, circulation through outside tunnels, etc. The reaction is continued for a period of time'sufficient to nitrate substantially all the alkyl aromatic hydrocarbons, usually from about 15 minutes to 2 hours.

The reduction of the above nitrated alkyl aromatic hydrocarbons to form the corresponding alkyl aromatic amino derivatives and alkyl anilines also may be carried out according to various methods such as catalytic hydrogenation, reduction by iron and acid, etc. In view of the uncommon nature of the long-chain alkyl aromatic compounds and their highly refractory character I have devised certain novel methods which are here also preferred. One such method using iron and hydrochloric acid or iron and ferric chloride has been found very suitable. At least 0.1 gram equivalents of a chloride-producing material such as FeCl3.6H2O, HCl, etc., per gram equivalent of nitro derivative is ordinarily required, and from about 0.2 to about 0.5 gram equivalents is preferred. A small amount of water, usually 4 to 5 moles per mole of nitro compound, is preferred to larger amounts of water. However, other small proportions of water, say from about 3 to 7 moles per mole of nitro derivative may also be used effectively. The small amount of water produces a higher chlorine ion concentration to give a greatly improved and much higher rate of reaction. From about 1 to 4 moles of iron per mole of alkyl nitro aromatic, and more suitably about 2 to 3 moles, are used. The iron may be present in the form of reduced iron powder, iron powder, iron filings, etc., with reduced iron powder being preferred for its greater reactivity and the shorter reaction time it allows. The temperature of the reduction is preferably maintained at about 100 0, although temperatures ranging between about 70 to 130 C. are suitable. The reaction time for a substantial conversion to the amine usually takes from about 1 to 10 hours depending on the reactivity of the iron catalyst and the other conditions of reaction. Since the reaction mixture becomes quite viscous toward the latter stages of the reaction, various solvents may be utilized such as isopropyl alcohol, n-butyl alcohol, xylene, petroleum naphthas, etc. For the present operations it has been found that petroleum naphtha permits the highest yields and most efficient mixing. The crude alkyl aromatic amino product may be purified by known methods such as vacuum distillation, clay treating, solvent extraction, etc.

The quaternization of the alkyl aromatic amino derivatives to produce the corresponding quaternary ammonium alkyl sulfate may be performed by various methods. The alkyl aniline may first be converted to a secondary or tertiary amine having the desired radicals by alkylating the nitrogen atom with any of the common alkylating agents which will produce the radicals previously described in relation to the structural formula set out above. Such agents are ethyl chloride, allyl chloride, benzyl chloride, 2,3-dichloro-propylene, p-chlorobenzyl chloride, ethylene oxide, etc. The product can then be quarternized with a short-chain dialkyl sulfate to give the quaternary ammonium alkyl sulfate. One method which found particularly suitable is to react the alkyl aromatic primary amine, or alkyl aniline, solely with a short-chain dialkyl sulfate such as methyl sulfate, ethyl sulfate, etc. A slight excess of the dialkyl sulfate is desirable and as much as 3 to 4 moles per mole of alkyl aniline is usually preferred. The reaction may be carried out in the presence of solvents such as ethyl acetate, di-isopropyl ether, methanol, etc. Temperatures in excess of about 25-35" C. are preferred, since the reaction proceeds sluggishly up to that point. Higher temperatures of around 55 C. or higher are also very suitable. Although the reaction may be carried out in an anhydrous medium, it is preferred that an aqueous solution be utilized to permit rapid neutralization of the excess sulfate ions formed in the reaction. Any neutralizing agent such as NaHCOs can be used for this purpose. The reaction mixture may be purified by distillation, clay treating or solvent extraction, as, for example, by dissolving the reaction mixture in an aqueous alcohol solution followed by extraction with petroleum ether to remove impurities, including unreacted materials.

Dry, free-flowing powder compositions, according to my invention, are prepared, using builders and bulking agents selected from a wide variety of materials as hereinafter disclosed. The particular material selected for incorporation in the composition of my invention will be determined somewhat by the processes utilized in preparing the composition and also by the particular use contemplated for the product. When the hydration process of preparing free-flowing powders is used, it is essential that the builder or bulking agent be of a type capable of forming a hydrate at temperatures below about 50 to 60 C., and of losing its hydrate characteristics at elevated temperatures above about 50 to 60 C. Suitable builders of this type are the alkaline builders such as borax, tetrasodium pyrophosphate, sodium tripolyphosphate, and the like. The preferred builders for the hydration process are the polymeric phosphates. These builders are also suitable for use in other processes than the hydration process for preparing the compositions of the present invention, as, for example, drum drying, spray drying, etc. Examples of other inorganic builders which also may be used in the heat-drying processes are the alkali metal carbonates, borates, silicates and phosphates such as sodium carbonate, sodium sesquicarbonate, sodium metaborate, sodium perborate, sodium tetraborate, sodium silicate, sodium metasilicate, disodium phosphate, sodium hexametaphosphate, their potassium equivalents and the like. The corresponding ammonium salts are also included. Still other builders which are suitable in the heat-drying or evaporative processes of preparing the germicidal compositions according to my invention are the neutral builders or neutral reacting inorganic salts such as sodium sulfate, sodium chloride, etc.

In addition to, or instead of, builders of the above types, the dry, free-flowing powder composition according to my invention may contain a filler or bulking agent to produce a less concentrated form. Although the fillers or bulking agents may be any of those heretofore known to the art, it is preferred that a water-soluble, non-hygroscopic, stable material be utilized. Sodium sulfate, already noted above as a neutral builder, is a'preferred filler or bulking agent since it is neutral, inexpensive and is water-soluble. Other materials including bentonite and various other colloidal clays, silica aerogel, etc., as well as known organic fillers such as dextrose, sugars, urea, salts of organic acids such as sodium acetate, etc., may also be used.

In addition to the above builders, fillers and bulking agents, my composition may contain various cationic and non-ionic surface active agents, abrasives, or other substances suitable for improving its physical properties in scouring, foaming, and cleansing applications. The surface active agents may be cationic detergents such as heat stable amines, sulfonium salts, phosphonium and arsomum bases, etc., or non-ionic detergents such as alkyl phenyl polyglycol ethers, etc. Abrasives, such as pumice, fulle'rs earth, kaolin, etc., are capable of producing satisfactory scouring compositions. Dyes and perfume may also be added if desired to alter the physical appearance and odor of the final product.

The quaternary ammonium alkyl sulfate germicidal compositions according to my invention as described above are characterized by their unusually high stability toward heat and alkaline materials. Temperatures as high as about 115 C. have no deleterious efiect on these compositions and, ordinarily, temperatures up to about 150 C. may be withstood for reasonable periods of time without noticeable degradation. Highly alkaline materials such as sodium carbonate and the like which have a pH of from about to 12 in water solution may be closely associated with my quaternary ammonium alkyl sulfate compositions without giving any evidence of decomposition. Other quaternary ammonium germicidal compositions such as the quaternary ammonium halides decompose badly at temperatures below 115 C. and become darkened in color. Such salts are also subject to degradation in the presence of alkaline substances as evidenced by their objectionable amine odor.

The following examples will serve to illustrate my invention, but are not to be construed as being in limitation thereof.

EXAMPLE 1 The preparation of alkyl-phenyl trimethyl ammonium methosulfate was carried out as follows:

125 g. of a propylene polymer-substituted benzene having about 12 to 15 carbon atoms in the alkyl radical was placed in a fiask cooled in an ice water bath and nitrated by dropwise addition of a mixture of 50 grams concentrated nitric acid. 40 grams sulfuric acid, and 90 grams fuming sulfuric acid. The lower, dark-colored acid layer was drawn off and discarded. The upper layer comprising the alkyl benzene nitro derivative was diluted with 100 g. of petroleum naphtha thinner and washed with water, followed by washing with a 1% sodium hydroxide solution and then another washing with water. The resultant material was substantially mono-nitroa1ky1 benzene in petroleum naphtha thinner.

About 240 g. of the above crude nitrated alkyl aromatic and thinner was placed in a flask with 120 g. of 160-mesh iron powder and 12.3 g. of ferric chloride hexahydrate. The mixture was stirred and heated up to about 100 C. at which point 10.2 ml. of water was added dropwise over a period of about 5 hours. The hot reaction mixture was then filtered to remove iron oxides. The filtrate, upon distillation, produced about 123 g. of alkyl aniline suitable for quaternization to the corresponding quaternary ammonium compound.

About 27 g. of the alkyl aniline prepared according to the preceding paragraph was placed in a flask along with 30 ml. of tap water and 21 g. of sodium bicarbonate. The flask was immersed in a cold water bath and 21.6 g. of dimethyl sulfate was added dropwise with stirring. The temperature of the mixture was maintained at about 25-40 C. during the addition which required about minutes. After the evolution of carbon dioxide had essentially ceased, the reaction mixture was warmed to 75 C. with stirring to complete the reaction and then cooled to about 30 C. ml. of methanol was then added, following which the reaction mixture was extracted with petroleum ether to remove the unreacted alkyl aniline. The aqueous portion left from the extraction with petroleum ether was then treated with ml. of water and ml. of benzene. This mixture was allowed to settle and the lower aqueous solution containing inorganic salts was removed and discarded. The benzenemethanol solution containing the quaternary ammonium methosulfate product was diluted with water and evaporated under reduced pressure to remove the benzene and methanol. The resulting aqueous solution of the product was then evaporated to dryness to give a colorless to tancolored gummy solid which was completely soluble in water and alcohol.

EXAMPLE 2 A dry, free-flowing stable composition of the alkylphenyl trimethyl ammonium methosulfate product of Example 1 and tetrasodium pyrophosphate was prepared by drum drying as follows:

20 parts of the alkylphenyl trimethyl ammonium methosulfate was placed in a mixing vessel with 80 parts of tetrasodium pyrophosphate (NasPaOmlOI-IaO) and thoroughly mixed. Sutficient water was added to form a slurry. The slurry was then dried in a small drum dryer heated with enclosed steam. The steam pressure ranged from about 20 to 25 pounds per square inch gauge producing a temperature of about 109 to 113 C. in the dryer. Only a few seconds were required to evaporate the water from the mixture. The dried product was a free-flowing germicidal composition possessing a clean white appearance. No decomposition of the quaternary salt was observed.

EXAMPLE 3 The alkyl-phenyl trimethyl ammonium methosulfate of Example 1 and trisodium phosphate were mixed to produce a dry, free-flowing stable composition using the following procedure:

20 parts of the alkyl-phenyl trimethyl ammonium methosulfate was placed in a mixing vessel with 80 parts of the trisodium phosphate (Na3PO4.12H2O) and thoroughly mixed. Water was then added in amount sufficient to produce a slurry of the foregoing mixture. The resulting slurry was transferred to a small drum drier heated with steam in an enclosed system. The steam pressure in the system was maintained at about 20 to 25 pounds per square inch gauge to produce temperatures of about 109 to 113 C. in the drier. The mixture after drying was a clean white free-flowing composition having germicidal properties and exhibited no visible indication of decomposition by the active quaternary ingredient.

EXAMPLE 4 A dry, free-flowing germicidal composition containing dodecyl-phenyl trimethyl amonium methosulfate and a non-ionic surface active agent was prepared by the hydration process as follows:

70 parts of anhydrous tetrasodium pyrophosphate was placed in a mixing vessel equipped with heating means. The tetrasodium pyrophosphate was heated to about C., at which point 5 parts of an iso-octyl-phenyl polyglycol ether, non-ionic surface active agent having approximately ten ethoxy groups in the ether radical was added along with 5 parts of the quaternary ammonium methosulfate. The materials were mixed thoroughly while maintaining the temperature at about 90 C. 20 parts of water were then added and the resultant slurry stirred until cool. The mixture when cooled gave a dry, free-flowing power that was clean and white in appearance. No decomposition of the active germicidal ingredient was observed which would be indicative of instability toward the alkaline tetrasodium pyrophosphate or the heat utilized in the preparation. One-half ounce of the product in a gallon of water provides an excellent detergent sanitizer solution characterized by high germicidal eificiency and improved drainage of rinse-water from glassware.

EXAMPLE 5 For the purpose of comparison, a mixture of an ordinary type of quaternary such as the quaternary ammonium halides illustrated by the long-chain alkyl-benzyl trimethyl ammmonium chlorides was prepared as follows:

22.8 parts of a 40% aqueous solution of an alkyl-benzyl trimethyl ammonium chloride having from 12 to 15 carbon atoms in the alkyl radical was mixed in a vessel with 92.6 parts of trisodium phosphate (NasPO4.12HzO). Additional water was added to form a slurry. The slurry was then dried as in the preceding example by passing it into a small drum drier heated with enclosed steam at a pressure of about 20 to 25 pounds per square inch gauge giving temperatures of about 109 to 113 C. After the water was evaporated from the mixture, the product was found to have darkened badly, indicating decomposition. The product also had a tendency to cling to the drum drier and did not produce a satisfactory free-flowing powder.

In the above examples the parts are on a weight basis unless otherwise indicated.

From Examples 2 and 3 above, it will be noted that the dry free-flowing germicidal compositions of my invention are stable to heat and alkaline builders. The drum-dried products are clean and White in appearance and show no visible decomposition of the active quaternary ammonium germicide ingredient. On the other hand, the attempted preparation of dry, free-flowing powders from other quaternaries, such as the quaternary ammonium halides illustrated by long-chain alkyl-benzyl trimethyl ammonium chloride, as set out in Example 5, was a complete failure. The products were a dirty battleship gray in appearance and decomposition of the active ingredient was plainly visible. Furthermore, it was impossible to produce free-flowing powders because of the sticky nature of the product undoubtedly due to the unstable quaternary ammonium ingredient. From these comparative examples, it is obvious that my novel germicidal compositions possess higher stability to heat and alkaline builders than compositions containing conventional quaternary ammonium salts, and have decidedly superior advantages in the production of dry, free-flowing quaternary ammonium germicidal and fungicidal preparations.

The efiicacy of various quaternary ammonium alkyl sulfate compositions, according to my invention as described above, is illustrated by the tests given in the following table.

TABLE pressions in mineral oil-water mixtures and show excellent emulsifying properties, indicating their utility as combined germicidal and cleaning compositions such as detergent-sanitizer formulations, scouring powders and the like.

In view of the foregoing disclosure, variations and modifications of the invention will be obvious to those skilled in the art. All such variations and'modifications as come within the scope of the appended claims are contemplated within this invention.

I claim:

l. The method of forming a dry, heat-stable, free-flowing part1culate quaternary ammonium germicide composition which comprises mixing a phosphate builder selected from the group consisting of trisodium phosphate and tetrasodium phosphate with from about 1% to about by weight of an alkylphenyl trimethyl ammonium methosulfate having from 12 to 15 carbon atoms Evaluation of the germicidal activities of alkyl-aryl trimethyl ammonium methosulfates by the phenol 00- my invention also possess valuable wetting and detergent properties. They possess marked interfacial tension deeflicient method Phenol eoeflicient (KP 0.)

No. Compounds T E. s. T. inn-F typhoaa aureas romceum digital ClH11Phl(CH3)lGH1 OF a2 a0 ounn-rh-riwmncmsor. 200 s 14 11 oumr-rh-fiwrmtontsor 280 241 20 34 4 ounrrkfiwnoiomsot- 250 270 100 145 omnu-rh-inomncmsor 65 as c.,-"Pn-1 i(cH.)tcH.so. 250 280 23 c., ,t-Pit-ri(om)iomsot- 130 135 01H, -I :(oH).),cH.so.--.-. 400 420 c., ,,PhI oB=),0H,sot- 4o The results set forth in the preceding table relating to in its alkyl radical, uniformly combining said mixture E. typhosa and S. aureus organisms were obtained by a with an aqueous medium and drying the composition so determination of the germicidal activity according to the formed at a temperature of about 109 C. to about method of testing antiseptics and disinfectants published 150 C. by the U. S. Food and Drug Administration in the De- 2. The method of claim 1 in which the phosphate partment of Agriculture Circular No. 198 of December builder is trisodium phosphate. I 1931. In these determinations the phenol coeflicient illus- 3. The method of claim 1 in which the phosphate trating the killing power of the quaternary ammonium builder is tetrasodtum phosphate. compositions was obtained at 20 C. using Letheen broth 4. The method of claim 1 in which said drying is in the sub-culture to prevent bacteriostasis. The effected at a temperature of from about 109 C. to

- T. rosaceum and T. interdigitale phenol coefficients were 113 C.

determined according to the method set out in Navy Department Specification 51 Dh 6 (SepteSmber 1944). References Cited in the file of this patent The first two organisms, E. typ osa and aureus, are

standard test organisms representing gram negative and W STATES PATENTS gram positive types. Trichophyton rosaceum and Tri- 2,097,640 P1ggott Nov. 2, 1937 chophyton interdigitale are fungi commonly found in 2,154,977 Furness Apr. 18, 1939 human skin infections and are standard test organisms 2,176,896 Epstein Oct. 24, 1939 in the method of evaluating the killing power of fungi- 2,500,024 Cornell Mar. 7, 1950 cides. 2,519,841 MacMahon Aug. 22, 1950 It may be concluded from the above table that the 2,541,248 Hibbs Feb. 13, 1951 quaternary ammfionium alkyl stlfftte ciotfnpositignls of my 2,584,056 Soule Jan, 29, 1952 invention are e ective germici a an ungici a agents.

In addition to the above germicidal and fungicidal FOREIGN PATENTS activities, other evaluations of these compositions indi- 490,285 Great Britain Aug. 11, 1938 cate that they are superior asphalt anti-stripping agents 505,429 Great Britain May 1, 1939 and ore flotation agents. The stability of my quaternary 618,433 Great Britain Feb. 22, 1949 ammonium alkyl sulfate compositions to heat is a distinct 155.653 Japan Mar. 26, 1943 advmtage (aver other types of qiuaternariesTlclommonly (Cited in Chem. Abst., vol. 44, 1950, pp. 5544 and 5545.)

use in asp a t anti-stripping app ications. e quaternary ammonium alkyl sulfate compositions according to OTHER REFERENCES Ludwig, Repertorium Pharmazeutischer Spezial Praparate, 1948, Beobachter, Basel, p. 252.

Claims (1)

1. THE METHOD OF FORMING A DRY, HEAT-STABLE, FREE-FLOWING PARTICULATE QUATERNARY AMMONIUM GERMICIDE COMPOSITION WHICH COMPRISES MIXING A PHOSPHATE BUILDER SELECTED FROM THE GROUP CONSISTING OF TRISODIUM PHOSPHATE AND TETRASODIUM PHOSPHATE WITH FROM ABOUT 1% TO ABOUT 20% BY WEIGHT OF AN ALKYLPHENYL TRIMCTHYL AMMONIUM METHOSULFATE HAVING FROM 12 TO 15 CARBON ATOMS IN ITS ALKYL RADICAL, UNIFORMLY COMBINING SAID MIXTURE WITH AN AQUEOUS MEDIUM AND DRYING THE COMPOSITION SO FORMED AT A TEMPERATURE OF ABOUT 109* C. TO ABOUT 150* C.