GB1574916A

GB1574916A - Surface-active amides and imidazolines

Info

Publication number: GB1574916A
Application number: GB2318077A
Authority: GB
Original assignee: Miranol Chemical Co Inc
Current assignee: Miranol Chemical Co Inc
Priority date: 1977-06-01
Filing date: 1977-06-01
Publication date: 1980-09-10

Description

(54) SURFACE-ACTIVE AMIDES AND IMIDAZOLINES (71) We, THE MIRANOL CHEMICAL COMPANY, INC., a Corporation organized and existing under the laws of the State of New Jersey, United States of America, of 277 Coit Street, Irvington, State of New Jersey, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to nitrogenous condensation products and hydrolysis products thereof and methods for their preparation. More specifically, the invention relates to substituted imidazolines, their hydrolysis products and methods for their preparation.

According to the present invention there is provided a novel reaction product useful as a foaming agent, a detergent and in compatibilizing cationic polymeric conditioning agents and anionic detergents, characterized by being produced by reacting a) the amide, imidazoline or mixed amide/imidazoline condensate of an optionally ethylenically unsaturated monocarboxylic acid of 5 to 26 carbon atoms and an N - aminoethyl C2-C4 alkanolamine condensate having its hydroxy group optionally oxyalkylated with up to 4 units of a C2-C4 alkylene oxide with b) either (i) an a, - unsaturated dicarboxylic acid of 4 or 5 carbon atoms or a partial ester of such an acid or a salt of such an acid or partial ester or (ii) an a - unsaturated monocarboxylic acid of 3 to 5 carbon atoms or a salt thereof to result in the saturation of the double bond thereby binding the acid residue through an ether linkage and in the case where said reactant (b) is a monocarboxylic acid or derivative thereof subsequently reacting said reaction product with an alkylating agent known per se to introduce an -R3COOM group at the tertiary nitrogen of said first reaction product wherein R3 is an alkylene group of 1 to 5 carbon atoms and M is hydrogen or a cation.

From a further aspect the invention provides the hydrolysis product of such a reaction product. Without wishing to be bound by any theory we believe that the imidazoline products are of the general formula:

wherein R is a hydrocarbyl group of 5 to 25 carbon atoms such as an alkyl or alkenyl group of 5 to 25 carbon atoms; n is 0 to 4; wherein m is 0 to 1; M is selected from the group consisting of H or a cation, and R3 is an alkylene group of 1 to 5 carbon atoms; each R1 is an alkylene group of 2 to 4 carbon atoms and may be the same or different; and Ac is selected from the group consisting of the saturated residue of an cur unsaturated dicarboxylic acid of 4 or 5 carbon atoms, or the saturated residue of a partial ester of one of said acids, a salt of said acid, a salt of said partial ester and -R2COOM wherein M is as defined above and R2 is an alkylene group of 2 to 4 carbon atoms; said Ac group being bound through an ether linkage; with the proviso that if Ac is -R2COOM then m is 1.

The hydrolysis products are believed to be of the formula:

where in R, R1 and n are as defined above, X is -R3CO2M wherein R3 and M are as defined above, m isO, 1 or 2, Y is -R3CO2M or hydrogen provided that if Ac is the residue of an a, - unsaturated monocarboxylic acid either Y is R3CO2M or m is 0 or 1.

Various imidazoline derivatives particularly those having amphoteric properties have been suggested and used in surfactant compositions. Thus, in United States Patent 3,408,361 of Hans S. Mannheimer dated October 29, 1968, certain hydroxyethyl imidazolines are described. Other prior art is described in United States Patent is U.S. 2,155,877 to Waldmann (1939) and 2,267,965 to Wilson (1941) and U.S. Patent 2,520,102 to Tryon (1950). These imidazoline products are obtained by reacting a diamine, for example, one of the formula NH2C2H4- NHR2-OH and an acid of generic formula R-COOH wherein R has 5 to 25 carbon atoms and is an alkyl or alkenyl group, R2 is R,(ORl)n in which R, is an alkylene group of 2 to 4 carbon atoms and n is 0 to 4. The amines used in preparing the condensates have two amino groups one being a primary amino group and the other a secondary amino group in 1:2 position to each other. In the aforesaid United States Patent 3,408,361 the diamine and fatty acid are reacted to remove water of reaction. When only one mole of water is removed an open-chain product is obtained, considered to be for example, in the instance where n is 0 of the formula:

which is as an amide. If more than one mole of water is removed the imidazoline ring structure is considered to be formed giving for example, in the instance where n is 0, product of formula:

For convenience the imidazoline ring structure in this specification is formalized; the correct formula is:

The imidazoline can be converted to the open-chain structure by hydrolysis and in the art these open-chain products whether originally or by hydrolysis are regarded from many aspects as having the equivalent properties to the imidazolines although not demonstrating the closed ring structure. Moreover, the initial condensation product generally contains a mixture of open-chain and ring closed (imidazoline) products.

The preparation of an imidazoline substituted in the 2 - position by a long chain aliphatic hydrocarbon radical is well described in the laterature and is readily carried out by reaction as described above between a carboxylic acid and a polyamine containing at least one primary amino group and at least one secondary amino group. Usually the hydroxy ethyl type amine is employed.

A nitrogen on the ring has been further reacted with an alkylating agent, for example, sodium chloroacetate, (United States Patent 2,528,378 of Mannheimer 1950) to provide structures considered as having the formula:

wherein R and R1 are as defined above and R3 is an alkylene group of 1 to 3 carbon atoms, for example, methylene.

When in hydrolyzed or open-chain form such structures could be regarded as having the structure:

Correspondingly, the imidazolines may be reacted with a monocarboxylic unsaturated acid or ester (United Kingdom Patent 1,078,101 of Arndt, 1967 and United States Patent 3,555,041 of Katz) to provide structures considered as having the formula:

wherein R and R, are as defined above and R2 is alkylene of 2 to 4 carbon atoms.

When in hydrolyzed or open chain form such structures could be regarded as having the structure:

As mentioned, in United States Patent 2,528,378 there is described the preparation of a condensate of a diamine with a fatty acid which is further reacted with a monohalo monocarboxylic acid particularly a metal salt thereof.

Such products have been found to demonstrate various surfactant or detergent properties and to be useful in products requiring good foaming properties and particularly those requiring fine bubble structure with good stability, for example, shampoo compositions. Nevertheless, despite the improvements obtained there is still a need for improvement in foam structure and stability of compositions particularly shampoo compositions. The present invention has as its objects imidazolines and the related open-chain structures which products can also be described as modified condensation products of diamines and fatty acids, having improved properties for use in detergent or surfactant compositions, for example, shampoos.

The fatty acid of the condensate employed in preparing the reaction products of the present invention is preferably lauric acid giving R as undecyl.

The preferred reaction products and unhydrolyzed products which have not been subjected to any further alkylation to introduce an -R3COOM group. They are believed to be of the formula:

wherein R is alkyl of 5 to 25 carbons and Ac, is a saturated residue of unsaturated dicarboxylic acid of4 to 5 carbons bound through an ether linkage, and particularly preferred as Ac, is the residue from fumaric or maleic acid or its half ester with an alcohol of I to 6 carbon atoms.

A preferred hydrolyzed form is believed to be of the formula:

wherein Ac is a residue of an acid selected from the group consisting of fumaric, maleic and itaconic acids wherein one of their carboxylic acid groups may be neutralized with a base or esterified.

Another preferred product is obtained by reaction of hydrolyzed reaction product as described above or one wherein the unsaturated dicarboxylic acid residue as Ace has been replaced by an unsaturated monocarboxylic acid, with an alkylating agent to introduce a ACH2)pCOONa for example, a compound of the formula Cl(CH2)-COONa to produce a compound believed to be of the formula:

wherein R is alkyl of 5 to 25 carbons, m is from 1 to 2 and Ac is a saturated residue of an unsaturated mono- or dicarboxylic acid or half ester thereof and particularly one in which R is undecyl, p is 1 or 2, m is from 1 to 1.3, and Ac is as defined above or -CH2CH2CO2.

The reaction products of the present invention are obtained by condensation of a diamine which is of formula NH2CH2CH2NHR,(OR,)OH wherein R, is as hereinbefore defined and preferably is R, which is alkylene of 2 to 4 carbon atoms with an acid of formula R-COOH wherein R is as hereinbefore defined with reaction product has from 1 to 2 moles of water removed during condensation. Said condensation product of the invention is the basic condensation product which is modified by condensation with an unsaturated dicarboxylic acid or a partial ester thereof. The resulting product can be further modified by alkylation to add the residue of an alkanoic acid. Instead of a dicarboxylic acid the basic condensation product can also be modified by condensation with a monocarboxylic unsaturated acid, but such a reaction product must be further alkylated to add the residue of an alkanoic acid.

These compounds can be prepared from a condensation imidazoline product as previously described in this specification.

Such imidazoline condensation products and the preparation thereof are described in detail in the art for example in United States Patent 3,408,361 to Mannheimer, although the preparation of the starting materials of this invention is not confined to such method and any technically appropriate method for the preparation of such starting materials can be employed. Essentially, one method for the preparation of the starting materials is to condense a suitable diamine and a monocarboxylic acid. The acids can be replaced by esters, amides, anhydrides or acid halides. Whatever the reactant employed in this step the product obtained is referred to as a condensate of the acid. When one mole of water is removed during such condensation the basic product will then be considered to be of the formula RC(O)NHCH2CH2NHR,OH More usually, more than one mole of water is removed and the product will then be considered to contain an appropriate amount of imidazoline ring structure of the formula

Hereinafter the term condensate is applied to the immediate product of such condensation of fatty acid and amine with up to 2 mols of water being removed. As already indicated a hydroxyalkyl amine can be employed.

The nature of the acid residue is a residue of an acid of 5 to 26 carbon atoms, preferably 8 to 22 carbon atoms. Typical acids are coconut, lauric, oleic, tall oil fatty acids, stearic, n-valeric, isovaleric, caproic, heptoic, caprylic, pelargonic, capric, undecylic, tridecyclic, myristic, pentadyclic, palmitic, margaric, octadecyclic, nonadecyclic, linoleic, erucic acid naphthenic and long chain fatty acids may be employed while certain unsaturated analogues may be used. The presence of minor or even major amounts of impuritity such as the unsaturated fatty acids for instance, is not necessarily detrimental and these can be used as the primary acid. The fatty acids can also include those obtained from the oils of fats of animal, marine or vegetable origin including coconut, palm kernel and palm oil acids which contain fatty acids having at least 11 carbon atoms, also from soy bean, linseed, olive, rape seed, cotton seed, and peanut oil. Mixtures of fatty acids can be employed. An ester can sometimes be employed, the alcohol being split off during the reaction and being removed as by distillation.

While the invention is primarily described in relation to R, as ethylene as already indicated other alkylene groups of 2 to 4 carbon atoms can be employed for example, propylene, particularly isopropylene, isobutylene, n-butylene or secondary butylene depending on the choice of amine. A preferred amine is N aminoethylethanolamine which gives R, as CH2-C112- and another preferred amine is aminoethylisopropanolamine. The alkylene amide adducts obtained by reacting a product wherein Ra is R1-OH with up to 4 mols of an alkylene oxide e.g., ethylene oxide or propylene oxide can be employed as the initial amine for condensation with the fatty acid. Polyoxyalkylene amines prepared by other techniques can also be employed.

The present invention is exemplified by a limited number of condensates.

However, in view of the extensive art on said condensates which are recognized as having equivalent properties it will readily be recognized by those skilled in the art that any given monocarboxylic acid or diamine as exemplified can be replaced and results obtained which are within the normal range of properties useable in the present invention.

The condensate whether regarded as pure imidazoline or as a mixture of imidazoline in open-chain product or simply as a condensate is then reacted to provide the products of the invention. The basic condensate is hereinafter referred to as the condensate.

Generally, the condensate is a mass which although solid at room temperatures can be melted without decomposition often at temperatures below 100"C. The initial reaction product of the invention with an unsaturated carboxylic acid can be obtained simply by adding the carboxylic acid to molten condensate.

Preferably, addition takes place over a period sufficient to allow even reaction without unnecessary concentration of the acid at any given time. The exact rate of addition of the acid to the molten condensate is simply a matter of technical expertise. The reaction conditions for the reaction between the unsaturated acid and condensation product can vary widely providing that the conditions are sufficiently vigorous to initiate the reaction between the reactants. A temperature range of approximately 200C to 100C is suitable, although at too high a temperature one may have degradation of some products. The unsaturated acid or partial ester should be added at such rate that the molar concentration in the reacting process at any given time is such as to minimize polymerization and particularly self-polymerization. The reaction can be carried out in solvents or simply by addition of the unsaturated acid to the molten mass of condensation product. In that the reaction can be regarded essentially as a reaction of a hydroxy group with an unsaturated carboxylic acid, those techniques available generally for such reactions can be employed, having regard to the physical properties of the reactants.

The unsaturated dicarboxylic acids must have two carboxylic groups on adjacent carbon atoms and either between these two carbons or immediately adjacent to them an unsaturated grouping. The preferred acids are maleic, fumaric and itaconic acids.

The unsaturated dicarboxylic acid residues which can occur in the final product include the partial esters thereof up to the half ester. A partial ester is preferably employed having from 25 to 50% esterification. By 2to/, esterification is meant that in a given amount of acid up to 25% of the acid groups present are esterified and 50% esterification would mean that the half ester was formed. A preferred ester is the half-ester or "50%" partial ester. While preferably in most instances the partial ester would be reacted with the condensate an alternative route would be to react the free acid and then esterify up to 50 /" the carboxylic groups in the product. Various conventional esterification techniques for use in this reaction are readily available to those skilled in the art. An alternative technique is to react a full ester and then hydrolize either to a partial ester (50 /" or below) or completely to free acid.

The partial esters of the dicarboxylic acids include methyl esters, ethyl esters and other lower alkyl esters of up to 6 carbons in the alkyl groups, e.g., the hexyl ester.

When the resulting product is prepared substantially from unhydrolyzed material it can be transformed into a hydrolyzed product by forming an aqueous solution and hydrolyzing preferably in the presence of a base for instance sodium hydroxide, potassium carbonate, ammonia, monoethylamine, diethylamine, triethylamine and mono-, di- or tri - ethanolamine.

The preferred base is sodium hydroxide. After hydrolysis it is generally desirable to neutralize the base when used by addition of an acid, particularly an inorganic strong acid such as hydrochloric acid. However, even without hydrolysis the reaction product of the condensate and a dicarboxylic acid or an ester thereof is a commercially significant product. In neutralizing, various acids can be employed including hydrochloric acid, sulfuric acid and nitric acid, although hydrochloric acid is preferred. In the final product M, if not hydrogen, can be one of the cations used customarily in the art of surfactant amphoterics but is customarily an alkali metal, for example, sodium or potassium, but organic bases can also be employed.

In this hydrolysis as indeed in all the hydrolysis reactions described herein fission of the imidazoline structure is most probably between the 2-carbon and 1nitrogen but can also be speculated as being at least partially between the 2-carbon and 3-nitrogen.

In many circumstances a final commercial product is obtained by addition of water to form a solution. The pH of such solutions will generally be from 4 to 10 but is usually slightly acid particularly for unhydrolyzed materials to minimize spontaneous hydrolysis.

The condensation product can be reacted with a compound which generates a residue of an unsaturated monocarboxylic acid of 3 to 5 carbons for example acrylic acid or methyl acrylate. The reaction can be effected by simple addition of, for instance, the acrylate at a temperature of from 30 to 100 C. Thus, the acrylate can be added over a period of say one to three hours followed by heating for from 1 to 24 hours at from 50 to 1100C. The final process can be performed under vacuum to remove any unreacted acrylate. The product can then be treated with water and caustic soda to hydrolyze and neutralize the acid groups. Acrylate monomers which are suitable for reaction may be acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, isopropylacrylate, acrylamide and/or acrylonitrile. The reaction is found to go to substantial completion under specific conditions and no particular catalyst is required since it appears that the basicity of the tertiary nitrogen atoms is sufficient to self-catalyze the acrylic monomer adduct reaction. Adduct formation can be obtained in some instances by simple addition of monomer acrylate to condensate at temperatures near room temperature although usually it is desirable to increase the temperature to 600C-1000C with removal of unreacted monomer under vacuum. When other than free acids are employed (e.g., acrylamide or acrylonitrile) a specific hydrolysis step will be required to produce the free acid. For example boiling in aqueous system in the presence of a base at 900--1000C until ammonia is completely removed (or alcohol for esters).

The maleate and itaconate salts and half-esters have little odor compared with the acrylate compound used in exercizing U.S. 3,555,041, and furthermore, leave little if any resistant odor in the final products, wherein the acrylate addition products always have rather strong odors attributable to the acrylate addition byproducts.

There can be an additional alkylating reaction, e.g., with a haloalkanoic acid, for instance sodium chloracetate. Preferably this reaction is effected with hydrolyzed products. Since this reaction involves alkylation and possible quaternization of one of the nitrogen atoms the reaction is primarily available with open-chain compounds, i.e., hydrolyzates rather than the imidazolines. When the original reaction of the condensate with the unsaturated carboxylic acid is with a monocarboxylic acid then this additional step is a necessary feature of the invention. The alkylation can be carried out in a single stage in which both hydrolysis and reaction with a haloalkanoic acid is simultaneous or there can be an hydrolysis of the product followed by the reaction with an alkylating agent such as a haloalkanoic acid.

A reaction with three mols of alkylating agent is visualized as shown in the Formulae substituting onto the l-position but substitution at the 3-position may be possible with consequent effect on the structure of the hydrolyzed products.

However, even if a 3-position substitution is effected hydrolysis may result in isomerizing to form the same hydrolysis products as the l-substitution.

A reaction with a haloalkanoic acid can be carried out under a variety of conditions either in the presence of a solvent or more usually in the presence of an aqueous system. For instance the sodium haloacetate can be added to the hydrolyzed system with heating and with or without the addition of a base.

Thus, the condensate reaction product with the unsaturated carboxylic acid can be reacted with a monohalocarboxylic acid in the presence of caustic soda (sodium hydroxide in aqueous solution). In a preferred form one mol of the reaction mass is added to an aqueous solution containing one mol of the monohalo carboxylic acid and from 2.2 to 2.5 mols of caustic soda and the mix is then heated to a temperature of approximately 950C until there is no change in pH. The pH normally drops from about 13 to approximately 8. Additional caustic soda is added to increase the sum of caustic soda to approximately 3 mols and the mass is maintained until there is a sparkling clear solution when adjusted to a pH of from 9 to 10.

Another reaction is as described in United States Patent 2,407,645 to Bersworth (1946) wherein the hydrolyzed condensate reaction product with an unsaturated acid is reacted with an alkali metal cyanide and a formaldehydeyielding substance then hydrolyzed to drive off ammonia. Such a reaction can be used to add 2 mols of alkanoic acid and then one could react with haloalkanoic acid to add a further carboxyalkyl group.

Typical haloalkanoic acids are the sodium or potassium salts of chloracetic acid, and a- or p - chloropropionic acids.

For reaction products obtained by the use of dicarboxylic acids up to three mols of alkanoic acid residue can be substituted preferably W2 mols. For reaction products obtained by the use of monocarboxylic acids there must be some alkylation and again up to three mols can be added but a preferred range is 1--2 mols.

In another method of reacting one can react the basic condensate with the unsaturated acid then simply add water and an alkali metal haloalkanoate.

Thereafter add alkali (e.g., sodium hydroxide) and heat to 100C for say one hour.

The final products are generally obtained in the form of an aqueous solution which may contain residual amounts of reactants employed in preparing the final product. The adduct of the unsaturated acid and the condensation product can be a commercial product as such without addition of water. As is customary in this art the pure product is often not recovered from the aqueous solution and determination of the structure of the product is an educated estimate based on the chemistry involved and the properties of the solution or adduct.

These products have amphoteric properties wherein the unreacted condensates are cationic in nature, therefore a test for completion of reaction is the extent to which the final product forms clear aqueous solutions at high and low pH values.

The products of the invention, particularly when in aqueous solution, are of value in various surfactant compositions and particularly in emulsions, cosmetics and detergents and can be combined with other surfactant Solutions of the products of the invention can comprise an aqueous solution with as major organic components, the product of the invention. The organic content of such a solution can measure from 20 to 90 /,, by weight thereof, for example, 30 to 70%. The solutions represent finished products of commerce although they are frequently later combined by customers with other materials to provide compositions for different purposes especially in the field of cosmetic compositions.

The products of the invention are particularly valuable in shampoos in assisting in the rendering of conditioning agents particularly for instance, polycationic cellulose derivatives, compatible with other surfactants, for instance sulfates. Moreover, certain of the products of the invention at the same time can assist in improving the skin and hair conditioning properties of cosmetic products.

The products of the invention are generally water-soluble as already indicated but some have the advantage of limited solubility in dilute solutions.

The products of the invention as already mentioned can be incorporated in cosmetic preparations where it is desired to emulsify an aqueous phase and the normally lipophilic phase such as mineral oil, which may be the continuous one.

The compounds and their organic sulfate complexes are generally non-antagonistic toward most cosmetic ingredients.

Certain of these products can form complexes which may be complex salts with organic sulfates, e.g., sodium lauryl sulphate, sodium polyoxyethylene (3.5) lauryl sulfates, sodium polyoxyethylene (3) tridecyl sulfate.

The compounds are useful as hair and skin conditioners, hair rinses, creams and fabric softeners, in laundry applications and as cationic emulsifiers and can be generally highly efficient hair and skin conditioners generally without markedly reducing foaming as do conventional conditioners when used in solutions. The ratio of compound employed to water can be from 1.00 to 99.9 /" of the organic compound. The compounds can also be used in the textile industry to improve textile finishing.

One of the most active areas in shampoo research is creating a conditioning property into the shampoo. It would be desirable is the necessity of a post-shampoo cream rinse could be eliminated. A most effective, and widely used conditioning agent is a polycationic cellulose derivative, for example, one made by reacting cellulose derivatives with epichlorhydrin, then condensing with trimethylamine (commercially available as "Polymer JR" which is a Trademark of Union Carbide Corp.). One of the problems in using this type of resin (usually at a level of about one percent of the shampoo formula) is that it is incompatible with many compounds used in shampoos which are anionic.

The products of this invention tend to couple and compatibilize such resins and organic sulfates. It is a valuable aspect of the products employing the residues of dicarboxylic acids and particularly partial esters of such unsaturated dicarboxylic acids that they act as coupling agents in shampoos containing such resins and organic sulfates. The shampoos have all the desirable properties of this general type of product, foaming and conditioning very well.

Adducts of esters of maleic acid, hydrolyzed and unhydrolyzed, couple organic sulfates and Polymer JR, to form clear or nearly clear solutions, whereas adducts prepared from maleic acid and itaconic acid form homogeneous but cloudy or pearlescent mixtures.

Adducts prepared from esters of maleic acid also seem to foam better than the other products, when combined into shampoo formulations containing both organic sulfates and Polymer JR resin.

Generally, products which are not alkylated have superior conditioning properties to alkylated products but the latter are superior in foaming and lathering.

The invention will now be illustrated by Examples.

I

Having regard to the particular method used for making this product it was considered to have primarily the aforesaid structure but it will be appreciated that certain small proportions of amide be present and different methods of preparation might give greater amounts of amide of the structure:

The approximate molecular weight of the condensate starting material of the present invention is 268.

Preparation of Reaction Product of Invention Lauric condensate plus itaconic acid A glass flask equipped with stirrer and thermometer was charged with 1185 g (approx. 4.4 moles) molten condensate. Over a period of two hours, 664 g (approx.

5.1 moles) itaconic acid was slowly added to the mass, starting at 550C and ending at 710C. Temperature was maintained at 690 to 720C, for 19 hours when 1849 g of water was added. The resulting thin, clear, amber colored product, cooled to room temperature had a pH of 4.3.

A 40% aqueous solution of this material, neutralized to pH 4.3 to 7 with 50 /" NaOH solution, vigorously massaged onto the scalp and hair after shampooing, foamed copiously, left the hair, after rinsing, relatively static- and snarl-free, with a smooth, soft feel.

The active content of this product is believed generally to conform the formula:

EXAMPLE II Lauric Condensate Plus Itaconic Acid, Hydrolyzed A glass flask equipped with stirrer, thermometer and reflux condenser was charged with 1849 g (approx. 4.4 moles) of the product of Example I just prior to additon of water. With stirring, the mass was heated to 700C and 1849 g of water and 500 g of 50 /n aqueous NaOH solution were added, lowering the temperature to 62"C. It was heated to 700 C. Fifty percent aqueous sodium hydroxide solution was added to the stirred mass at 709 to 720C, over a three hour period, keeping the pH, measured at 300 C, at 9.0 to 9.4. A total of 668 g 50% aqueous sodium hydroxide solution was used. The mass was cooled and 265 g of 31.5% hydrochloric acid solution was used to neutralize the product to pH 7.8. The final product was clear and viscous.

A 40% aqueous solution of this material, neutralized to pH 4 to 7 with hydrochloric acid, vigorously massaged onto the scalp and hair after shampooing, foamed copiously, left the hair, after rinsing, relatively static- and snarl free, with a smooth, soft feel.

The active content of this product is believed to conform to the following formula:

EXAMPLE III Lauric Condensate Plus Maleic Acid A glass flask equipped with stirrer and was charged with 474 g (approx. 1.77 moles) molten condensate of Example I. Over a period of two hours, 237 g (2.04 moles) maleic acid was slowly added to the mass, starting at 650C and ending at 73"C. The mass was maintained at 66" to 740C, for 19-1/2 hours, when 711 g of water was added. The resulting thin, clear, amber colored product, cooled to room temperature, had a pH of 2.98.

A 40 /n aqueous solution of this material, neutralized to pH 4 to 7 with 50 /n NaOH solution, vigorously massaged onto the scalp and hair after shampooing, foamed copiously, left the air, after rinsing, relatively static- and snarl-free, with a smooth, soft feel.

The active content of this product is believed to conform to the formula:

EXAMPLE IV Lauric Condensate Plus Maleic Acid, Hydrolyzed Example III was repeated using 1232 g (approx. 4.6 moles) condensate of Example 1, 616 g (5.31 moles) maleic acid and 1849 g of water. The heating period was 16 hours at 72" to 850C. After the water had been added, 555 g of 50 /O sodium hydroxide solution was added. The mass was heated six hours at 680 to 72"C, as an additional 100 g of 50 /n sodium hydroxide solution was slowly added to maintain the pH at 9.0 to 9.2.

1535 g of this final reaction mass was neutralized to pH 7.58 with 81.0 g 31.50/, HCI solution.

A 40% aqueous solution of this material, neutralized to pH 4 to 7 with 50 /n NaOH solution, vigorously massaged onto the scalp and hair after shampooing, foamed copiously, left the hair, after rinsing, relatively static and snarl-free, with a smooth, soft feel.

The active content of this product is thought generally to conform the following formula or one of its isomers:

EXAMPLE V Lauric Condensate Plus Maleic Acid Plus Sodium Monochloroacetate A glass flask equipped with stirrer, thermometer and condenser was charged with 2772 g (approx. 2.93 moles) of the reaction product of Example IV prior to having been neutralized with HCI. To this was added 512 g (approx. 4.39 moles) sodium monochloroacetate over a 20 minute period between 50 and 53"C. The mass was heated to 970C, over a period of 1-1/2 hours, while 512 g water slowly was added and 50% sodium hydroxide solution was added to maintain the pH of the reaction mass at 8.6 to 9.4 (measured at 300C). Stirring with heating at 970 to 100 C, was continued for an additional 2-1/4 hours, maintaining the pH (30"C) at 8.7 to 9.4. In all a total of 400g of 50 sodium hydroxide solution was used. With cooling, an additional 1000 g water was added to yield a thin, clear, light amber colored product having a pH of 9.42, non-volatile content of 41.1 and a sodium chloride content of 5.02 /".

A 40 aqueous solution of this material, neutralized to pH 4 to 7 with HCI gave a good head of foam when used as a hair shampoo, leaving the hair soft and manageable. It was practically non-irritating to the eyes of rabbits as tested according to the method of Draize.

The active content of this product is believed generally to conform to the following formula or one of its isomers:

EXAMPLE VI Lauric Condensate Plus Acrylic Acid Plus Sodium Monochloroacetate A glass flask equipped with stirrer, thermometer and reflux condenser was charged with 1400 g (5.22 moles) condensate of Example I. With stirrer, 434 g (6.03 moles) acrylic acid was added over a 4 hr 10 min period at between 65" and 70"C.

The mass was stirred and maintained at 570 to 770C, for 21-1/2 hours, after which 1834 g water was added.

To 680 g (approx. 0.97 moles) of this reaction material was added 174.8 g (1.5 moles) sodium monochloroacetate over a 20 minute period, from 500 to 600 C. The mass was heated to 980C over a period of 1-3/4 hours, while 50^/a sodium hydroxide solution was added to maintain the pH of the reaction mass at 9.0 to 9.6 (measured at 30"C). Stirring with heating at 980C, was continued for an additional 3-1/4 hours, maintaining the pH (300C) at 9.0 to 9.3. In all a total of 194 g of 50% sodium hydroxide solution was used. With cooling, 175 g water was added to yield a thin, clear, light amber colored product having a pH of 9.36, non-volatile content of 49.4 and a sodium chloride content of 7.22%.

A 40 / > aqueous.solution of this material, neutralized to pH 4 to 7 with HCI gave a good head of foam when used as a hair shampoo, leaving the hair soft and manageable. It was practically non-irritating to the eyes of rabbits as tested according to the method of Draize.

Example VII A condensate is prepared according to Preparation I from each of the following acids: Run 1 Caproic acid 2 Capric acid 3 Myristic acid 4 Behenic acid 5 Oleic acid 6 Linoleic acid 7 Palmitic acid Each of the condensation products is individually reacted with: (1) Maleic acid (2) Itaconic acid (3) Fumaric acid (4) The half ethyl ester of maleic acid.

Runs 1, 3 and 7 are repeated with N - aminoethylisopropanolamine and each of the products is reacted separately with maleic acid.

The method employed is that of Example I in each case.

In each case a product is obtained which is soluble in water and has good foaming properties.

EXAMPLE VIII Each of the condensation products of Runs 1 to 7 of Example VII is reacted with maleic acid and hydrolyzed following the procedure of Example IV. A satisfactory product is obtained in each case in terms of foaming properties.

EXAMPLE IX Each of the products from the reaction with maleic acid in accordance with the first part of Example VIII is hydrolyzed as in Example V and reacted with sodium chloroacetate using the conditions of Example V. The product is satisfactory in each case in terms of foaming properties.

EXAMPLE X Amino ethyl ethanolamine (NH2C2H4NHC2H4OH) is reacted as described in United States Patent 2,528,378 to Mannheimer with lauric acid (Example I, references are the Examples of 2,528,378, capric acid (Example 3), linseed fatty acid (Example 4), caproic acid (Example 5), stearic acid (Example 6), myristic acid (Example 8). Thereafter each condensate obtained is reacted with one of the following unsaturated carboxylic acids, maleic, fumaric or monoethyl maleate following the procedure of present Example I.

Each of the products when formed into solution as in Example I have satisfactory foaming properties. The condensates with lauric acid and caproic acid are reacted with acrylic acid as in Example VI and the resulting product is then reacted with in one instance sodium chloracetate and in the second instance with sodium bromopropionate following the procedure of Example VI to obtain an aqueous solution. The resulting solutions have satisfactory foaming properties.

EXAMPLE XI Lauric Condensate Plus Ethyl Maleate A glass flask equipped with stirrer and thermometer was charged with 938 g (approx. 3.5 moles) molten condensate of lauric acid and amino ethyl ethanolamine. Over a period of about two hours, 616 g (approx. 4 moles) of a 94% ethanol solution of monoethylmaleate was slowly added to the mass, starting at 60"C and ending at 73"C. The temperature was maintained at 70"C to 750 C, for about 22 hours. 1554 g water was added, to yield a clear, light amber liquid having a pH of 4.1 and a solids content of 46.7%.

EXAMPLE XII Lauric Condensate Plus Ethyl Maleate, Hydrolyzed 2138 g of the product of Example X using lauric acid and ethyl maleate as starting material was heated, with stirring, with 122 g 50 /n NaOH, to 90"C, the boiling point of the solution. A total of 300 ml distillate was collected and replaced with water as the temperature slowly rose to 1000C. Fifty percent NaOH was added during this time to keep the pH above 9.0. A total of 339 g of 50% NaOH was used in all. When the boiling point of 100"C was reached, indicating essentially all the ester was hydrolyzed and the ethanol removed, and the reaction product was cooled, 300 ml of water was added back to the reaction mass. The resulting clear, amber solution has a pH of 10.0 and a solids content of 44.3.

EXAMPLE XIII Lauric Condensate'Plus Maleic Acid Alkylated To 10 mols of the product of Example III is added 4 mols of caustic soda, eight mols of sodium cyanide are added and 7.5 mols of formaldehyde are added. The conditions and methods of addition are as described in Example I of United States Patent 2,407,645. Addition of sodium cyanide and formaldehyde is repeated after evolution of ammonia ceases for each batch addition. The resulting product in aqueous solution has excellent foaming properties.

EXAMPLE XIV A number of examples of shampoos were prepared. Some typical formulations follow: % By Wt Active A. Condensate of lauric acid and 22.6 10.0 aminoethylethanolamine reacted with monoethylmaleate, hydrolyzed Sodium polyoxyethylene (3) 11.6 8.0 tridecyl sulfate Polymer JR 400, 2 /n aq. soln. 50.0 1.0 Water 15.8 0 100.0 19.0 neutralized to pH 6.7 with HCI.

This shampoo formula is a clear, syrupy liquid which foams very well when used as a hair shampoo. After rinsing, the hair is left with exceptional wet-comb and untangling properties.

Product of Invention % By Wt /n Active B. Condensate of lauric acid and 30.0 14.0 aminoethylethanolamine reacted with monoethylmaleate, unhydrolyzed C. Condensate of lauric acid and 31.6 14.0 aminoethylethanolamine reacted with monoethylmaleate, hydrolyzed D. Condensate of lauric acid and 29.2 14.0 aminoethylethanolamine reacted with monomethylmaleate E. Condensate of lauric acid and 29.6 14.0 aminoethylethanolamine reacted with monomethylmaleate, hydrolyzed Sodium polyoxyethylene (3.5) 20.0 5.0 lauryl sulfate Polymer JR-400 1.0 1.0 Water q.s. 0 all neutralized by pH 6.7 with either NaOH or HCI.

Results: B. Clear, syrupy liquid with good cream rinse action and conditioning properties when used as a hair shampoo.

C. Very slightly hazy, syrupy liquid. Good wet-comb and untangling properties when used as a hair shampoo.

D. Very slightly hazy, syrupy liquid. Very good cream rinse action and wetcomb properties when used as a hair shampoo.

E. Very slightly hazy, syrupy liquid. Very good wet-combing properties when used as a hair shampoo.

O/, By Wt O/, Active Condensate of lauric acid and 26.8 12.7 aminoethylenethanolamine reacted with monoisopropylmaleate Sodium polyoxyethylene (3.5) 18.2 4.6 lauryl sulfate Dimethylcocoamine oxide 9.1 3.6 Polymer JR-400 0.9 0.9 Water 45.0 0 neutralized to pH 6.7 with NaOH.

This is a very slightly hazy, syrupy liquid, which foams well when used as a hair shampoo.

WHAT WE CLAIM IS: I. A novel reaction product useful as a foaming agent, a detergent, and in compatibilizing cationic polymeric conditioning agents and anionic detergents, characterized by being produced by reacting a) the amide, imidazoline or mixed amide/imidazoline condensate of an optionally ethylenically unsaturated monocarboxylic acid of 5 to 26 carbon atoms and an N - aminoethyl C2-C4 alkanolamine the condensate having its hydroxy group optionally oxyalkylated with up to 4 units of a C2-C4 alkylene oxide with b) either (i) an a, - unsaturated dicarboxylic acid of 4 or 5 carbon atoms or a partial ester of such an acid or a salt of such an acid or partial ester or (ii) an a, - unsaturated monocarboxylic acid of 3 to 5 carbon atoms or a salt thereof to result in the saturation of the double bond thereby binding the acid residue through an ether linkage and in the case where said reactant (b) is a monocarboxylic acid or derivative thereof subsequently reacting said reaction product with an alkylating agent known per se to introduce an -R3COOM group at the tertiary nitrogen of said first reaction product wherein R3 is an alkylene group of 1 to 5 carbon atoms and M is hydrogen or a cation.

2. A reaction product according to Claim 1, wherein said reactant (b) is a dicarboxylic acid, characterized in that said reaction product is subsequently reacted with an alkylating agent known per se to introduce an -RCOOM group at the tertiary nitrogen of said reaction product wherein R3 is an alkylene group of I to 5 carbon atoms and M is hydrogen.

3. A reaction product according to either of the preceding claims, characterized in that said reaction product is hydrated in the case where an alkylation to introduce a -R3COOM group is effected, said hydration preferably being effected prior to alkylation.

4. A reaction product according to any one of the preceding claims, characterized in that said condensate is the condensate of lauric acid and N aminoethyl ethanolamine.

5. A reaction product according to any one of the preceding claims, characterized in that as reactant (b) there is employed an et, - dicarboxylic acid selected from maleic, fumaric and itaconic acid and half-esters thereof.

6. A reaction product according to any one of Claims 1 to 4, characterized in that as reactant (b) there is employed acrylic acid or methacrylic acid.

7. A reaction product according to any one of the preceding claims, characterized in that there is employed as alkylating agent to introduce the -R3COOM group sodium monochloracetate.

8. A reaction product according to any one of Claims 1--5 and 7, characterized in that there is employed as reactant (b) an ester of the a, - unsaturated acid and the product is subsequently saponified in manner known per se.

9. A reaction product according to any one of Claims 1, 5, 7 and 8, wherein the aminoethyl lower alkanolamine employed in the production of the condensate is N - aminoethyl ethanolamine and the a, - unsaturated acid employed is an a - unsaturated dicarboxylic acid or a partial ester thereof with an alcohol of 1 to 6 carbon atoms.

10. A reaction product according to Claim 5, wherein the initial condensate employed is derived from undecylenic acid.

11. A reaction product according to any one of the preceding claims, wherein there is employed an alkylating agent and said alkylating agent is such as to introduce a -R3COOM group wherein R3 is -CH2-.

12. A reaction product according to any one of Claims 1 to 5 and 7 to 11, wherein said a, - unsaturated dicarboxylic acid is employed in the form of a diester and the product of the condensation is hydrolyzed at least to the extent of the partial ester.

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **.

This is a very slightly hazy, syrupy liquid, which foams well when used as a hair shampoo.

WHAT WE CLAIM IS: I. A novel reaction product useful as a foaming agent, a detergent, and in compatibilizing cationic polymeric conditioning agents and anionic detergents, characterized by being produced by reacting a) the amide, imidazoline or mixed amide/imidazoline condensate of an optionally ethylenically unsaturated monocarboxylic acid of 5 to 26 carbon atoms and an N - aminoethyl C2-C4 alkanolamine the condensate having its hydroxy group optionally oxyalkylated with up to 4 units of a C2-C4 alkylene oxide with b) either (i) an a, - unsaturated dicarboxylic acid of 4 or 5 carbon atoms or a partial ester of such an acid or a salt of such an acid or partial ester or (ii) an a, - unsaturated monocarboxylic acid of 3 to 5 carbon atoms or a salt thereof to result in the saturation of the double bond thereby binding the acid residue through an ether linkage and in the case where said reactant (b) is a monocarboxylic acid or derivative thereof subsequently reacting said reaction product with an alkylating agent known per se to introduce an -R3COOM group at the tertiary nitrogen of said first reaction product wherein R3 is an alkylene group of 1 to 5 carbon atoms and M is hydrogen or a cation.
2. A reaction product according to Claim 1, wherein said reactant (b) is a dicarboxylic acid, characterized in that said reaction product is subsequently reacted with an alkylating agent known per se to introduce an -RCOOM group at the tertiary nitrogen of said reaction product wherein R3 is an alkylene group of I to 5 carbon atoms and M is hydrogen.
3. A reaction product according to either of the preceding claims, characterized in that said reaction product is hydrated in the case where an alkylation to introduce a -R3COOM group is effected, said hydration preferably being effected prior to alkylation.
4. A reaction product according to any one of the preceding claims, characterized in that said condensate is the condensate of lauric acid and N aminoethyl ethanolamine.
5. A reaction product according to any one of the preceding claims, characterized in that as reactant (b) there is employed an et, - dicarboxylic acid selected from maleic, fumaric and itaconic acid and half-esters thereof.
6. A reaction product according to any one of Claims 1 to 4, characterized in that as reactant (b) there is employed acrylic acid or methacrylic acid.
7. A reaction product according to any one of the preceding claims, characterized in that there is employed as alkylating agent to introduce the -R3COOM group sodium monochloracetate.
8. A reaction product according to any one of Claims 1--5 and 7, characterized in that there is employed as reactant (b) an ester of the a, - unsaturated acid and the product is subsequently saponified in manner known per se.
9. A reaction product according to any one of Claims 1, 5, 7 and 8, wherein the aminoethyl lower alkanolamine employed in the production of the condensate is N - aminoethyl ethanolamine and the a, - unsaturated acid employed is an a - unsaturated dicarboxylic acid or a partial ester thereof with an alcohol of 1 to 6 carbon atoms.
10. A reaction product according to Claim 5, wherein the initial condensate employed is derived from undecylenic acid.
11. A reaction product according to any one of the preceding claims, wherein there is employed an alkylating agent and said alkylating agent is such as to introduce a -R3COOM group wherein R3 is -CH2-.
12. A reaction product according to any one of Claims 1 to 5 and 7 to 11, wherein said a, - unsaturated dicarboxylic acid is employed in the form of a diester and the product of the condensation is hydrolyzed at least to the extent of the partial ester.
13. A reaction product according to any one of Claims 1 to 4, 6, 7, 8, 10 and -II,

wherein said a, - unsaturated monocarboxylic acid is employed in the form of an ester, amide or nitrile and the product of the condensation is hydrolyzed.
14. A reaction product whenever obtained by a process substantially as described in any one of the Examples.