GB2226557A - Alkeline oxide-containing amphoteric surfactants - Google Patents

Description

1 Case 156-7096 ALKYLENE OXIDE-CONTAINING AMPHOTERIC SURFACTANTS This

invention relates to a new class of surface active agents. More particularly, it relates to certain alkylene oxide-containing amphoteric compounds and to their use as surface active agents in a wide variety of consumer product areas. The alkylene oxide-containing amphoteric compounds are especially useful in the cosmetics and toiletries areas, e. g., as surfactants in shampoo compositions.

To an outsider looking in, the search for a surfactant for use in shampoo compositions is relatively easy since new surfactants appear in the literature regularly. However, and as is well known by those skilled in the art, the formulation of shampoo compositions for human hair is a highly specialised field involving many considerations, viz., cleaning ability, foaming action, mildness, etc. More often than not, a surfactant is chosen primarily on the basis of its cleaning ability at the expense of serious compromises in overall product be- is haviour.

In the past, soap-based shampoo compositions were employed. Unfortunately, they suffered from the disadvantage of dulling the hair due to the precipitation thereon of lime and magnesium soap or the like, especially in hard water. In addition, such precipitates con- siderably reduced the foaming action of the shampoo compositions. Faced with the problems exhibited by soap-based shampoo coifipositions, those skilled in the art attempted to overcome these drawbacks by the substitution, in part, of synthetic organic detergents, e.g., sulphates and sulphonates, for the soap. However, shampoo compositions based on mixtures of synthetic detergents and soaps appear to be Case 156-7096 rather deficient and offer little in value to the demanding consumer.

For instance, when such mixtures are brought into contact with calcium ions in water, the lime soaps which necessari,?-...7 form must be dispersed by the synthetic detergent. Consequently, r,'...i-ily is a part of the soap lost by binding to calcium, when such s are present, but also part of the synthetic detergent is consume. s a dispersing agent for the lime soap formed and thereby loses a c ain degree of its clean ing action. In this connection, it should h kept in mind that in the washing of human hair, even a professional L irdresser normally uses tap water.

More recently, shampoo co4positions have surfaced which contain, as the essential cleaning component, a synthetic detergent or a mixture thereof, exclusively. However, although such shampoo compositions exhibit acceptable cleaning and foaming properties, the presence of the synthetic detergent or mixture thereof appears to enhance the irritation potential of the shampoo compositions, thereby making them unacceptable from a mildness standpoint. In an effort to overcome the enchanced irritation potential of synthetic detergent-based shampoo compositions, the skilled artisan has modified the synthetic detergent component, e.g., a higher alkyl ether sulphate of the formula R(OCH2CH2)n-OSO3M where R is C10-Clsalkyl, m is an integer 1 to 3 and M is a cation, by increasing the level of ethylene oxide. However, such a modification, although somewhat ameliorating the irritation potential of the above- identified alkyl ether sulphates, adversely affects the foaming properties of the shampoo compositions.

Accordingly, it is an object of the present invention to provide a new class of surface active agents which are useful in a wide variety of consumer product areas. It is another object of the present in- vention to provide certain alkylene oxide-containing amphoteric surfactants which are especially useful in the cosmetics and toiletries areas. It is still another object of the present invention to provide certain alkylene oxide-containing amphoteric compounds which may be employed as the essential surfactant in shampoo compositions, wherein said compositions exhibit exceptional cleaning and foaming properties. Furthermore, these amphoteric surfactants exhibit a high degree of Case 156-7096 salt tolerance, thereby enabling high active levels of said compounds to be achieved at lower viscosities.

The attainment of the above objects is made possible by certain alkylene oxide-containing amphoteric compounds of formula I 0 H R, R0-4C314, 0),--4C2 H4 0) n --CH2 -C-N-CH,? CH2 -19N XF9 I I R2 CH2CH20H in which R is n X19 is C6-C22 straight or branched chain alkyl or a group R3-CGH5-p where R3 is C6-C16 straight or branched chain alkyl; RjL is -CH2COOM, where M is hydrogen or a cation selected from alkali metal, alkaline earth metal, ammonium, mono-, di- and tri-C2-C4alkanolammonium and mono-, di-t tri- and tetra Cl-C4alkylammonium; R2 is hydrogen or -CH2COOM, where M is as defined above; m is 0 or an integer 1 to 10; is an integer 2 to 15; and is an anion, or a mixture of said compounds.

RI With respect to the ammonium salt-ON 1 R2 CH2CH20H xe.

formula I shows one possible ionic form. However, it is clearly evi- dent that, in aqueous solution, solvation of the ions would lead to an equilibrium condition which would allow the corresponding zwitterionic form to exist with the solvated MID. and XP. ions according to the reaction sheme below:

R2 Xe R2 -GN-CH2C009 M3) ---eN-CH2C009 +M9. + X95 CH2CH20H CH2CH20H When R is straight or branched chain alkyl, said alkyl group preferably contains 8 to 20 carbon atoms, more preferably 10 to 20 carbon atoms, and even more preferably 12 to 18 carbon atoms.

Case 156-7096 When R is a group R3-C6H5-, the R3 portion preferably contains 6 to 14 carbon atoms, more preferably 8 to 12 carbon atoms, and even more preferably 9 to 12 carbon atoms.

The hydroxy group of any C2-C4hydroxyalkyl group in M is on other 5 than the a-carbon atom. When M has more than one C2-C4hydroxyalkyl or C1C4alkyl group, they may be the same or different but are preferably the same. Preferably, M does not contain more than two tertiary butyl groups. The preferred alkali metals as M are lithium, sodium and potassium and the preferred alkaline earth metals are magnesium, calcium, barium and strontium.

The variable m is preferably 0 or an integer 1 to"5, more preferably 0 or an integer 1 to 3, and even more preferably 0 or an integer 1 or 2.

The variable n is preferably an - integer 2 to 12, more preferably an integer 3 to 10, and even more preferably an integer 4 to 9.

The variables m and n, and also p, q, r, t, u and v as defined below, are average values. As is clearly evident, the variables m, n, p, q, r, t, u and v must be whole numbers in the individual compounds of this invention.

The anion X9 is preferably a halide, more preferably chloride or bromide, and even more preferably chloride.

The preferred compounds of formula I are those of formula Ia 0 H R,, R.-0-4C3 H6 OP-4C2H4 0)q-CH2 -C-N-CH2 CH2 -'9N 1 ''R2 CH2CH20H in which R. is CS-C20 straight or branched chain alkyl or a group R3.-C6H5-, where R3. is C6-C14 straight or branched chain alkyl; x,9 Ia R,, is -CH2COON, where M. is hydrogen or a cation selected from alkali metal, alkaline earth metal and ammonium; R2A is hydrogen or -CH2COON, where M. is as defined above; p is 0 or an integer 1 to 5; q is an integer 2 to 12; and X.19 is halide, v Case 156-7096 or a mixture of said compounds.

The more preferred compounds of formula I are those of formula Ib 0 H Rib Ot-CH2 A r -4C2 H4 -C-N-CH2 CH2 -ON Xbe Ib 1 \ R2b CH2CH20H in which Rt, is C10---;20straight or branched chain alkyl or a group R3b-C6H5-, Where R3b is C$-C12 straight or branched chain alkyl; Rib is -CH2C00Mbl where Mb is hydrogen or a cation selected from alkali metal and ammonium; R2b is hydrogen or -CH2C00Mbp where Mb is as defined above; r is 0 or an integer 1 to 3; t is an integer 3 to 10; and Xbe is chloride or bromide, or a mixture of said compounds.

The even more preferred compounds of formula I are those of formula Ic 0 H R, 11 1 Rr-O--C3H60)u--4C2'H4 0) v -CH2 -C-N-CH2 CH2 -'9N Xceic 1 R2c 122CH20H where R, is C12-C18 straight or branched chain alkyl or a group R3c-C6H5-, where R3c is C9-C12 straight or branched chain alkyl; Ric is -CH2COOMct where Mc is hydrogen or a cation selected from sodium, potassium and ammonium; R2. is hydrogen or -CH2COON, where M,, is as defined above; is 0 or an integer 1 or 2; is an integer 4 to 9; and Xce is chloride, or a mixture of said compounds.

Case 156-7096 Suitable alcohol precursors of the alkylene oxide-containing amphoteric compounds of this invention are straight or branched chain primary alcohols having from 6 to 22 carbon atoms. Typical examples of alcohols having a branched chain configuration are isodecyl and isostearyl. A mixture of alcohols may be used and this will generally be the case when using commercial alcohols which are often available as a blend of several alcohols. Specific examples are a mixture of C12-CI5 straight chain alcohols available commercially from Union Carbide; a mixture of C12-CIS predominantly straight chain alcohols containing approximately 20% branching available commercially from Shell Chemical Co. ; and a mixture of alcohols, at least 70 mol % of which is branched 1- decanols available commercially from Exxon Chemical Co. When employing a mixture of alcohols, the number of carbon atoms in the alcohol is referred to as an average numberwhich can be determined by vapour phase chromatography and the hydroxyl number.

Othersuitable precursors of the alkylene oxide-containing amphoteric compounds of this invention are straight or branched chain alkylphenols having from 6 to 16 carbon atoms in the alkyl portion thereof. Typical examples of alkylphenols having a straight chain configuration are n-hexaphenol, n-decylphenol, n-dodecylphenol, n- tetradecylphenol, etc., whereas i-octylphenol and branched chain nonylphenol-are exemplary of alkylphenols having a branched chain configuration.

The compounds and mixtures of formula I are produced by conven- tional methods. Thus, the alkylene oxide-containing amphoteric compounds of this invention may be prepared by carboxyalkylating the adduct resulting from the propoxylation and/or ethoxylation of a straight or branched chain primary alcohol having from 6 to 22 carbon atoms or a straight or branched chain alkylphenol having from 6 to 16 carbon atoms in the alkyl portion thereof, reacting the carboxyalkylated adduct resulting therefrom with an appropriate amine via a condensation reaction and then carboxyalkylating the amidoamine inter-' mediate resulting therefrom to realize a compound of formula I where R2 is hydrogen. Further carboxyalkylation of said compound results in a compound of formula I where R2 is -CH2COOM.

Case 156-7096 The alkoxylation step may be carried out in the presence of an alkaline catalyst, e.g., alkali metal hydroxides, sodium ethoxide, sodium methoxide, alkali metal acetates and dimethylamine, and mixtures thereof, preferably sodium or potassium hydroxide, in an amount 2' to 1%, preferably 0.3% to 0.75%, by weight of the total 5 e.g. f rom 0. /c 4, reaction Optionall.y, a small amount of a reducing agent may be added to the alcohol, or m:. -,re thereof, or alkylphenol to be alkoxylated to minimize discoloral. a of the resulting polyalkaxylated alcohol or alkylphenol. Suitable reducing agents which may be employed include sodium borohydride, lithium aluminium hydride and diborane, preferably sodium borohydride.

In preparing a polyoxyalkylated alcohol or alkylphenol in which the polyoxyalkylene chain contains a propylene oxide first block and is an ethylene oxide second block, an amount of propylene oxide calculat- ed to provide the desired degree of propoxylation is introduced and the resulting mixture is allowed to react until the propylene oxide is consumed, as indicated by a drop in reaction pressure. A similar introduction and reaction of a calculated amount of ethylene oxide serves to provide the second block which completes the alkoxylation. Customarily, the alkoxylated product is finally treated with weak acid, e. g., glacial acetic acid, to neutralize any basic catalyst residues.

It should be understood that each separate alkoxylation procedure serves to introduce a desired average number of alkylene oxide units per alcohol or alkylphenol molecule. Thust for example, the initial treatment of an alcohol, or mixture thereof, or alkylphenol with m moles of propylene oxide per mole of alcohol or alkylphenol serves to effect the propoxylation of each alcohol or alkylphenol moiety with propylene oxide to an average of m propylene oxide moieties per alcohol or alkylphenol moiety, although some alcohol or alkylphenol moieties will have become combined with more than m propylene oxide. moieties and some will have become combined with less than m. In general, the maximum number of propyleneoxy units in a single molecule will not exceed 20 and the number of ethyleneoxy units in a single molecule will not exceed 25. The variation in the number of alkylene Case 156-7096 oxide moieties is not critical as long as the average for the number of units in each block is vh(ithin the limits set out for the m and n terms in formula I above, which terms, as average values, are other than whole numbers in some instances.

Each alkoxylation is conducted at an elevated temperature and pressure. Suitable reaction temperatures are from 120 to about 220% preferably 130 to 180C and more preferably 140 to 1600C. A suitable reaction pressure is achieved by introducing to the reaction vessel the required amount of propylene oxide or ethylene oxide, each of which has a high vapour pressure at the desired reaction temperature. The pressure serves as a measure of the degree of reaction and each alkoxylation is considered to be complete when the pressure no longer decreases with time.

For best results, it is desirable to carry out the alkoxylation under relatively moisture-free conditions and to avoid side reactions which form water. To dry the reaction vessel and connections, they may be swept out with dry, oxygen-free gas, e.g., nitrogen, before introducing the charge. The catalyst or catalyst mixture should also be dry, or substantially so. The propylene oxide and ethylene oxide should preferably be purified to remove moisture and any impurities which are capable of entering into side reactions which yield water.

The resulting alkyl or alkaryl polyalkoxide intermediates are then carboxymethylated by the Williamson synthesis, involving reaction with the appropriate chloro- or bromocarboxylic acid or a salt thereof in the presence of a strong base, e.g., sodium hydroxide, sodium-carbonate, etc., or by catalytic oxidation. Such reaction is ordinarily not complete; hence, the reaction product often contains minor amounts of uncarboxylated alkyl or alkaryl polyalkoxide. While methods are available for separating the uncarboxymethylated material as well as for assuring essentially complete carboxymethylation, they are usually tedious and expensive. Fortunately, it has been found that minor prpportions of such uncarboxymethylated material are not particularly harmful, and may even be advantageous. The carboxymethylation involving reaction with the.gppropriate chloro- or bromocarboxylic acid or a salt thereof in the presence of a strong base is preferred for Case 156-7096 completeness.

The amidoethylamine intermediates may be prepared via a condensation reaction comprising reacting the alkyl or alkylphenyl polyoxyalkylene carboxylic acids and the appropriate amine, e.g., 2-aminoethylethanol amine, in a;.,.,Lit equimolar proportions at elevated temperatures of between 100 220C and reduced pressures while removing water of condensatior.

Alterna-.vely, the amidoethylamine intermediates may be prepared via a condensation reaction involving the corresponding alkyl or alkylphenyl polyoxyalkylene carboxylic acid lower alkyl estersp e.g.t methyl, ethyl, isopropyl, etc., or halides, and the appropriate amine in about equimolar proportions at a temperature of between 50 and 150C. For examplev the amidoethylamine intermediates may be prepared via a condensation reaction involving the isopropyl ester of the cor- responding alkyl or alkylphenyl polyoxyalkylene carboxylic acid and the appropriate amine, with removal of isopropyl alcohol. When the corresponding carboxylic acid halide is used the reaction is conducted in a 0.45-1.10 mole ratio of carboxylic acid halide to amine, the use of an excess amine being necessary to trap the hydrochloric acid that is formed during the reaction. Optionally, a basic amine, e.g.f triethylamine or pyridine, may be added to the reaction mixture to trap the hydrochloric acid. If so, the reactants may be employed in about equimolar proportions. The reaction is usually conducted in the presence of an inert organic solvent, e.g., an aliphatic hydrocarbon such as dichloromethane, at a temperature of from 25 to 50C.

The resulting amidoethylamine intermediates are then carboxylated by formation of an ammonium salt via a nucleophilic displacement reaction. A base need not be added due to the basicity/nucleophilicity of the amine functionality. Therefore, when an amidoethylamine inter- mediate and the chloro- or bromocarboxylic acid salt are reacted in about equimolar proportions in the presence of a common solvent, e.g., water or alcohol, at a temperature of from 25 to 1000C, preferably between 50 and 90C, a compound of formula I in which R2 is hydrogen is prepared. A solvent need not be employed if the viscosity of the reaction mass allows for efficient stirring and good mass transfer.

1 Case 156-7096 Any further carboxylation, i.e., for preparing compounds of formula I in which R2 is -CH2COOM, may be carried out by the displacement reaction described above, including the presence of a strong base to deprotonate the ammonium ion and render it nucleophilic toward the chloro- or bromocarboxylic acid salt. The reaction conditions are essentially identical to that described above regarding the preparation of compounds of formula I in which R2 is hydrogen.

The compounds of formula I are useful as surface active agents, and are suitable as emulsifiers, dispersing agents, detergents, wett- ing agents, levelling agents and the like in the textile, leather, paper, lacquer, personal care, e.g., toiletries, cosmetics, etc., and rubber industries. For instance, they can be used as wetting agent5or detergents in the treating and refining of textiles; and for converting liquid or solid substances which are insoluble in water (such as hydrocarbons, higher alcohols, oils, fats, waxes and resins) into creamy emulsions, clear solutions or fine, stable dispersions.

In addition, the compounds of formula I are valuable emulsifiers for insecticide compositions and agricultural sprays such as DDT, 2,4-D and the like; are useful as additives to petroleum products, hydraulic fluids, lubricating oils, cutting oils and greases; may be employed as coating aids for use in coating compositions comprising a hydrophilic, film-forming colloid; may be employed as tackifiers in the adhesive layer of adhesive tapes in, e.g., the photographic industry; and as foaming agents and emulsifying agents in a wide variety of food products.

The amphoteric compounds of the instant invention are especially useful as a surfactant component in shampoo compositions. Their incorporation serves to enhance not only the detergent and foaming properties of the shampoo compositions but the tactile properties as well. Such shampoo compositions will normally contain from about 5% to about 55% of an amphoteric compound of formula I, preferably from about 10% to about 45%, and more preferably from about 10% to about 40%. Although the amphoteric compounds of the invention may be employed as the sole surfactant thereof, i.e., totally replace the conventional anionic surfactants such as the alkyl-EO sulphates, the i Case 156-7096 more preferred feature of the instant invention is to employ the amphoteric compounds of this invention in combination with conventional surfactants, i.e., partially replace the latter. In such shampoo compositions, the amphoteric surfactants of the instant ins vention wLI1. 1 normally comprise between 20% and 50% by weight of the mixture, prc..,,- ably between 30% and 45%.

The sham---z compositions can contain other ingredients commonly found in such t:,pe compositions. For example, a fatty alkanolamide, or a mixture therecf, may be employed to assist in foam stabilization, foam boosting and in providing a cosmetically acceptable viscosity. In general, a Ce-Cle mono- or dialkanolamide of the 1:1 variety (prepared by reacting equimolar amounts of the methyl ester of the appropriate -carboxylic acid and the mono- or dialkanolamine) is employed. A suitable example of a monoalkanolamide is cocomonoethanolamide, and typical examples of suitable dialkanolamides are lauric diethanolamide and cocodiethanolamide.

Conditioners may also be employed and such may be quaternary ammonium compounds such as dimethyl distearyl ammonium chloride and cationic polymers such as Cartaretin F-23 (Sandoz Corporation) and Polymer JR (Union Carbide). These materials are utilized to improve the combability and manageability of damaged hair and to reduce static build- up on dry hair.

In order to improve.the sheen of the hair, an oil may be present in the shampoo compositions. Such may be a silicone oil such as dimethylpolysiloxane or other conventional polysiloxanes, olive oil, or a light mineral oil.

The amount of water or aqueous vehicle to be included depends upon the desired consistency of the final product. It is possible to vary the amount of water present to formulate, for example, a thick-flowing liquid, lotion or gel. Inorganic salts such as sodium chloride can also be employed to control the viscosity.

Other conventional additives typically employed in shampoo com--positions may be utilized. Fragrance oils, which mask the odour and provide cosmetic appeal, can be employed. Non-toxic and compatible dyes may be utilized to colour the compositions, as desired. Preservatives, such as methyl paraben, propyl paraben and formaldehyde Case 156-7096 may be utilized.

In addition, other ingredients can be employed beneficially to provide shampoo compositions tailored to a specific use. For example, a sun screen additive such as octyl dimethyl para-aminobenzoic acid can be employed to provide hair protection. Also, products designed to provide dandruff protection can be formulated with agents such as zinc omadine (Olin).

The following examples in which all parts are by weight and all temperatures in degrees centigrade illustrate the invention.

EXAMPLE 1: N-[2-(NI-carboxymethyl-N'-(2-hydroxyethyl)mmoniua)ethyl] lauryl-tetraethoxy acetamide chloride C12H2!5-0---C2H40-)4-CH2CNHCH2CH2-ON CH2COONa ..I 1 H C112CH20H a) Preparation of N-[2-(2-hydroxyethylamino)ethylj lauryl- tetraethoxyacetamide cle 282.6 Parts of lauryl-tetraethoxy acetic acid are placed in a reaction flask, heated to 70 under vacuum (water aspirator) to remove residual water, sparged with nitrogen and cooled to 250. To the reaction vessel are added, in a continuous stream with stirring under a -nitrogen flow at 25, 52.07 parts of 2-aminoethylethanolamine. The temperature of the reaction mixture is gradually warmed to 49, over a period of 1 hour, after which time the reaction mixture is heated to 160 under a nitrogen flow. After 10 parts of water have been collected, the heating is discontinued and the resultant product is allowed to cool to 25 to yield a liquid product of the formula 0 11 C12H25-0-C2H40)4CH2CNHCH2CH2-NH 1 Un2CH20H Preparation of the title compound All- i Case 156-7096 102.15 Parts of the compound prepared in la) above are dissolved in 180.3 parts of distilled water and the resultant solution is placed in a reaction vessel. 17.55 Parts of sodium monochloroacetate are then added to the reaction vessel, with stirring. The reaction mixture is then heated to 70', and this temperature is maintained for 5 hours The heating is then discontinued, which resulted in the title compound being obtained as a 40% active solution. Upon cooling, the title compound is obtained as a clear yellow gel.

EXAMPLE 2: N-[2-(NI,Nl-bis(carboxyaethyl)-N,-(2-hydroxyethyl)wmonium) ethyl]p-nonylphenoxy-nonaethoxy acetamide chloride 0 11 H19C9 0-4C2B40)9CH2CNRCH2CH2-'9N 1 CH2COONa CH2COONa CH2CH20H a) Preparation of N-[2-(2-hydroxyethylamino)ethyl]p-nonylphenoxy- nonaethoxyacetamide C19 Following essentially the procedure of Example la) above, and using in place of lauryl-tetraethoxy acetic acid, an approximately equivalent amount of pnonylphenoxynonaethoxy acetic acid, a compound of the formula 0 11 H19C9 0-4-C2H40)q-CH2CNHCH2CH2NH Un2CH20H is obtained.

Preparation of the title compound 218 Parts of the compound prepared in 2a) above are dissolved in 416 parts of distilled water and the resultant solution is placed in a reaction vessel. After stirring has been initiated, 30.2 parts of sodium monochloroacetate are added to the reaction vessel. The re- action mixture is then heated to 75', and this temperature is maintained for 4 hours. The mixture is then cooled to 500 and 20.8 parts of a 50% sodium hydroxide solution are added. After stirring for 30 Case 156-7096 1 minutes, 30.2 parts of sodium monochloroacetate are added to the mixture. The resultant mixture is allowed to react overnight, while the temperature is maintained at 500. The heating is then discontinued, which results in the title compound being obtained as a light yellow, aqueous solution containing approximately 40Z active.

EXAMPLE 3: N-[2-(N',Nl-bis(earboxymethyl)-N,-(2-hydroxyethyl)amonium) ethyl]iscdecyl-dipropoxyhexaethoxy acetaside chloride 0 CH2COONa iso-ClOH21-0---C3H60-)2--C2H40-)6-CH2CNHCH2CH2'SN C19 I \ CH2COONa CH2CH20H a) Preparation of N-[2-(2-hydroxyethylamino)ethyl]isodecyldipropoxy-hexaethoxy acetamide Following essentially the procedure of Example la) above, and using in place of lauryl-tetraethoxy acetic acid, an approximately equivalent amount of isodecyl-dipropoxy-hexaethoxy acetic acid, a compound of the formula 0 11 iSO-C1OH21-0--(--C3H60-)2---C2H40-)6-CH2CNHCH2CH2NH 1 Ull 2 U1 2 Ull is obtained.

Preparation of the title compound Following essentially the last step of the procedure in preparing the compound of Example 2, and using in place of the compound prepared in Example 2a), an approximately equivalent amount of the compound prepared in 3a) above, the title compound is obtained as a light yellow, aqueous solution containing approximately 40% active.

11 Case 156-7096 EXAMPLE 4: N-[2-(NI,Nl-bis(carboxymethyl)-N,-(2-hydroxyethyl)aaaonium) ethylllauryl-tetraethoxy acetamide chloride 0 CH2COONa 11 C12H25-04C2H40)4CH2CNHCH2CH2-19N 1 CH2COONa C19 CH2CH20H Following essentially the last step of the procedure in preparing the compound of Example 2, and using in place of the compound prepared in Example 2a), an approximately equivalent amount of the compound prepared in Example la), the title compound is obtained as a pale yellow, aqueous solution containing approximately 40% active.

It should be understood that in all of the examples above, the indicated number of propyleneoxy units and ethylencoxy units are average values.

EXAMPLE 5

To demonstrate the high degree of salt tolerance exhibited by the amphoteric compounds of the instant invention, the compound of Example 3 was tested against Miranol C2M (a commercially available amphoteric surfactant containing a coconut hydrophobe having an average chain length of 12 carbon atoms). Test samples were prepared containing 20% active surfactant and levels of sodium chloride varying from 3% to 13%. The viscosities were measured employing a Brookfield LVT visco- meter at 60 rpm. As can be clearly seen from FIG. 1, the compound of Example 3 has a significantly lower viscosity at each level of salt. In addition, as the salt level increases, the viscosity response of the compound of Example 3 is less than that of Miranol C2M. Therefore, it can be concluded that the compound of Example 3 is more suitable in formulating products that contain high levels of ionic materials than is Miranol C2M. Moreover, it can additionally be concluded that the compound of Example 3 would be moreeffective in tertiary oil recov6ry where saline conditions are high than is Miranol C2M.

Case 156-7096 EXAMPLE 6

The following represent typical formulations useful as shampoo compositions.

Ingredients Compound of Example 4 (on a 100% active basis) 9.20 Sodium Myristyl ether sulphate 11.70 Triethanolamine Lauryl sulphate - Lauric Acid diethanolamide 3.00 Sodium Laureth-13-Carboxylate 0.50 Cetyl C12-15 Pareth-9-Carboxylate 1.00 PEG-6000 Distearate 0.50 Polymer JR-400 2 is Germaben 11 3 Dow 193 Surfactant 4 Water (citric acid) pH (adjusted with citric acid) Total Solids (Cenco 5) Formulation A B Weight Percent 16.67 38.90 3.30 - 0.30 1.00 1.00 72.10 Total 100.00 6.5 19.0 40.83 100.00 6.5 32.0 Viscosity (60 rpm; spindle 4; Brookfield LVT) 4720cps 4760cps

Foam Height (Ross-Miles; 0.1%; mm 0/5 min.) 172/172 152/150 1 The reaction product of polyethylene glycol (MW = 6000) with stearic acid (2 equivalents); 2 the reaction product of hydroxyethyl cellulose and epichlorohydrin which is subsequently quaternized with trimethylamine, available commercially from Union Carbide Corp.; 3 a mixture of diazolidinyl urea, methyl para-aminobenzoate and propyl para-aminobenzoate in propylene glycol, available commercially from Sutton Labs, Inc.; 4 dimethicone copolyol, available commercially from Dow Corning.

Type of moisture balance which utilizes an infra red lamp to remove moisture.

m

Claims (16)

Claims in which R Case 156-7096 1. A compound of formula I R0-4CO.))a-4C2H40)n-CH2-C-N-CH2CH2-0)N R, 1 "\ R2 CH2CH20H xe I is Cr5-C22 straight or branched chain alkyl or a group R3-C6H5-1 Where R3 is C6-C,6 straight or branched chain alkyl; R, is -CH2COOMI where M is hydrogen or a cation selected from alkali metal, alkaline earth metal, ammoniumt mono-p di- and tri-C2- C4alkanolammonium and mono-, di-, tri- and tetraCl-C4alkylammonium; R2 is hydrogen or -CH2COOMI where M is as defined above; is 0 or an integer 1 to 10; is an integer 2 to 15; and X9 is an anion, or a mixture of said compounds. is 2. A compound according to Claim 1 of formula Ia 0 H 11 1 11.11 R.-0(C3 H6 0) p -(C2 H4 0),-CH2 -C-N-CH2 CH2 -ON q R,.

1 1,11 R2a CH2CH20H in which R. is Ce-C20 straight or branched chain alkyl or a group R3.-C6H5-, where R3. is C6-CI4 straight or branched chain alkyl; R,. is -CH2COON, where M, is hydrogen or a cation selected from alkali metal, alkaline earth metal and ammonium; R2a is hydrogen or -CH2COON, where M. is as defined above; p is 0 or an integer 1 to 5; is an integer

2 to 12; and X.a Ia CI Case 156-7096 X.9 is halide, or a mixture of said compounds.

3. A compound according to Claim 2 of formula Ib R1b Rb-O-G3H6 0) r---(C2 H4 0)t-CH2 -C-N-CH2CH2 -IBN 1 "'R2 h CH2CH20H -5 in which Rb is C10-C20 straight or branched chain alkyl or a group R3h-C6H5-, where R3b is C&-CI2 straight or branched chain alkyl; R1h is -CH2COONb, where Mb is hydrogen or a cation selected from alkali metal and ammonium; R2b is hydrogen or -CH2C00Mb, where Mb is as defined above; r is 0 or an integer 1 to 3; t is an integer 3 to 10; and Xbe is chloride or bromide, or a mixture of said compounds.

X,,e Ib

4. A compound according to Claim 3 of formula Ic H Rt-O-(C3H60)u-(C2H40),-CH2-C-N-CH2CH2-ON R2c U Rj 1 ' R2C CH2CH20E in which R, is C12-C18 straight or branched chain alkyl or a group R3.-C6H5-1 where R3c is C9-C12 straight or branched chain alkyl; RIc is -CH2COON, where Mc is hydrogen or a cation selected from sodium, potassium and ammonium; is hydrogen or -CH2COOM,, where M. is as defined above; is 0 or an integer 1 or 2; v is an integer 4 to 9; and Xce ic 11 - - Case 156-7096 XcE) is chloride, or a mixture of said compounds.

5. A compound according to Claim 4 having the formula 0 CH2COONa C12H ON 25-0-4C2H40)4CH2CNHCH2CH2- CH2CH20H Cie

6. A compound according to Claim 4 having the formula 0 CH2COONa H19C9 0--C2H CH @N 40)9CH2MCH2 2J""CH2COONa CH2CH20H

7. A compound according to Claim 3 having the formula 0 11 Cle CH2COONa iso-ClOH21-0-±C3H60-)2-(-C2H40-)6-CH2CNHCH2CH2'BN Cie I \CH2COONa CH2CH20H

8. A compound according to Claim 4 having the formula 0 CH2 COONa 11 C,2H25-04C2H40)4CH2CNHCH2CI12-'3N "----'CH2COOD1a 1 Cie CH2CH20H

9. A compound as claimed in Claim 1 as described in any one of Examples 1 to 4.

10. A shampoo composition comprising, as the essential surfactant component, from about 5% to about 55% by weight of a compound accord15 ing to any one of Claims 1 to 9, or a mixture thereof.

11. A composition according to Claim 10 wherein the essential surfactant component is present in an amount of from about 10% to about 45% by weight.

- 20 Case 156-7096

12. A composition according to Claim 11 wherein the essential surfactant component is present in an amount of from about 10% to about 40% by weight.

13. A composition according to Claim 11 wherein the essential 5 surfactant component is a compound having the formula CH2COONa 0 11 C121125-0-C21140)4CR2CNHCH2CH2-ON CH2COONa 1 CH2CH20H Cie

14. A shampoo composition comprising, as the surfactant component, a mixture of an anionic surfactant and a compound of formula I accord ing to Claim 1, the latter being pre - sent in an amount of from about 20% to about 50Y. by weight of the mixture.

15. A composition according to Claim 14 wherein the compound of formula I is present in an amount of from about 30% to about 45% by weight of the mixture.

16. A shampoo composition as described in any one of Examples 6A 15 and 6B.

Published 1990 atThe PalentOffi0e,State House.66P71 High Holoorn. London WCIA 47?. Further copies maybe obtanedfrom The Patent Office. irkw techniques ltd, St M&rj Cray, Kent. Con. 1/87 Sales Branch, St Maxy Cray, Orpington. Kent BR5 3RD. Printed bY Mult'