US2491992A - Detergent composition - Google Patents

Description

' John David Malkemiis, sue dale, N. J., assignor to Colgate-Palmolive-Pcet Company, Jersey City, N. 3., a corporation of Delaware Application December 29, 1945, Serial No. 688,470

on (in. 252-152) The present invention relates to new synthetic detergent compositions of the type of modified sulphated and sulphonated organic materials having improved surface-active characteristics, and to a process for producing said compositions.

Inorganic builders, such as carbonates, phosphates, etc., have been employed with synthetic detergents for modifying pH, and various other inorganic compounds are useful as extenders, but such materials have not been found fully adequate, in general, for improving the surfaceactive characteristics of the synthetic detergent to whicli'they are added. Thus, the use of these inorganic builders with synthetic detergents does not provide appreciably improved foaming and detergency characteristics.

It has recently been found that certain organic bodies, when added to synthetic detergents of the type of sulphated and sulphonated materials, modify the properties of said detergents, especially with respect to their foaming characteristics. Such modification is very valuable and useful in many fields, but, so far as is known, no significant improvement in detersive properties accompanies the improved foaming characteristics.

It is an object of the present invention to provide novel surface-active compositions of relatively high detersive eiiiciency.

It is also. an object of this invention to provide a modified anionic surface-active agent havingimproved detersive characteristics.

It is another object of the invention to provide a novel method for producing new organic surfaceactive compositions of high detergency.

Other objects and advantages of this invention will be apparent from the following description.

According to the present invention, it has now been found that the incorporation of a proportion of a cationic surface-active agent, such as an aliphatic carboxylic acid monoester or aliphatic monoether derivative of a N,N'-dialkanol piperazine, with a non-soap anionic surface-active compound such as detergents, emulsifiers and wetting agents of the type of sulphated or sulphonatezi organic materials, provides a compositerials which are applicable for sulphonation ("true sulphonation and/or sulphation), especially those having about eight to about twentysix (and preferably about twelve to about twenty) carbon atoms to the molecule, including fatty oils, unsaturated fatty acids, mineral oils, mineral oil extracts, monoand diglycerides, partial esters or ethers of polyglycols, esters or ethersi of glycols, poly lycols and polyalcohols, aromatic and alkylated aromatic compounds, alcohols and oleflnes, coal tar distillates, and numerous other organic compounds and mixtures of compounds. Such compounds can be sulphonated by any of several methods and may form any of several products, depending upon the method of col phonation employed. The sulphonated or sulphated organic compounds include sulphonated mineral oil; conventional mineral oil refinery sludges; sulphonated mineral oil extracts; sulphonated fatty acids and oils, including sulphonated castor oil, sulphoricinoleic acid, sulphonated olive oil, and sulphooleic acid; aliphatic sulphonates and sulphates, including cetyl sulphuric acid, dodecyl acid sulphate, and tetradecanehydroxy sulphonic acid-1,2; aliphatic ether and ester sulphonates including the dodecyl ether of hydroxy ethyl sulphonic acid, the cetyl ether of glyceryl sulphonic acid, and coconut oil monoglyceride monosulphate; sulphonates pre= pared by treatment of organic materials with sulphur dioxide and chlorine in the presence of light followed by hydrolysis of the product; sulphonates tion with markedly enhanced detersive characteristics. Similarly, incorporation of a proportion of the sulphated or sulphonated material deprepared by treatment of organic bodies with sulphuryl chloride and an activating agent in the presence of light followed by hydrolysis of the product; fatty acid amides of amino alkyl sulphonic acids, including lauric'amide of taurine and tall oil acid amide of amino glyceryl sulphonic acid; sulphonic acids of naphthenes and naphthenic acids; lignin sulphonic acids; aromatic and alkylated aromatic sulphonic acids, including naphthalene sulphonic acid, octadecyl benzene sulphonic acid, and dodecyl naphthalene sulphonic acid; the product of a mineral oil extract sulphonated while dissolved in liquid sulphur dioxide; and innumerable other organic sulphonic .and sulphuric acid derivatives or'mixtures thereof. These organic sulphate and true sulphonate compounds include those in which the organic radicals of the molecule are unsubstituted or those which contain substituents, such as hal ogens, halogenoids, hydroxyls. nitrogen-contaim ing groups, acyl groups, acyloxy groups, alkoxy groups, etc.

The aliphatic carboxylic acid monoester or sea-ea,

monoether derivatives of N,N'-dialkanol pi er azines, which may be added to sulphated and/or sulphonated compounds to achieve the desirable-- results described, are those represented by the general structural formula:

where R is an alkyl or acyl radical having aboutflve to about twenty-three, preferably about eight to about eighteen, carbon" atoms; A and Bare as halogens, hydoxyls. acyl groups, acyloxy groups, alkoxy groups, nitrogen-containing groups, heterocyclic groups. alicyclic groups, aryl groups, etc., although it is generally preferred that substituent groups of hydrophilic character be located near or adjacent to the piperazyl alkoxy group. Where R is an alkyl or substituted alkyl group, the organic builder 'is an ether; and where R is anacyl or substituted acyl group, the compound employed is an ester.

In the case of the compounds being an ester, the acyl group may be the residue of any suitable carboxylic acid, including lauric acid, myristic acid, palmitic acid, stearic acid, hydroxystearic acid, oleic acid, iinoleic acid, linolenic acid, ricinoleic acid, caproic acid, isocaprylic acid, a-aminocapric acid, undecylenic acid, lignoceric acid, erucic acid, lauryl succinic acid, chloropalmitic acid, mixed coconut oil fatty acids,

- mixed tallow fatty acids, mixtures of any of these acids, etc. Where the compound is an ether, the alkyl group may be any corresponding to a suitable carboxylic acid, such as the above-mentioned, including lauryl, myristyl, palmityl, stearyl, hydroxystearyl, oleyl, linoleyl, linolenyl, ricinoleyl, hexyl, isooctyl, p-aminodecyl, etc.

The dialkanol piperazine residue of the ester or ether employed may be symmetrical or mixed. That is, m and n may be the same number or they may be different numbers. In general, it is preferred to employ symmetrical N,N"-dialkanol piperazines, such as N,N'-diethano1 piperazine, N,N'-dipropanol piperazine, N,N'-diisopropanol piperazine, 3,6-dimethyl-1,4-(p-hydroxy ethyl)- piperazine, 3,6-dimethyl-l,4-di(p-hydroxy propyl) piperazine, etc., and especially the symmetrical dialkanol piperazines having both hydroxyl groups in omega position with respect to the piperazyl radical. However, mixed piperazines of the type of 1-fi-propanol-4-,8-ethanol piperazine, l-fi-ethanol-w-butanol piperazine, etc., can also be used.

7 Suitable esters for use in the compositions of this invention include N,N'-diethanol piperazine monolaurate, ricinoleic acid monoester of 3,6- dimethyl-lA-dKfl-hydroxy propyl) piperazine, di-w-butanol piperazine monostearate, coconut oil fatty acid monoesters of N,N'-diethanol piperazine, etc. Ethers suitable for employment in the novel compositions include l-(fi-lauroxy ethyl) -4-(phydroxy ethyl) -piperazine, 3,6-dimethyl -1- (p-myristoxy propyD- 4 (fl-hydroxy propyl) -piperazine, etc.

While mixtures of the N,N'-dialkanol piperazine monoester or-monoether with active sulphonated ingredient. may be ,used. in all; 'propor-' tions,-in general rangingfrom about.1% to about" 509%, it. is preferredto incorporate about-109% to about 200%, and more preferably about 20% to 100%, of monoester or monoether-- based upon:

the weight of sulphonated material. The optimum proportion employed-will vary 'with the particular active ingredient or mixture ofactive ingr'edients used; with the fproportion of other ingredients present, if any; and to some degree with the strength or concentrationof solution to be formed in use;

The diaikanol piperazine monoester or monoether may be incorporated with the active sulphonated ingredient to form the novel composition of thisinvention at any point during the vmanufacturing process at which subsequent operations will not destroy or objectionably modify the monoester or monoether or cause a deleterious reaction between the same and any other material in the composition. In general, it is preferred to add the piperazine derivative at a point in the manufacturing subsequent to the hydrolyzing 'and/or neutralizing step. This t i may be accomplished by adding the piperazine derivative in solid form or in solution to solutions containing the active sulphonated ingredient or.

by adding the sulphonated ingredient in solid form or in solution'to solutions containing the piperazine derivative to form concentrated solutions or solutions ready for use; by mixing the piperazine derivative with the solid sulphonate'd ingredient in comminuted form; or by adding the piperazine derivative to a solution of the sulphonated ingredient and thereafter subjecting the solution containing active sulphonated ingredient and piperazine monoester or monoether to spray-drying, roll-drying, etc., to form a solid composition.

Thus, the novel compositions provided may be made up in solutions, preferably concentrated,

or a dry or partially hydrated solid product or a' paste may be formed. The product may be made in a more or less finely divided condition, which permits its ready transformation into flakes or other physical forms, for example by passing between a pair of properly spaced rolls, or by milling or pressing into cakes, or by other means, with or without addition or modifying agents.

Adjuvant materials may be-admixed with the sulphonate salts by mixing the adjuvant materials with the sulphonated organic compounds and/or the neutralizing agents before neutrali-' zation or flashing, by simultaneously flashing a second solution containing such adjuvant materials, and or by mixing the final product therewith. When added. after neutralization, the adjuvant materials may be added before, after, or simultaneously with the dialkanol piperazine derivative. Such adjuvant materials may include any of the substances employed by the art in-admixture with sulphonated organic detergents generally, care being exercised to avoid the use of any material which would remove orotherwise substantially diminish the efiectiveness of thedialkanol piperazine monoester or monoether in--v I corporated. Th type of addition agent will depend upon the ultimate use of the new composition.

, added, as will appear hereinafter.

the pH, such as sodium chloride, sodium sulphate, etc., serve as extenders.

The novel and improved synthetic detergents, emulsifiers and/or wetting agents of this invention, comprising sulphated and/or sulphonated organic compounds (with or without adluvant materials) and a proportion of the diallranol piperazine monoester and/or monoether described, produce solutions which, under controlled conditions, have higher detersive efiiciency than either the active sulphonated ingredient or the monoester or monoether alone. Thus, employing a standard multiple swatch launderometer test on wool soil at 105 C. over a five-minute period, the detersive eficiencies of (a) a synthetic detergent comprising 40 parts by weight of coconut oil monoglyceride monosulphate sodium salt to 60 parts of sodium sulphate, (b) a composition comprising approximately 50% coconut fatty acid monoester of diethanol piperazine, and (c) a novel composition according to the present invention comprising about 70% of the synthetic detergent (a) and 30% of the composition (b) were compared. These materials (a), (b) and (ciwere made up in aqueous solution of about equal concentration, the pH of solution being adjusted to a pH of 6.0. It is notable that, while solution (a) showed a detersive efiiciency of 44% in removing carbon soil from wool and solution (1)) gave only 58% emciency, solution (0) showed a detersive efilciency of 67%.

The following examples, described hereinafter, are merely illustrative of the present invention, and it will be understood that the invention is not limited thereto.

EXAMPLE I v The monosulphate of monogylcerides of coconut oil fatty acids is disposed in a mixture in the proportion of about 40 parts by weight to about 60 parts of sodium sulphate. Solutions of this active organic material are made up containing varying proportions of coconut oil fatt acid monoesters of N,N '-diethanol piperazine (that is, monoesters of 1,i-di(,8-hydroxy ethyl) piperazine), and the pH and detersive efiiciency of each successive mixture is determined. In each case a total concentration in aqueous solution of 0.25% of monoglyceride monosulphate agent and the diethanol pi-perazine monoester is employed, and the aqueous solution also contains 300 parts per million of calcium and magnesium hardness (calculated as calcium carbonate). The detersive emciency is determined by the multiple swatch launderometer test on cotton soil at 115 F. ,over a twentyminute period, and the standard employed for comparison is the detersive efilciency of a 0.55% aqueous solution of tallow soap which gives an arbitrary emciency in this test of 100%. The following table shows the results obtained:

Table Ratio Deter- Mono- H sive glyceride D ietha1 iol P ammonopiperazmo ciency sulphate monoester agent Per cent Per cent Per cent The solution containing 00% of monoglyceride monosulphate agent and 10% or diethanol piperazine monoester is then adjusted from a DH of 8.8 to a pH of 10.4 by addition of sodium pyrophosphate, and the detersive efiiciency, upon redetermination, is found to have increased to 93% EXAMPLE II The monosulphate Of monogylcerides of coconut oil fatty acids, as prepared, is purified by extraction with ether and is dissolved in water to form an aqueous solution containing about 40% by weight of solids. Oleic acid monoester of N,N'-diethanol piperazine in an amount equivalent. to about 10% by weight of said active sulphated ingredient is added to the solution. The solution is then roll-dried to produce a surfaceactive material having excellent detersive characteristics in aqueous solution.

EXAMPLE 111 One part by weight of 1- (fl-lauroxy ethyl) 4-03- hydroxy ethyD-piperazine is added to about 20 parts of a sulphonate prepared by treating a Pennsylvania white mineral oil of paramn base and having an average molecular weight of 235 with sulphur dioxide and chlorine in the presence of light and neutralizing the product with sodium hydroxide. Sodium sulphate is then added, and the ingredients are thoroughly mixed. The resulting detergent composition provides aqueous solutions of excellent detergent characteristics.

EXAMPLE IV The Edeleanu extract of a naphthene base mineral oil is dissolved in about twice its volume of liquid sulphur dioxide and sulphonated with oleum. A dry, flufiy powder containinng about 96% of active ingredient is obtained. An amount of tallow fatty acid monesters of 3,6-dimethyl-L4- diqB-hydroxy propyl) piperazine equivalent to about 20% of the weight of the total solids present is stirred into the mixture. The composition thus produced provides solutions of fine detersive characteristics.

The use of the term sulphonated with reference to organic compounds in the following claims will be understood to include sulphated as well as true sulphonated materials.

The piperazine derivatives and the method of preparing them form the subject matter of applioants copending application Serial No. 638,471, filed December 29, 1945, now Patent No. 2,421,707. issued June 3, 1947.

Although the present invention has been described with reference to particular embodiments and examples, it will be apparent to those skilled in the art that variations and modifications of this invention can be made and that equivalents can be substituted therefor without departing from the principles and true spirit of the invention.

I claim:

1. A detergent composition comprising essentially a, surface-active organic sulphuric reaction product in the form of a water-soluble salt having detergent properties and having in its molecular structure a radical selected from the group consisting of sulphonic acid and sulphuric acid ester radicals, and an amount of a piperazine derivative equivalent to about 1% to about 500% by weight of said sulphonated organic compound,

7 said piperazine derivative being represented by the structural formula:

A nocno..-i-/ N- cn.).-on

where R is a member of the gr p on n o alkyl and acyl radicals having about to about 23 carbon atoms, A and B are members of the group consisting of an ethylene radical and alkyl derivatives thereof wherein any number of hydrogens in the ethylene radical are replaced by alkyl radicals of not more than two carbon atoms, and m and n are integers of 2 to about 5.

2. A detergent composition comprising essentially a surface-active organic sulphuric reaction product in the form of a water-soluble salt having detergent properties and having in its molecular structure a radical selected from the group consisting of sulphonic acid and sulphuric acid ester radicals, and an amount of a piperazine derivative equivalent to about to about 200% by weight of said sulphonated organic compound, said piper-azine derivative being represented by the structural formula:

A nocn, ..-N N- om).on

where R is a member of the group consisting of I alkyl and acyl radicals having about 5 to about 23 carbon atoms, A and B are members of the group consisting of an ethylene radical and alkyl derivatives thereof wherein any number of hydrogens in the ethylene radical are replaced by alkyl radicals of not more than two carbon atoms, and m and n are integers of 2 to about 5.

3. A detergent composition comprising essentially a surface-active organic sulphuric reaction product in the i'orm of a water-soluble salt having detergent properties and having in its molecular structure a radical selected from the group consisting of sulphonic acid and sulphuric acid ester radicals, and an amount of a piperazine derivative equivalent to about 10% to about 200% by weight of said sulphonated organic compound, said piperazine derivative being represented by the structural formula:

where R is a member of the group consisting of alkyl and acyl radicals having about 8 to about 18 carbon atoms, A and B are members of the group consisting of an ethylene radical and alkyl derivatives thereof wherein any number of hydrogens in the ethylene radical are replaced by alkyl radicals of not more than two carbon atoms, and m and n are integers of 2 to about 5.

4. A detergent composition comprising essentially a surface-active organic sulphuric reaction product in the form of a water-soluble salt having detergent properties and having in its molecular structure a radical selected from the group consisting of sulphonic acid and sulphuric acid ester radicals, and an amount of a piperazine derivative equivalent to about 10% to about 200 by weight of said sulphonated organic compound, said piperazine derivative being represented by the structural formula:

is where R is a member of the group consisting of alkyl and acyl radicals having about 8 to about 18 carbon atoms, and m and n are integers of 2 to about 5.

5. A detergent composition comprising essentially a surface-active organic sulphuric reaction product in the form of a water-soluble salt having detergent properties and having in its molecular structure a radical selected from the group consisting of sulphonic acid and sulphuric acid ester radicals, and having about 8 to about 26 carbon atoms per molecule, and an amount of a piperazine derivative equivalent to about to about 100% by weight of said sulphonated organiccompound, said piperazine derivative being represented by the structural formula:

I where R is a member of the group consisting of ester radicals, and havin about 8 to about 26 carbon atoms per molecule, and an amount of a derivative of N,N'-diethanol piperazine equivalent to about 10% to about 200% by weight of said sulphonated organic compound, said derivative being represented by the structural formula:

where R is a member of the group consisting of alkyl and acyl radicals having about 8 to about 18 carbon atoms.

'7. A detergent composition comprising essentially a surface-active organic sulphuric reaction product in the form of a water-soluble salt having, detergent properties and having in its molecular structure a radical selected from the group consisting of sulphonic acid and sulphuric acid ester radicals, and having about 12 to about 20 carbon atoms per molecule, and an amount of a derivative of N,N'-diethanol piperazine equivalent to about 20% to about by weight of said sulphonated organic compound, said derivative being represented by the structural formula:

CHr-CH, 30-01m- N-mmon CHr-C 3 where R is a member of the group consisting of alkyl and acyl radicals having about 8 to about 18 carbon atoms.

8. A detergent composition comprising essentially an alkali metal salt of the sulphuric acid ester of a coconut oil fatty acid monoglyceride, and an amount of a fatty acid monoester of 1,4-di(p-hydroxy ethyl) piperazine equivalent to about 10% to about 200% by weight of said alkali metal salts and-wherein the fatty acid residue contains about 8 to about 18 carbon atoms.

. 9. A detergent composition comprising essentially an alkali metal salt of a sulphuric acid ester of a coconut oil fatty acid monoglyceride, and an amount of the coconut oil fatty acid monoesters memes of 1,4-d1(p-hydroxy ethyl) plperazlne equivalent to about 10% by weight-er said alkali metal salt. REFERENCES CITED 10. A detergent composition comprising essen- The following references are of record in the tlally a mineral oil sulphonate produced by treatfile of this patent: in: a mineral oil with sulphur dioxide and chlo- 5 lin in the presence of actinic light and substan- UNHED STATES PATENTS tially neutralizing the product of said treatment, Number Name Date and an amount of l-(p-lauroxy ethyl) -4-(fi-hy 2,174,506 Fox Sept. 26, 1939 'droxy ethyl) -piperazine' equivalent to about 5% 2,206,923 h et 1- July 1940 by-z weight of said mineral oil sulphonate. 10 2,236,328 Muncie Apr. 1, 1941 JOHN DAVID MALKEMUS. 2,383,737 Richardson Aug- 1945