US 3565927 A
Description (OCR text may contain errors)
xa 3565927 R,
UIIIICU Ol'dLCD 1 cent Oflice 3,565,927 Patented Feb. 23, 1971 3,565,927 QUATERNARY AMMONIUM COMPOUNDS HAV- ING A BRANCHED CHAIN ALIPHATIC ACID ANION Reginald L. Wakeman, Philadelphia, Pa., and Joseph F. Coates, Washington, D.'C., assignors to Millmaster Onyx Corporation, New York, N.Y., a corporation of New York No Drawing. Continuation-impart of application Ser. No. 295,217, July 15, 1963. This application Mar. 12, 1968, Ser. No. 712,376
Int. Cl. C091? 7/00 U.S. Cl. 260--404 6 Claims ABSTRACT OF THE DISCLOSURE Microbiocidal compounds having a cation derived from a microbiocidal quaternary ammonium compound where in there is at least one alkyl group of 8 to 22 carbon atoms attached to the quaternary nitrogen and an anion derived from a branched chain aliphatic acid, containing at least seven carbon atoms.
This is a continuation-in-part of co-pending application Ser. No. 295,217, filed July 15, 1963 now abandoned.
This invention relates to the preparation of substantially water-insoluble microbiocidal compounds by reaction of certain quaternary ammonium hydroxides or their salts of inorganic acids with branched chain aliphatic acids or their salts containing nine or more carbon atoms, pref erably between 9 and 21 carbon atoms. Particularly advantageous are those aliphatic acids referred to as neoacids. The quaternary ammonium compounds used as starting materials are those which contain at least one carbon chain of 8 to 22 carbon atoms attached to the quaternary nitrogen.
Typical examples of the quaternary ammonium compounds used as starting materials are alkyl trimethyl ammonium chloride, alkyl-benzyl trimethyl ammonium chloride, and alkyl dimethyl benzyl ammonium chloride in which the alkyl group may have from 8 to 22 carbon atoms, alkyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride in which the alkyl radical may be isooctyl or nonyl, 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, trimethyl, tetramethyl, ethyl, diethyl, isopropyl,- tertiary butyl and isoamyl, or with one, two or more halogen atoms such as chlorine, and alkyl dimethyl menaphthyl or tetrahydromenaphthyl ammonium chloride in which the alkyl radical contains from '8 to 22 carbon atoms, and mixtures of the aforesaid quaternary ammonium compounds.
It has been discovered, however, that contrary to genernary ammonium compounds such, for example, asthose methyl pentadecanoic acid derived by oxidation of the aldehyde mixture obtained through the 0x0 process by reaction of carbon monoxide with pentadecene-l. Such a composition, for example, is obtainable by oxidation of an aliphatic alcohol blend containing about 40% of the branched chain fatty acid together with about 50% of hexadecanoic acid together with minor amounts of other materials.
As suitable acids we may employ any acyclic aliphatic acid having a branched chain or mixtures of same. Thus, for example, we may oxidize alcohols containing one or more methyl groups attached to various points along the carbon chain derived from oxo aldehydes. When alpha olefins are employed, the principle branching consists of a methyl group alpha linked relative to the carboxyl group.
, When propylene or butylene polymers, for example, are
of the preceding types are not compatible, that is to say,
lose their microbiocidal activity in the presence of anionic materials, particularly in the presence of soaps.
It has been discovered, however, that contrary to general belief the reaction of microbiocidal water-soluble quaternary ammonium compounds which do not contain heterocyclic nitrogen with branched chain aliphatic acids such as the neo-acids, or with their water-soluble salts, yields products which in many cases are equally as microbiocidal as the parent quaternary ammonium compounds from which they are derived. Insome cases they are more active.
It is possible, if desired, to employ mixtures of branched chain aliphatic acids together with straight chain aliphatic acids of the fatty type. Thus, for example, we may employ synthetic mixtures of hexadecanoic acid and alpha employed, the chain may be highly branched. A typical oxo alcohol derived from a propylene pentamer, for example, has the following structure:
This compound may be oxidized by conventional methods to a branched chain hexadecanoic acid whereby the 'CH OH group is oxidized to a COOH group.
Very suitable branched chain aliphatic acids are those produced from olefins by means of the so-called Koch reaction involving the inter-action of olefins, water and carbon chain derived from oxox aldehydes. When alpha (See, for example, U.S. Pats. 2,831,877 and 2,876,241.) Acids of this nature contain a neo-carbon atom to which the carboxyl group is attached and they possess the following structure, wherein R R and R are straight or branched chain alkyl radicals, and preferably one being a methyl radical:
Such neo acids containing 9, 10 and 13 carbon atoms are commercially available under the trademark Versatic from the Shell Chemical Company. Thus, for example, Versatic 911 is a mixture of neo acids containing 9, 10 and 11 carbon atoms, the neo acid content being approximately of the technical product.
Other branched chain aliphatic acids prepared by any convenient method may also be employed for the purposes of this invention. Thus, for example, it is possible to oxidize by conventional methods 5-ethyl-nonanol-2.
The acids suitable for use in the process of this invention may, if desired, be substituted by halogen atoms such as chlorine or bromine. The aliphatic acids are preferably reacted in the form of their water-soluble salts such as their sodium, potassium or ammonium salts or in the form of the free acid if solubility relationships permit.
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:
RI RIII RI! where R is selected from the group consisting of an alkyl radical containing from 8 to 22 carbon atoms; an alkyl benzyl phenoxy ethyl radical in which the alkyl radical contains 8 to 9 carbon atoms and in which the phenyl radical may be substituted by a methyl group; R and R" are methyl radicals, R' is a methyl radical or a benzyl group or a halo substituted benzyl group such, for example, as a monochloro benzyl radical, a dichloro benzyl radical or mixture thereof, or an alkyl benzyl, such as a methyl benzyl, dimethyl benzyl, ethyl benzyl, diethyl benzyl, isopropyl benzyl, tertiary butyl benzyl, or any other benzyl radical containing from 1 to 4 carbon atoms as side chains, either as a single side chain or a multiplicity of side chains, and in which X represents an anion, such as a halogen, hydroxyl, alkoxy, sulfate and methosulfate radical.
In general, any quaternary ammonium compound may be used as a starting material if it has a phenol coetiicient of at least 100 with respect to Staphylococcus aureus and Salmonella typhosa at 20 C. and where there is at least one alkyl of 8 to 22 carbon atoms attached to the quaternary nitrogen.
The compounds of this invention may be prepared by mixing aqueous solutions of the quaternary ammonium salts or hydroxides with an aqueous solution of a watersoluble salt of the acid in question.
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 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 products on the material. They 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 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 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.
The compounds made according to this invention 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 plastic. 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 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 actvity.
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 carboxylic acid 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, binders, 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 microorganisms, fungi, mold and algae.
(11) Wool preservative.
(12) Plant and tree spray to combat fungi.
(13) Antimycotic agents for soap wrappers.
(14.) Self-sanitizing brushes.
(l5) Mildewproofing agent in and on plastic and film.
(l6) 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 and curtains.
(21) Egg preservation.
(22) Adhesive preservation.
(23) Preservation of latex paints.
The microbiological activity of our compounds has been evaluated for microbiological static 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 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.
It is a surprising fact that the reaction products of the branched chain aliphatic acids with quaternary ammonium compounds in general exhibit greater bacteriological activity than the corresponding derivatives made from fatty acids. Thus, for example, in the Standard Tube Dilution Test heretofore described, the static dilution level of alkyl dimethyl benzyl ammonium chloride in which the alkyl radical is 55-60% G is $5,000,000 when tested against Staphylococcus aureus. The corresponding salt derived by reaction of this quaternary ammonium compound with dodecanoic acid on the other hand has a static dilution level of less than whereas the reaction product with .neo-tridecanoic acid is still $4,000,000 as is also the reaction product of this quaternary ammonium compound with Versatic 911. It should be noted that although the static dilution levels in this case are the same for quaternary ammonium compound and for its salts with neotridecanoic acid and Versatic acid, the actual quaternary ammonium content is only about 50% of the total weight of the salt. Hence, the dilution levels based on quaternary ammonium content of its branched chain salts are actually about twice as high in the salts as in the free quaternary ammonium chloride.
Where lauryl dimethyl ethyl benzyl ammonium chloride is compared to the lauric acid and to neo-tridecanoic acid and Versatic 911, the results are even more startling. Thus, for example, with respect to Staphylococcus aureus the static dilution level of the quaternary itself is $4 The static dilution level of the corresponding lauric acid salt is less than whereas the static dilution level of the corresponding salt of neo-tridecanoic acid is A and the static dilution level of the corresponding Versatic 9].]. salt is /loopoo ooo.
The invention is illustrated by, but not restricted to, the following examples.
EXAMPLE 1 To 130 ml. of a 5% solution of the sodium salts of mixed C9-C11 branched chain acids, average molecular weight 183 (Versatic 911 acid), in a 500 ml. separatory funnel was added 125 ml. of an 11% solution of alkyl dimethyl ethyl benzyl ammonium chloride, average molecular weight 388 (technical grade wherein alkyl=C 50%, C 30%, C 17%, C 3%). The funnel was agitated for one minute. Approximately 50 ml. of benzene was added to facilitate layer separation. The benzene layer was separated and the benzene and water removed from this layer in a vacuum oven to give a 96% yield of a yellow liquid.
EXAMPLE 2 To 130 ml. of a 5% solution of the sodium salts of C -C branched chain acids, average molecular weight 183 (Versatic 911 acid), in a 500 ml. separatory funnel was added 134 ml. of a solution of alkyl dimethyl benzyl ammonium chloride, average molecular weight 380 (technical grade wherein a1kyl=C 60 C 30%, C 5%, C 5%). The funnel was agitated for one minute. Approximately 50 m1. of benzene was added to facilitate layer separation. The benzene layer was separated and the benzene and water removed from this layer to give 18.5 g. of a yellow liquid.
EXAMPLE 3 To 60 ml. of a 10% solution of the sodium salts of a mixture of branched chain C acids, average molecular weight 236 (neo-tridecanoic acid), was added 90 ml. of an 11% solution of alkyl dimethyl ethyl benzyl ammonium chloride, average molecular weight 388 (technical grade wherein alkyl=C 50%, C 30%, C 17%, C
6 3%). The funnel was agitated for one minute. Approxi-= mately 50 ml. of benzene was added to facilitate layer separation. The benzene layer was separated and the benzene and water removed from this layer in a vacuum oven to give 15 g. of product, a light yellow liquid.
EXAMPLE 4 To 60 ml. of a 10% solution of the sodium salts of a mixture of branched chain C acids, average molecular weight 236 (neo-tridecanoic acid), was added ml. of a 10% solution of alkyl dimethyl benzyl ammonium chloride, average molecular weight 380 (technical grade wherein alky1=C C15 C12 5%, C18 The funnel was agitated for one minute. Approximately 50 ml. of benzene was added to facilitate layer separation. The benzene layer was separated and the benzene and water removed from this layer in a vacuum oven to give 14.5 g. yield of a light yellow liquid.
EXAMPLE 5 The results of static dilution tests performed upon the products of Examples 1 to 4 are shown in the following tables.
TABLE I.-BACTERIOSTATIC ACTIVITY ()1? VARIOUS QUA- TERNARY AMMONIUM SALTS OF BRANCHED CHAIN TERNARY AMMONIUM SALTS OF BRANCHED CHAIN ALIPHATIC ACIDS Reciprocal of static dilution level of product vs.
Asper- Penicil- Pullugillus ium laria Quaternary Acid niger luteum pullulans Myristyl dimethyl Neo-trideca- 10 2.5)(10 10 benzyl ammonium noic acid. chloride (technical grade BTC-824). Same Versatic 911. 10 Lauryl dimethyl Neo-tridecanoic 10 ethyl benzyl amacid. monium chloride (technical grade BTC471). Same Versatic 911"- 10 2.5)(10 10 EXAMPLE 6 Three hundred grams of a 10% solution of the sodium salts of mixed branched chain C acids (neo-decanoic acid), were placed in a 1 liter separatory funnel. Five hundred and eighty grams of a 10% solution of alkyl dimethyl ethyl benzyl ammonium chloride, molecular weight 388, were added and the funnel well shaken. On standing, layer separation occurred. The upper layer was separated and dried in a vacuum oven to give 81.5 g. 100%) yield of a yellow liquid.
EXAMPLE 7 Three hundred grams of a 10% solution of the sodium salts of mixed branched chain C acids (neo-decanoic acid), were placed in a 1 liter separatory funnel. Five hundred and eighty grams of a 10% solution of alkyl dimethyl benzyl ammonium chloride, molecular weight 380, were added and the funnel well shaken. One hundred ml. of benzene were added to facilitate layer separation. The upper layer was separated and the benzene and water 7 removed in a vacuum oven to give 74 g. (92% yield) of a yellow liquid.
EXAMPLE 8 In a 250 cc. separatory funnel was placed 97 g. of a 10% solution of alkyl dimethyl ethyl benzyl ammonium chloride, molecular weight 388. To this was added 11 g. of a 40% solution of sodium 2-ethyl hexanoate. The solutions were well mixed by shaking and then the layers were allowed to separate. The upper layer was drawn oil? and dried in a vacuum oven to give 11.9 g. (94% yield) of alkyl dimethyl ethyl benzyl ammonium 2-ethyl hexanoate, a yellow liquid.
EXAMPLE 9 A 25 weight percent solution of each of the compounds of Examples 1 to 8 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 out 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 90% relative humidity for three weeks. At the end of this time, no fungus growth was visible.
EXAMPLE 10 Four parts of each of the 25% solutions of the eight compounds of Examples 1 to 8 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 Pullularz'a pullulans and incubated as in Example 9. At the end of three weeks, no fungus growth was visible in the latex.
EXAMPLE 1 1 A cutting and grinding compound was prepared by blending 15 parts of an alkyl benzene sodium sulfonate, 78 parts of kerosene, 3 parts of diethanolamine, 2 parts of butyl carbitol and 4 parts of oleic acid, together with 2 parts of the product of Example 1.
When diluted with water in the ratio of 1 part of the above composition to 40 parts of Water, the product gave satisfactory performance as a cutting and grinding fluid which was not subject to bacterial contamination.
The invention claimed is:
1. A quaternary ammonium compound consisting of (1) a quaternary ammonium cation constituting the cationic portion of a quaternary ammonium compound having a phenol coefiicient of at least 100 with respect to Staphylococcus aureus and Salmonella lyphosa at C. and having an alkyl group of 8 to 22 carbon atoms attached to the quaternary nitrogen, and (2) an anion constituting theanionic portion of a branched chain alkyl or alkenyl acid, said anion containing from nine to twenty-one carbon atoms.
2. The compound of claim 1 wherein the alkyl or alkenyl acid is substituted by chlorine or bromine.
3. The compound of claim 1 wherein the anion is a neo acid anion having the structure:
wherein R R and R are straight or branched chain alkyl groups and wherein the total number of carbon atoms is between 9 and 21.
4. The compound of claim 1 wherein the anion is a branched chain hexadecanoic acid residue having the structure:
CH CH CH CH3 [OH.A.H CH..A H caoaoaamtacm] 5. The compound of claim 1 wherein the branched chain alkyl or alkenyl acid has 9 to 11 carbon atoms and an average molecular weight of about 183.
6. The compound of claim 1 wherein the branched chain alkyl or alkenyl acid is neo-tridecanoic acid having an average molecular weight of about 236.
References Cited UNITED STATES PATENTS OTHER REFERENCES Bashkirov et al., The Reaction Mechanism of Oxidation of P-araffin Hydrocarbons in the Liquid Phase (1959), CA 55, pp. 3409 (1961).
LEWIS GOTTS, Primary Examiner G. HOLLRAH, Assistant Examiner U.S. Cl. X.R.
Patent No. 65, 927 Dated February 23, 197] Inventor(s) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 1, line 55: "discovered, however, that contrary tc gen-" should read --generally thought that microbiocidal quat- Column 2, line 40, in the formula: "R" should read ---R column 4, line 61 "static" should read ---stasis---.
Signed and sealed this 23rd day of November- 1 971 (SEAL) Attest:
EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Acting Commissioner of Patent;
FORM P -1n uqrnMM-nr am