US2936251A - Amido carboxylic acids - Google Patents

Description

Amt) QAFZB'ZIBXYLKC ACIDS Bertram .l. Garcean and Charles A. Robinson, Providence, 12.1., assignors to Arnold Hoffman 81. Co., incorporated, Providence, Rh, a corporation of Rhode island No Drawing. Appiieation December 5, 15 57 Serial No. 700,744

16 Ilaima (Cl. ilk-139.5)

This invention relates to new organic compounds having a free carboxyl group.

It is an object of the present invention to provide novel water dispersible organic compounds.

Another object is to provide new anionic products which are suitable for treating textiles.

A further object is to provide agents which will give improved anti-soiling properties to textiles.

Still further objects and the entire scope of applicability of the present invention will become apparent from the detailed description given hereinafter; it should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications Within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

It has now been found that these objects can be attained by the preparation and use of a special group of half amides of particular alkylene dicarboxylic acids. These compounds have the formula:

O=C(OHz)nOOOH where R and R are aliphatic hydrocarbon radicals having at least carbon atoms, R and R are -CH CH or CH2CH2CH2- OI CH2CH- and n is an integer from 4 to 8 inclusive. Preferably, R and R are aliphatic hydrocarbon radicals having 5 to 17 carbon atoms. R and R can be saturated aliphatic hydrocarbon radicals or ethylenically unsaturated aliphatic hydrocarbon radicals.

Typical examples of compounds coming withinthe instant invention are N,N-di-(stearamidoethyl)-adipamic acid, N,N-di-(stearamidoethyl)-azelaarnic acid, N,N-di- (stearamidoethyl)-sebacamic acid, N,N-di-(caprylamidoethyl) sebacarnic acid, N,N di (olearnidoethyD-azelaamic acid, N,N-di-(stearamidopropyl)-adipamic acid, N- stearamidoethyl-N-caproamidoethyl-adipamic acid, N,N- di-(stearamidoisopropyl)-sebacamic acid, N,N-di-(stearamidoethyD-pimelamic acid, N,N-di-(stearamidoethyl)- suberamic acid, N,N di (caproamidoethyl) sebacamic acid, N,N-di-(myristamidopropyl)-adipamic acid, N-lauramidoethyl-N-palmitamidoethyl-azelaamic acid, etc.

The compounds of the present invention are anionic in nature and are useful in the treatment of textiles. They provide inexpensive, highly effective textile lubricants and softeners and impart anti-soiling properties to textile carpet yarns and fibers.

The compounds of the present invention, being half amides of dicarboxylic acids, differ from the full amides in having a free carboxyl group present in the molecule. It is this free carboxyl group which forms alkali metal 2,936,251 Patented May to, 1960 salts, thus rendering the molecule truly anionic. The full amides on the other hand cannot form salts and cannot be used directly to form anionic textile treating agents, but instead must be modified by the incorporation of alkali soaps and the like. It has been found that the anionic half amides of the present invention are preferred over the corresponding non-anionic full amides as softeners for wool, antisoiling finishes for carpets, and for use in conjunction with other anionic textile finishing agents.

While the compounds of the present invention are frequently prepared and used in the form of the free acids, they are also frequently used in the form of their alkali metal salts, e.g., potassium and sodium salts such as sodium N,N-di-(stearamidoethyl)-adipamate, potassium N,N-di-(stearamidoethyl)-azelaarnate, sodium N,N-di- (oleamidopropyl)-sebacamate, etc. The alkali metal salts are considered the full equivalents of the free acids, therefore.

Unless otherwise indicated, all proportions and percentages in the specification and claims are by weight.

The compounds of the present invention are readily formed by condensing an amido amine containing two amide groups and one secondary amino group With an equimolar quantity of a dicarboxylic acid according to the equation:

O H RiiNHRzNRQNHJD RI+HO0C(CHi),.COOH-q where R, R R R and n are as defined above. It is critical that equimolecular proportions be used since the use of only one-half mol of the dicarboxylic acid per mol of amido amine results in the formation of the diamide of the dicarboxylic acid. Excess dicarboxylic acid can be used if desired over equimolecular proportions, but this is somewhat wasteful and has no material advantage over the use of equimolecular proportions.

In place of the free dicarboxylic acid, there can be employed the anhydride, ester or acyl halide thereof. In the case of the ester or acyl halide, a hydrolyzing agent normally must be added to form the free acid group on the finished product.

The condensation of the amido amine with the dicarboxylic acid is normally carried out at an elevated temperature, sufi'iciently high to cause the evolution of one mol of Water, e.g., to 225 0., preferably C. to 205 C. The water formed in the reaction can be removed with the aid of an inert azeotroping agent, e.g., aliphatic and aromatic hydrocarbons such as xylene, benzene, toluene, hexane, etc.

The amido amines employed as starting materials for the most part are old compounds and can be prepared by the condensation of one mol of the ap; ropriate di alkylenetriamine with two mols of a fatty acid. Unsymmetrically substituted amido amines (R and. R are different) can be prepared by the condensation of the dialkylenetriamine first with an equimolar quantity of one fatty acid and then with an equimolar quantity of a different fatty acid.

As the dialkylenetriarnine, there can be used diethylenetriamine, dipropylenetriamine (3,3'-iminobispropylamine) and diisopropylenetriamine.

As the fatty acids, there can be used saturated fatty acids such as caproic, capyrlic, capric, pelargonic, myristic, lauric, palmitic, stearic, or hydrogenated animal and vegetable fatty acids or unsaturated fatty acids such as oleic, linoleic, eleostearic acid, etc. Mixtures of fatty acids can be used, such as the mixtures obtained by saponifying animal and vebetable fats and oils, e.g., cottonseed oil, soybean oil,-' peanut oil, fish oil, hydrogenated' peanut oil, hydrogenated soybean oil, linseed oil, etc.

As the alkylene dicarboxylic acids, there can be used adipic, pimelic, azelaic, suberic and sebacic acids.

According to the preferred process, an amide amine of the type set forth above is heated with an equimolar quantity of the alkylene dicarboxylic acid at a temperature sufliciently high to cause the evolution of one molecular equivalent of water. Alternatively, one mol of the dialkylenetriamine is heated With two molecular equivalents of a monocarboxylic acid of the type set forth until two mols of water have been evolved. Then, without interrupting the process, one mol of the alkylene dicarboxylic acid is added at such a temperature that no reaction occurs until all of the dicarboxylic acid has been added, after which the mixture is heated until the evolution of water is complete. The yields of the desired semi-amides are essentially quantitative.

For example, one molecular equivalent of N,N-(iminodiethylene) bisstearamide, prepared by the condensation of two mols of stearic acid with one mol of diethylenetriamine, was mixed with one molecular equivalent of adipic acid and heated with stirring at 200 to 205 C. As the reaction proceeded to completion, the amount of water evolved increased to one mol per mol of adipic acid employed and the neutral equivalent of the product increased to the theoretical value.

Analytical evidence showed that the products of the invention were predominately the indicated structure. Neutral equivalents on the crude products indicated molecular weights within 10% of the theoretical values in all cases. Titration of the crude products with acid indicated that the amide amines used as starting materials were converted to amido amides to the extent of at least 85%. Unreacted adipic acid in crude N,N-di-(stearamidoethyl)-adipamic acid, as determined by repeated extraction with water, amounted to less than 10% of that used in its preparation.

The products of the invention are light in color and range from viscous liquids to hard, brittle, wax-like solids. The alkali metal salts, e.g., the sodium, potassium, rubidium and caesium salts, of the products are either soluble or dispersible in water.

For use as textile finishing agents, alkali metal salts of the products are converted by conventional procedures to homogeneous aqueous pastes, which can be readily dissolved or dispersed in water. These products are outstanding in their softening effect on textile fabrics. They are also useful as lubricating agents for yarns and textile constructions and are particularly valuable as soilresistant lubricants for carpeting.

Some of the products of the invention, as well as alkali metal salts thereof, exhibit surface active properties, making them suitable as wetting or re-wetting agents and detergents.

EXAMPLE 1 N,N-di-(stearamidethyl)-adipamic acid In a 1 liter 3-neck flask fitted with stirrer, thermometer, Dean-Stark tube with condenser, and nitrogen inlet tube, a mixture of 304 g. (0.50 mol) of N,N-(iminodiethylene) bis-stearamide and 73 g. (0.50 mol) of adipic acid was heated to 200 C. with vigorous stirring under nitrogen atmosphere. After heating at 200 C. to 205 C. for one and one-half hours, 8.9 g. of water had collected in the Dean-Stark tube and the evolution of water had ceased.

After cooling to about 85 C., the clear, pale orange product was poured out in a porcelain dish to cool. The hard, wax-like solid, which was pale tan in color, had a neutral equivalent of 705 (theoreticalmol. wt. 735) and a melting point (flow) of 76 C. to 79 C.

.This product was found to be exceptionally well suited to the preparation of non-soiling lubricants for textile carpets.

*tion in each case and drying, produced a substantial im- For this purpose, a paste of the potassium salt of the product was prepared by adding 73.6 g. of the molten amide-acid in 12 g. of diethylene glycol to a solution of 8.0 g. of potassium hydroxide in 200 g. of water at 65 C. with constant agitation. The resulting homogeneous gel formed a soft paste on cooling which was easily dispersible in warm water.

Application of 1% of this anionic paste to viscose carpeting by spraying followed by drying afiorded excellent anti-soil properties.

EXAMPLE 2 N,N-di-(stearamid0ethyl) -azelaamic acid In a 2 liter 3-neck flask fitted with stirrer, thermometer, dropping funnel, Dean-Stark tube with condenser, and nitrogen inlet tube, 810 g. (3.0 mols) of T.P. stearic acid (neut. equiv. 270) was heated to C. under an atmosphere of nitrogen. Diethylenetriamine g.; 1.5 mols) was added dropwise over one-half hour while allowing the temperature to rise to 160 C; The mixture was then heated at C. to C. until 55 g. of water had collected in the Dean-Stark tube. After cooling, the resulting N,N-(iminodiethylene)bis-stearamide to 175 C., 285 g. (1.5 mols) of azelaic acid (neut. equiv. 95) was added as fast as possible. The temperature was then raised to 200 C. to 205 C. and maintained until the evolution of water ceased; 27 g. of water was collected in five hours. Removal of the water from the reaction vessel to the Dean-Stark tube was facilitated by a very slow stream of nitrogen throughout. The cooled product was a pale tan-colored, hard, wax-like solid; weight, 1168 g. The neutral equivalent was 729 compared to a theoretical value of 777 and the melting point (flow) was 74 C. to 77 C. The amine content, as determined by titration, was 0.000175 mol per gram.

The application of 0.5% of the potassium salt of this product to cotton fabric by padding from an aqueous solution of 0.75% concentration resulted in an exceptionally soft handle. The light-fastness of the direct dyed cotton was not impaired by the softening treatment.

EXAMPLE 3 N ,N -di-(stearam idoethyl -adipamic acid The procedure of Example 2 was followed with the exception that 304 g. (1.5 mols) of sebacic acid (neut. equiv. 101) was employed in place of the azelaic acid. The resulting cream-colored, brittle solid weighed 1190 g.; neutral equivalent, 748 (theoretical mol. wt. 791); melting point (flow) 74 C. to 79 C. The amine content, as determined by titration, was 0.00016 mol per gram. 7

A paste of the potassium salt of this product was prepared by adding a mixture of 79 g. of the amido acid in 39 g. of diethylene glycol at about 105 C. to 196 g. of 3.7% aqueous potassium hydroxide solution at about 50 C. with agitation. On cooling, a nearly colorles s, homogeneous paste was obtained. One percent of this anionic paste, applied to swatches of wool, cotton, Dacron (polyethylene terephthalate) and Orlon (an acrylonitrile polymer) by padding from an aqueous soluprovement inthe softness of the fabrics. Fabrics treated in this manner exhibited excellent resistance to scorching and yellowing andshowed essentially no chlorine retention.

EXAMPLE 5 N,N-di-(caprylamidoethyl) -sebacamic acid EXAMPLE 6 N,N-di-(oleamidoethyl)-azelaamic acid Following the process of Example 2, the stearic acid was replaced by 845 g. (3.0 mols) of commercial oleic acid. (iodine value 88). The resulting clear, viscous, red liquid had a neutral equivalent of 765 (theoretical mol. wt., 802) and an amine content of 0.00013 mol per gram.

EXAMPLE 7 N ,N -di- (stearam ia'opropyl -adipamic acid The procedure of Example 2 was followed with the exception that 202 g. (1.5 mols) of 3,3'-iminobispropylamine and 219 g. (1.5 mols) of adipic acid were used in place of the diethylenetriamine and azelaic acid, respectively. The product was a pale tan-colored, hard, waxline solid exhibiting a neutral equivalent of 694 (theoretical value, 763) and a melting point (flow) of 64 C. to 68 C.

EXAMPLE 8 N-stearamidoethyl-N-caproamidoethyl-aa'ipamic acid In a 2 liter 3-neck flask fitted with stirrer, thermometer, dropping funnel, Dean-Stark tube with condenser, and nitrogen inlet tube, 405 g. (1.5 mols) of T.P. stearic acid (neut. equiv. 270) was heated to 60 C. under an atmosphere of nitrogen. Diethylenetriamine (160 g.; 1.5 mols) was added over about six minutes, allowing the temperature to rise to 128 C. The mixture was then heated at about 175 C. until 27 g, of water had been evolved, after which the temperature was rapidly reduced to 160 C., and 174 g. (1.5 mols) of caproic acid (neut. equiv. 116) was added over about six minutes. After heating the orange liquid at 180 C. to 185 C. for one hour, 28.5 g. of water had collected in the Dean- Stark tube and the free fatty acid had dropped to 3.1%. After cooling the reaction mixture to about 125 C., 219 g. (1.5 mols) of adipic acid was added rapidly, The temperature was then raised to about 200 C. and maintained until the evolution of water ceased. The resulting product was a sticky, wax-like solid which had a neutral equivalent of 596 (theoretical mol. wt., 582).

EXAMPLE 9 N,N-di-(stearamidoisopropyl)sebacamic acid Following the procedure of Example 1, a mixture of 320 g. (0.50 mol) of the distearamide of diisop-ropylene triamine and 100 g. (0.50 mol) of sebacic acid was heated at 195 C. to 200 C. until the evolution of water ceased; 9.4 g. was collected. The resulting product was a brittle, Wax-like solid.

EXAMPLE 10 N,N-di-(slearamidoethyl)-adipamic acid The procedure of Example 1 was followed except that 70 g. of xylene was added to the reaction mixture as an azeotroping agent. The mixture was allowed to reflux gently until 10 g. of water had collected in the Dean- Stark tube. After removing the xylene by distillation under vacuum, the hard, wax-like solid had a neutral equivalent of 685.

We claim:

1. Compounds having the formula:

where R and R are aliphatic hydrocarbon radicals having at least 5 carbon atoms, R and R are selected from the group consisting of -CH CH -CH CH CH and and n is an integer from 4 to 8 inclusive.

2. Compounds according to claim 1 wherein R and R3 are CH CH 3. Compounds according to claim 1 wherein R and R3 are '-CH CH CHg--.

4. Compounds according to claim 1 wherein R and R are 5. Compounds according to claim 1 wherein R and R are aliphatic hydrocarbon radicals having 5 to 17 carbon atoms.

6. Compounds according to claim 1 wherein R and R are saturated aliphatic hydrocarbon radicals having 5 to 17 carbon atoms.

7. Compounds according to claim 1 wherein R and R are ethylenically unsaturated aliphatic hydrocarbon radicals.

8. A process of making the compounds of claim 1 comprising reacting one mol of a dialkylene triamine having 2 to 3 carbon atoms in the alkylene group with two mols of a fatty acid having at least 6 carbon atoms to form a diamide and reacting the diamide thus formed with one mol of an alkylene dicarboxylic acid having 4 to 8 carbon atoms in the alkylene group to form a half amide of the dicarboxylic acid.

9. A method of imparting anti-soiling properties to textile fibers comprising applying to the textile fibers the compound of claim 1.

10. A method according to claim 9 wherein the compound is applied in the form of an aqueous dispersion and the textile fibers are thereafter dried.

11. A method according to claim 10 wherein the fibers are cellulosic fibers.

12. A method according to claim 10 wherein the fibers are polyester fibers.

13. A method according to claim 10 wherein the fibers are polyamide fibers.

14. A method according to claim 10 wherein the fibers are wool fibers.

15. Textile fibers having improved anti-soiling properties coated with the product of claim 1.

16. A process of making a half amide of a dicarboxylic acid comprising reacting one mol of an amide having the formula:

wherein R and R are aliphatic hydrocarbon radicals .from the group consisting of -CH CH 4 8 having 5 to 17 carbon atoms and R and R are selected References Cited in the file of this patent UNITED STATES 15ATENTS -CH2CH2CH2 I 5 2,609,381 Goldstem et a1. Sept. 2, 1952 cm FOREIGN PATENTS with an alkylene dicarboxylic acid having 4 to 8 carbon 738,379 Great Britain Oct. 12, 1955 atoms in the alkylene group.

Claims (2)

1. COMPOUNDS HAVING THE FORMULA:

9. A METHOD OF IMPARTING ANTI-SOILING PROPERTIES TO TEXTILES FIBERS COMPRISING APPLYING TO THE TEXTILE FIBERS THE COMPOUND OF CLAIM 1.