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Publication numberUS3431265 A
Publication typeGrant
Publication dateMar 4, 1969
Filing dateMar 17, 1964
Priority dateMar 17, 1964
Publication numberUS 3431265 A, US 3431265A, US-A-3431265, US3431265 A, US3431265A
InventorsJoseph E Coates, Reginald L Wakeman
Original AssigneeMillmaster Onyx Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Quaternary ammonium salts of glyceryl sulfates and sulfonates
US 3431265 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

3,431,265 QUATERNARY AMMONIUM SALTS F GLYCERYL SULFATES AND SULFONATES 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 New York No Drawing. Filed Mar. 17, 1964, Ser. No. 352,631 U.S. Cl. 260-286 4 Claims Int. Cl. C07d 35/18; C07c 143/00 ABSTRACT OF THE DISCLOSURE Quaternary ammonium salts of coconut monoglyceride sulfates and sulfonates, and alkyl glyceryl ether sulfates and sulfonates, having germicidal activity, are described.

The present invention has for its object the preparation of microbiologically active compounds by reaction of certain quaternary ammonium hydroxides or their salts of inorganic acids With alkyl or acyl glyceryl ether or ester sulfates or sulfonates in which the alkyl or acyl radicals contain from 8 to 22 carbon atoms.

The products of this invention conform, in general, to the following structure:

wherein R is an alkyl or acyl radical of the aliphatic series, either straight or branched chain, containing from 8 to 22 carbon atoms; Z is a sulfate or sulfonate group and Q is the cation of a microbiologically active quaternary ammonium compound.

The intermediate alkyl glyceryl ether sulfates and sulfonates and the intermediate acyl glyceryl ester sulfates and sulfonates used as reactants in this invention are well known anionic surfactants, each of which may be produced by any desired method. Because of the com plexity of their structure, they will usually be constituted of mixtures containing lesser amounts of by-products obtained during the course of their manufacture, but the mono alkyl ether or mono acyl ester derivatives predominate in all of these compounds.

The alkyl glyceryl ether sulfonates may be prepared, for example, by application of the Strecker reaction to the condensation product of a fatty alcohol and epichlorohydrin as described in US. Patent No. 3,024,273. The alkyl glyceryl ether sulfates may be prepared, for example, by reaction of sulfuric acid with alkyl glycid-yl ethers. The acyl glyceryl ester sulfonates may be prepared, for example, by reaction of a fatty acid soap with sodium glyceryl monochlorohydrin sulfonate as described in US. Patent No. 2,289,391. A Wide variety of methods are available for production of acyl glyceryl ester sulfates and some of these products, especially Where the acyl radical is that derived from coconut oil, are produced commercially.

The alkyl glyceryl ether sulfonates used according to the process of this invention comprise, for the most part, RO'CH CH(OH)CH SO M and the corresponding sulfates are largely Where M is the cation of a Water-soluble salt and R is an alkyl radical containing from 8 to 22 carbon atoms such as octyl, decyl, lauryl, myristyl, palmityl, stearyl, arachidyl, behenyl or any branched chain isomeric alkyl radical. Instead of an alkyl radical, an alkylphenyl radical or alkylphenoxyethyl radical containing from 8 to 22 carbon atoms may be used if desired such, for example,

nited States Patent 0 as octylphenyl, nonylphenyl, octylphenoxyethyl or nonylphenoxyethyl groups.

The acyl glyceryl ether sulfonates used according to the process of this invention comprise, for the most part, R OCH CH('OH)CH SO M, Where R is an aliphatic acid radical containing from 8 to 22 carbon atoms such as octanoyl, decanoyl, lauroyl, myristoyl, palmitoyl, stearoyl, arachidoyl, behenoyl or any branched chain isomers. The acyl sulfates possess corresponding structures.

Typical examples of the quaternary ammonium compounds which may be used in this invention are the alkyl trimethyl ammonium chlorides, alkyl-benzyl 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 5 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 halogen atoms such as chlorine or bromine, alkyl pyridinium chlorides, alkyl isoquinolinium chlorides and bromides, 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 ethoxy ethyl dimethyl benzyl ammonium chloride in which the alkyl radical may be iso-octyl or nonyl and in which the phenyl 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.

In general, the quaternary ammonium compounds useful in this invention are the higher alkyl quaternary ammonium hydroxides, halides (chlorides and bromides), sulfates, methosulfates and the like possessing the following formula:

where R is an alkyl or alkaralkyl radical containing from 8 to 22 carbon atoms or an alkyl phenoxy ethoxy ethyl radical in which -R is an alkyl radical containing from 8 to 9 carbon atoms and in which the phenyl radical may be substituted by a methyl group; R and R" are methyl or ethyl radicals or members of a heterocyclic ring system such as pyridine, isoquinoline, pyrrolidine and morpholine; R' is a methyl radical or a benzyl group or a substituted-benzyl group which, for example, as a monochlorobenzyl radical or a dichlorobenzyl radical or mixture thereof or a methyl benzyl, dimethyl benzyl, ethyl benzyl, diethyl benzyl, isopropyl benzyl, tertiary butyl benzyl or another benzyl radical containing from 1 to 5 carbon atoms as side chains, either as a single side chain or a multiplicity of side chains including mix tures thereof or a menaphthyl groupor hydrogenated menaphthyl group. When R and -R" are members of a. morpholine or pyrrolidine ring, R' is a methyl, ethyl, propyl, or butyl group. When R and R" are members of an unsaturated heterocyclic ring such as pyridine or isoquinoline, R is the same radical as R". X in the above formula corresponds to a halide radical such as chloride, bromide or iodide or to any other water-soluble anion such as methosulfate.

In general, we prefer to use such quaternary ammonium compounds which have a phenol coefficient of at least 100 with respect to both Staphylococcus aureus and Salmonella typhosa at C. when determined by the standard method given in the Official Methods of Analysis of the Association of Oflicial Agricultural Chemists, Ninth Edition (1960) pp. 63 et seq.

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 layer 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 ammonium compound 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 atfecting 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, for example, as sulfonated castor oil or pine oil and diluting with water. In preparing aqueous dispersions, 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 compound 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 antimildew 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 hacteriostatic films and molded objects deposited from such latices.

The compounds can be incorporated into cutting 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 cationic quaternary ammonium compound used in their preparation as well as the anionic compound reacted therewith.

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.

(1 2) Plant and tree spray to combat fungi.

(13) Antimycotic agents for soap wrappers.

(14) Self-sanitizing brushes.

(15) 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.

(25) Additives for soap and for both anionic and nonionic detergents in liquid, bar, powder, bead, solution and other forms to impart bacteriostatic and fungistatic properties thereto.

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 applica tions, 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 EXAMPLE I In a two liter separatory funnel were placed 394 grams of a 10% solution of sodium coconut monoglyceride sulfate (molecular weight 382) and 400 grams of a 10% solution of alkyl dimethyl ethylbenzyl ammonium chloride (ETC-471, Onyx Chemical Corporation. Alkyl distribution: C 50%; C 30%; C 17%; C 3%) was added along with 100 ml. of benzene. The funnel was well shaken and layer separation allowed to occur. The organic product layer was separated and dried first on a steam bath and then in a vacuum oven to give 42 grams (57% yield) of a yellow gel of alkyl dimethyl ethylbenzyl ammonium coconut monoglyceride sulfate.

EXAMPLE II In a two liter separatory funnel were placed 402 grams of a 10% solution of sodium coconut monoglyceride sulfate (molecular weight 382) and 400 grams of a 10% solution of alkyl dimethyl benzyl ammonium chloride (BTC-824, Onyx Chemical Corporation. Alkyl distribution: C 60%; C 30%; C C 5%) was added along with 100 ml. of benzene. The funnel was Well shaken and layer separation allowed to occur. The organic product layer was separated and dried first on a steam bath and then in a vacuum oven to give 76 grams (100% yield) of a yellow paste of alkyl dimethyl benzyl ammonium coconut monoglyceride sulfate.

EXAMPLE III Using the technique of Example II, equimolar quantities of lauryl isoquinolinium bromide (Isothan Q75, Onyx Chemical Corporation) and sodium coconut monoglyceride sulfate were reacted to give a 100% yield of a tan paste of lauryl isoquinolinium coconut monoglyceride sulfate.

EXAMPLE IV Using the Standard Tube Dilution Test described above, the following bacteriostatic levels against Staphylococcus aureus (S. a.), Salmonella typhosa (S. t.) and Aspergillus nz'ger (A. n.) were determined:

Bacteriostatic dilution level vs.

Product from- 5.3. S.t. A.n.

Example I 10 10 Example II 10 10 10 Example III. 10 10 10 Instead of the sodium salt of coconut monoglyceride sulfate used in Examples I to III, the coresponding sulfonate was employed with similar results.

Comparable products with microbiological activity Were also produced from the sodium salt of lauryl glyceryl ether sulfate and from the sodium salt of lauryl glyceryl ether sulfonate.

We claim:

1. A compound having the structure:

wherein R is a straight chain or branched chain alkyl or acyl having 8 to 22 carbon atoms; Z is a sulfate or sulfonate group; and Q is the cation of a quaternary ammonium compound having an alkyl of from 8 to 22 carbon atoms attached to the quaternary nitrogen and a phenol coeflicient of at least with respect to both Staphylococcus aureus and Salmonella typhosa at 20 C.

2. Alkyl dimethyl ethylbenzyl ammonium coconut monoglyceride sulfate wherein the alkyl has 8 to 22 carbon atoms.

3. Alkyl dimethyl benzyl ammonium coconut monoglyceride sulfate wherein the alkyl has 8 to 22 carbon atoms.

4. Lauryl isoquinolinum coconut monoglyceride sulfate wherein the alkyl has 8 to 22 carbon atoms.

References Cited UNITED STATES PATENTS Re. 20,636 1/1938 Harris 260-400 X 2,285,773 6/1942 Harris 260-400 2,693,479 11/1954 Ross 260-400 2,710,250 6/1955 Andrews et al 260-400 X 2,894,009 7/1959 Schmolka 260-400 ALEX MAZEL, Primary Examiner.

D. G. DAVIS, Assistant Examiner.

US. Cl. X.R.

Patent Citations
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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3797574 *Oct 27, 1972Mar 19, 1974Texaco IncMiscible oil recovery process
US3871454 *May 3, 1973Mar 18, 1975Harrison William MWater flood process in clay-bearing subsurface formations
US3950258 *Dec 6, 1974Apr 13, 1976Sanyo Chemical Industries, Ltd.Aqueous lubricants
US3977471 *Sep 26, 1975Aug 31, 1976Exxon Production Research CompanyOil recovery method using a surfactant
US4051047 *Mar 24, 1976Sep 27, 1977Chevron Research CompanyGroup II metal mixed salts of two different organic acids in lubricant
US4130494 *Feb 6, 1978Dec 19, 1978Exxon Research & Engineering Co.Synthetic lubricant composition
US4163850 *Dec 15, 1977Aug 7, 1979Petrolite CorporationPolycyclic full quaternary nitrogen-heterocyclic phosphonates
US4303543 *Jul 23, 1979Dec 1, 1981The Procter & Gamble CompanyMethod for cleansing and conditioning the skin
US4536309 *Jul 29, 1982Aug 20, 1985Mobil Oil CorporationZwitterionic quaternary ammonium sulfonates and sulfates and lubricants containing same
US4581149 *Jun 5, 1985Apr 8, 1986Mobil Oil CorporationZwitterionic quaternary ammonium sulfonates and sulfates and lubricants and fuels containing same
US4581150 *Jun 5, 1985Apr 8, 1986Mobil Oil CorporationZwitterionic quaternary ammonium sulfonates and sulfates and lubricants and fuels containing same
US4588522 *Apr 13, 1983May 13, 1986Hoechst AktiengesellschaftBetaine-amine oxides, a process for their preparation and their use as surfactants
US4764214 *Apr 9, 1987Aug 16, 1988Dr. Wolman GmbhWood preservatives containing 2-iodobenzanilide
US5833741 *Jan 16, 1997Nov 10, 1998Lonza Inc.Waterproofing and preservative compositons for wood
EP0011311A2 *Jun 11, 1979May 28, 1980FMC CorporationAlkyl glyceryl ether sulfate salts, process for their preparation and composition of matter containing them
EP0011311A3 *Jun 11, 1979Feb 11, 1981Fmc CorporationAlkyl glyceryl ether sulfate salts, process for their preparation and composition of matter containing them
Classifications
U.S. Classification546/151, 426/614, 162/8, 554/92, 8/188, 544/108, 510/384, 510/504, 508/405, 510/391, 504/157, 510/496, 504/156, 508/261, 554/90, 504/160, 106/18.32, 562/110, 510/133, 508/389, 106/3, 546/347, 8/127.6, 510/131, 252/8.57, 504/155
International ClassificationE21B43/22, C07C305/10
Cooperative ClassificationC10M2219/042, C10M1/08, C10M2219/044, C10N2240/108, C10N2240/401
European ClassificationC10M1/08
Legal Events
DateCodeEventDescription
Jun 9, 1983ASAssignment
Owner name: BARCLAYS AMERICAN, 1 BUSINESS CREDIT, INC. 111 FOU
Free format text: SECURITY INTEREST;ASSIGNOR:MILLMASTER ONYX GROUP, INC., A DE CORP.;REEL/FRAME:004139/0941
Effective date: 19821222
Owner name: MILLMASTER ONYX GROUP, INC., A DE CORP.
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:KEWANEE INDUSTRIES, INC.;REEL/FRAME:004139/0909
Effective date: 19830407