|Publication number||US3687870 A|
|Publication date||Aug 29, 1972|
|Filing date||Mar 13, 1969|
|Priority date||Mar 13, 1969|
|Publication number||US 3687870 A, US 3687870A, US-A-3687870, US3687870 A, US3687870A|
|Inventors||Loboda Jon A, Muzyczko Thaddeus M, Shore Samuel|
|Original Assignee||Richardson Co|
|Export Citation||BiBTeX, EndNote, RefMan|
|Referenced by (7), Classifications (24)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent 3,687,870 Patented Aug. 29, 1972 3,687,870 DETERGENT COMPOSITIONS Thaddeus M. Muzyczko, Melrose Park, Samuel Shore, Roselle, and Jon A. Loboda, Chicago, Ill., assignors to The Richardson Company, Melrose Park, Ill. No Drawing. Filed Mar. 13, 1969, Ser. No. 807,119 Int. Cl. C11d 1/40, 1/62, N65 US. Cl. 252-545 9 Claims ABSTRACT OF THE DISCLOSURE This invention is directed to detergent compositions containing arylsulfonamidoamines, their salts or mixture thereof. Illustrative of this class of compounds is the hydroxyethyl chloride salt of N-dodecylbenzenesulfonamidopropyl-N,N-dimethylamine. In addition to properties descriptive of cationic detergents, these compounds exhibit remarkable compatibility with alkylaryl sulfonates and other anionic detergents.
BACKGROUND This invention relates to detergent compositions and more particularly to compositions containing arylsulfonamidoamines, their salts or mixtures thereof. These compounds are useful as cationic detergents and as modifiers in formulations containing anionic detergents.
Commonly, cationic-active agents or surfactants having detergency properties are classified as cationic detergents. As such, they are useful in a variety of applications and particularly in liquid compositions with a pH belowabout 8.
Frequently, in compositions such as cosmetic preparations, these cationic surfactants are part of formulations developed to exhibit a desired combination of properties. It is therefore advantageous that the cationic surfactant provide more than one useful property in order to limit the cost and complexity of the formulations.
Also, it is not uncommon that compatibility problems are encountered with formulations containing cationic surfactants in combination with anionic surfactants such as the alkylarylsulfonates. In several instances, precipitates are formed limiting the usefulness of the product and the flexibility in varying formulations of these components.
Therefore, the development of new detergent compositions with improved performance is of commercial importance.
SUMMARY Briefly, the invention is directed to detergent compositions containing as a cationic surfactant an arylsulfonamidoamine, its salt, or mixtures thereof. The arylsulfonamidoamine of particular importance is characterized by the following general formula:
2 s Oz-lTI-(CH2)..N\
wherein R is aliphatic or aryl modified aliphatic, R is hydrogen, alkyl, hydroxyalkyl, aminoalkyl or aryl, R and R each is R m is an integer of 1-5, and n is an integer of about 1-10.
Detergent compositions with the above cationic surfactant exhibit a useful combination of detergency, emulsifying, softening, wetting, flotation and other properties. In addition, they exhibit stability over relatively wide pH ranges. Moreover, the cationic surfactants are characterized by remarkable compatibility with alkylaryl sulfonates and other anionic surfactants in detergent compositions.
DETAILED DESCRIPTION with R, R R R in and n as described above.
It is understood that (R) represents 15 and advantageously 1-2 organic substituents, on the benzene ring. Each substituent also usually is characterized by l-30 and advantageously about 8-22 carbon atoms to provide a balance of hydrophilic-hydrophobic properties. Organic substituents include saturated and olefinically unsaturated aliphatics and aryl groups modified by aliphatics as in alkaryls and aralkyls and their unsaturated counterparts. It is also understood that these groups can have polar groups such as halo and nitro groups which do not unduly hinder the desired performance of the resulting compound. Illustrative substituents include methyl, propyl, butyl, octyl, dodecyl, hexadecyl, octadecyl, docosyl, triacontyl, the corresponding aliphatics with 1-2 unsaturated groups, and the corresponding aliphatic substituted phenyls and phenyl substituted aliphatics. Advantageously, R is alkyl or alkaryl and is a single substituent. Preferably, R is hydrocarbon and m is 1.
R in the formula represents hydrogen or an organic substituent on the amido nitrogen. When R is hydrogen, the resulting composition is particularly useful in aqueous systems having pH values ranging from acidic, neutral to basic.
Suitable groups for R include alkyl, aryl, hydroxyalkyl, haloalkyl, aminoalkyl, and the like, although advantageously, R is alkyl, hydroxyalkyl, aminoalkyl, ethoxylated form of the latter two, or is aryl, aralkyl or the like. Advantageously, the oragnic R has about 1 to about 8 carbon atoms and is alkyl, aryl, or mixture thereof. Preferably, R is hydrogen.
R and R each is represented by R as described above. Advantageously, R and R each is alkyl of l-8 carbon atoms and preferably 1-4 carbon atoms. Also preferably R and R are both alkyl.
The integer n is from 1 to 10, advantageously 2 to 6, and preferably 3 because of the availability of the corresponding reactant amines and the effect of the proximity of the two nitrogen atoms.
The process for producing the compositions comprises reacting an arylsulfonylchloride with the appropriate aminoalkylene amine in a suitable inert solvent such as carbon tetrachloride, benzene, toluene, petroleum ether and the like at 0 to C. A one to two hour reflux period after the initial reaction is generally used. The desired amine is then obtained by treating the amine hydrochloride with a suitable base such as sodium hydroxide.
Quaternary salts may be prepared by adding the appropriate alkyl halide to an alcohol solution of the amine. The salts usually are of alkyl halides having 1-8 carbon atoms and are characterized by biocidal properties.
Inorganic and organic acids salts are prepared by simple neutralization of the amine. Generally, organic acids have about 22() carbon atoms. Acids such as hydrochloric, phosphoric, propanoic, hexanoic, dodecanoic, hexadecanoic and the like are usually employed. These salts are advantageous since they form water-soluble, foaming, detergent compositions.
-Betaines and carbethoxy chlorides are prepared by adding sodium chloroacetate or ethyl chloroacetate respectively to alcoholic solutions of the amine, advantageously with refluxing. These salts are also useful as watersoluble, foaming, detergent compositions.
The detergent compositions containing the arylsulfonamidoamines, their salts or mixtures thereof are useful for treating fabrics, washing foods, conditioning hair and the like. The amine or its salt can be added to aqueous or similar system as the primary detergent and is particularly useful in aqueous systems with a pH of below about 8. They can also be used in combination with anionic surfactants, non-ionic surfactants or mixtures thereof. When used alone, the cationic surfactant is present in amounts suificient to provide detergency to the aqueous system. Generally about 0.140.0 weight percent is present with the more optimum amounts dependent on the particular utility.
Often, the cationic surfactant is used with an anionic, nonionic or mixture of the two surfactants to provide a formulation with unusual detergency and stability properties. In these formulations, the cationic surfactant is present in amounts ranging from values in the order of 0.1 weight percent to 99 Weight percent. The remainder is dependent on the particular formulation. In simple systems, the other components are primarily the other surfactant or surfactants. In other systems, appreciable amounts of an aqueous solvent such as water or wateralcohol and various additives are usually present.
Advantageously, the mixture contains cationic with anionic or nonionic surfactants or combinations of the three surfactants. Illustrative anionics include salts of the sulfonated oils, sulfonated alkyl aromatics, and the like such as the sodium salt of sulfonated coconut oil, sodium dodecylbenzene sulfonate and disodium N-octadecylsulfosuccinamate, sodium salts of sulfated fatty alcohols and the like.
Suitable nonionics include those commonly used in detergent systems such as the alkylaryl polyether alcohols such as polyethoxynonylphenol, polyglycol esters such as polyethyleneglycol stearate and the like.
The following examples illustrate some of the embodiments of this invention. It is to be understood that these are for illustrative purposes only and do not purport to be wholly definitive to conditions or scope.
Example I N dodecylbenzenesulfonamidopropyl-N,N-dimethylamine was prepared from dodecylbenzenesulfonyl chloride and dimethylaminopropylamine. In the process, about 11.2 gms. of the amine was added dropwise to about 33.4 gms. of the sulfonyl chloride in about 255 gms. of carbon tetrachloride. During the addition, the tempera ture increased from about 25 C. to about 60 C.
After being mixed for about one hour at 60 C., the mixture was cooled and converted by a sodium hydroxide solution to the free tertiary amine. The carbon tetrachloride layer was separated and an ether extract was evaporated, leaving a waxy solid, N-dodecylbenzenesulfonamidopropyl-N,N-dimethylamine. Nitrogen, sulfur and infrared spectra confirmed the sulfonamide structure.
Example H In a similar manner, N-methylbenzenesulfonamidopropyl-N,N-dimethylamine was prepared from methylbenzenesulfonylchloride and dimethylaminopropylamine.
Example III N [2 (l,4,5,6,7,7 hexachloro-(2,2,1)-2-heptene)- benzenesulfonamidopropyl]-N,N-dimethylamine was prepared from the corresponding organic compound and sulfonyl chloride, followed by reaction of the product with dirnethylaminopropylarnine.
Example IV A solution of about 2.0 gms. of N-dodecylbenzenesulfonamidopropyl-N,N-dimethylamine in about 10.0 ml. of
isopropanol was neutralized with 10 weight percent lactic acid to a pH of about 7.0. This solution of the lactic acid salt easily formed foam in pH ranges of 1.0 to 12.0 and was a good emulsifier for kerosene.
Example V A quaternary salt was prepared from N-dodecylbenzenesulfonamidopropyl N,N dimethylamine and ethylene chlorohydrin. In the process about 1.3 gms. of the amine in about 10.0 gms. of isopropanol and 5 gms. of water was refluxed with 0.2 gm. of ethylene chlorohydrin for about 24 hours to form the quaternary salt. In solution, the salt exhibited useful emulsifying and detergent properties.
Example VI A solution of about 1.1 gms. of N-dodecylbenzenesulfonamidopropyl-N,N-dimethylamine in about 15 gms. of isopropanol and 5 gms. of water was refluxed with approximately 0.3 gm. of sodium chloracetate to form primarily N dodecylbenzenesulfonamidopropyl-N,N-dimethyl-N-carboxymethylammonium betaine. This solu tion was an excellent emulsifier for kerosene water systerns.
Example VII An aqueous solution of about 1 weight percent N- dodecylbenzenesulfonamidopropyl N,N dimethylammonium acetate and a pH of about 6.2 was prepared. A second aqueous solution of about 1 weight percent sodium dodecylbenzene sulfonate was also prepared and equal quantities of each 'were mixed. The resultant solution was a clear foamy composition even when the pH was changed through a range of 1.0 to 12.0 using 5 percent HCl and 5 percent NaOH.
The addition of an ethoxylated octyl phenol in an amount of about 1 weight percent to the initial mixture of the above two surfactants was carried out and the resultant solution of cationic, anionic, and non-ionic surfactants remained free from any noticeable turbidity.
In a similar manner, a quantity of a solution (about 1 weight percent) of N,N-dicoco-N,N-dimethylammonium chloride was mixed with an equal quantity of a solution (about 1 weight percent) of sodium dodecylbenzene sulfonate. This combination of cationic and anionic surfactants produced a precipitate. Addition of the ethoxylated octyl phenol as a non-ionic surfactant did not clear up the solution.
Example VII'I About 0.50 g. of N-dodecylbenzenesulfonamidopropyl- N,N-dimethylamine was added to about 0.75 g. of dodecylbenzene sulfonic acid and then combined with about 4.0 g. of kerosene to prepare a detergent suspension. About 1 part of this mixture was shaken with about 5 parts of tap water and formed an emulsion which was stable for a period of over 3 hours.
These results demonstrate that a combination of the cationic and anionic surfactants is useful with kerosene and provides stable emulsions.
1. A detergent consisting essentially of (a) from about 0.1% to 99% by weight of an arylsulfonamidoamine cationic surfactant and salts thereof wherein said salts are selected from the group consisting of alkyl halide quaternary ammonium salts having 1 to 8 carbon atoms, inorganic acid salts, water soluble salts of organic alkanoic acids having 2 to 20 carbon atoms, and lactic acid and the remainder being (b) a material selected from the group consisting of anionic surfactants selected from the group consisting of sulfonated oils, alkylaryl sulfonates and sulfated fatty alcohols, and non-ionic surfactants selected from the group consisting of alkylaryl polyethoxy ether alcohols and polyethylene glycol esters and mixtures of such surfactants, the cationic surfactant having the formula wherein R is selected from the group consisting of alkyl, alkenyl, unsubstituted and halo, nitro and alkyl substituted alkaryl and aralkyl having 8 to 22 carbon atoms, R R and R are selected from the group consisting of hydrogen and alkyl having from 1 to 8 carbon atoms, m is an integer of from 1 to and n is an integer of from 1 to 10.
2. The detergent composition of claim 1 wherein the cationic surfactant is an alkyl halide quaternary ammonium salt with about 1-8 carbon atoms in the alkyl group.
3. The detergent composition of claim 1 wherein the cationic surfactant is salt of an alkanoic organic acid containing about 2-20 carbon atoms.
4. The detergent composition of claim 1 wherein R is dodecyl, R is hydrogen, R is methyl, R is methyl, m is 1 and n is 3.
5. The detergent composition of claim 1 wherein the cationic surfactant is the hydrochloride salt and R is dodecyl, R is hydrogen, R is methyl, R is methyl, m is 1 and n is 3.
6. The detergent composition of claim 1 wherein the cationic surfactant is the lactic acid salt and R is dodecyl, R is hydrogen, R is methyl, R is methyl, m is 1, and n is 3.
7. The detergent composition of claim 1 wherein the cationic surfactant is the quaternary hydroxyethyl ammonium chloride salt and R is dodecyl, R is hydrogen, R is methyl, R is methyl, m is l, and n is 3.
8. The detergent composition of claim 1 in an aqueous system.
9. The detergent composition of claim 8 wherein the composition is an aqueous solution with a pH below about 8.
References Cited UNITED STATES PATENTS 4/ 1956 Kopp 252106 4/1956 Cross 252-152 X HERBERT B. GUYNN, Primary Examiner
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US4069254 *||Oct 7, 1975||Jan 17, 1978||Banyu Pharmaceutical Co., Ltd.||ω-(Arylsulfonamido)-alkylamine|
|US4122266 *||Dec 29, 1975||Oct 24, 1978||Chevron Research Company||Reaction of aryl sulfonic acid ester and amines|
|US4260497 *||Nov 26, 1979||Apr 7, 1981||Colgate-Palmolive Company||Methanesulfonamides as antistatic agents for laundered fabrics|
|US4261925 *||Apr 5, 1978||Apr 14, 1981||The Dow Chemical Company||Surfactants|
|US4303543 *||Jul 23, 1979||Dec 1, 1981||The Procter & Gamble Company||Method for cleansing and conditioning the skin|
|US4665227 *||May 23, 1986||May 12, 1987||American Home Products Corporation||N-substituted-4(3)-nitrobenzene sulphonamides|
|US5591503 *||May 10, 1995||Jan 7, 1997||The Dow Chemical Company||Magnetic recording medium having a thin film magnetic layer and a sulfonamide lubricant|
|U.S. Classification||510/488, 510/350, 510/126, 564/87, 564/94, 510/111, 510/494, 510/123|
|International Classification||A61K8/46, C07C311/15, B03D1/004, B03D1/012, A61Q5/12, C07C311/00, A61K8/30, C11D1/00|
|Cooperative Classification||B03D1/012, C11D1/002, A61Q5/12, A61K8/466|
|European Classification||A61Q5/12, B03D1/012, C11D1/00B, A61K8/46F|