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Publication numberUS2344259 A
Publication typeGrant
Publication dateMar 14, 1944
Filing dateApr 14, 1941
Priority dateApr 14, 1941
Publication numberUS 2344259 A, US 2344259A, US-A-2344259, US2344259 A, US2344259A
InventorsDavis Mcleod Earle, Morgan Willard L
Original AssigneeArnold Hoffman & Co Inc
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Alkali salts of fatty carbamino compounds
US 2344259 A
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Description  (OCR text may contain errors)

Patented Mar. 14, 1944 2,344,259 mu SALTS or FATTY cn'nmumo COMPOUND Willard L. Morgan, Edgewood, and Earle Davis McLeod, Rumford, R. 1., assignors to Arnold, Hoffman & Co. Incorporated, a corporation of Rhode Island No Drawing. Application April 14, 1941,

' Serial No. 388,558

26 Claims.

This invention relates to salts of condensation products which are suitable as assistants for the modification of the properties of textile fibers, which assistants cannot be removed by washing or dry cleaning and which have no deleterious efiects on the fastness to light of colored fabrics. Many materials have been used as textile assistants for altering the softness, the easy wetting or the repellency of textile fibers, but each has been subject to some fault, thus tallows, oils or sulphonated tallows have long been used in the finshing of textiles for softening effects, but these effects are not permanent and are lost the first time the goods are washed. These materials also suffer from rancidity or objectionable odor development in the goods. Fatty alcohols and simple aliphatic amides, which do not become rancid, have also been used as textile softeners, but these also wash out.

It is known that the quaternary salts of aliphatic amides which are formed by the reaction of aliphatic amides with acids as well as similar aliphatic quatemaries produced from pyridines or the betaines and aliphatic imidazoles solubilized as salts by treatment with acids are useful as textile modifying agents, and in particular as textile softeners, particularly as these materials alter or soften the fibers and cannot thereafter be washed off. In a similar way quaternary salts have been formed from these various aliphatic amino bases by reaction of solubilizing acids, such as, acetic, hydrochloric, etc., and also by treatment with alkylating agents, such as diethyl sulphate, ethyl chloride or chloracetic acid. The quaternary salts of fatty acid condensations with aliphatic polyamines have particularly been used for these purposes.

In copending application, Serial No. 351,200

filed August 3, 1940, Patent No. 2,304,369 Decemher 8, 1942, by the joint inventors of this case there has been set out new aliphatic amino condensation products particularly characterized in that the products are substituted ureas, guanidines, biurets, guanyl ureas, and diguanidines of high molecular weight, in which each of th terminal carbamyl nitrogens has been substituted through linkages with a polyamino acid amide. We have found that these compounds are particularly useful for the modification of and particularly for imparting softness to textile fibers. Fabrics treated with these materials in only very small amounts showed marked softening with a maximum resistance to washing and dry cleaning and a complete freedom from any tendencies to either become rancid or yellow under heat or light in storage.

As a consequence of the marked advantages secured with the aliphatic amino quaternarie on textiles, their use has been very extensive, but it has been found unfortunately when used on printed or colored cloth that all of these aliphatic amino compounds have caused a very serious alteration in the light fastness of the colored textiles. In the case of commercial colors or direct dyestuffs and the basic type dyestuffs these eflects have been particularly severe and in many cases the resistance to fading is reduced to practically nil. Direct dyestuffs are perhaps used more than any other dyestufl! in the cotton trades because of their general brightness and generally good resistance to light fading. The serious reduction in light fastness arising with the various types of aliphatic amino quaternary substances is also found with acid type dyestuffs which are the main type used on wool fabrics. Other types of dyestuffs, such as, rapidogens, indigosols and vats, as well as acetate colors are aflected in many cases although not universally as it appears to be particularly true in the direct, basic, and acid colors.

While there is some slight variation in the deleterious effects of the various types of aliphatic amino quaternary substances on dyestuffs, none of these is in any way completely fre of the difficulty and the use of any of them on colored goods constitutes a considerable trade hazard and has been the source of loss in the textile trade and unsatisfaction to the consumer employing the goods because of a very poor light resistance. As an example, a fabric dyed with Diphenyl Blue Green BL, directv dyestuff, E. I. du Pont de Nemours, which readily gives a 40-hour fading test in an ultraviolet fadeometer or resists a three months outdoor service without any evidence of fading will after treatment in a solution or less of any of the aliphatic amino quaternaries described show evidence of failure within a five hour fading test, and at forty hours the dyestufl is ahnost completely faded out.

It is an object of this invention to provide a new class of textile assistants, such as, wetting, washing, softening, lubricating and waterproofing agents.

It is also an object of this invention to provide a new class of textile assistants, such as, wetting, washing, softening, lubricating. nd waterproofing agentshaving improved properties and characterized by not having any deleterious fading effect employed on the colored cloth.

A still further object of our invention is to describe new salts of fatty'carbamino compounds which may be used to lubricate either yarnsfor fabrics so as to make the mechanical flow of these in weaving or sewing proceed smoothly.

We havefound that the deleterious effects on fading of dyestuffs by the ordinary aliphatic amino quaternary acid salts which have generally been described as cationic active materials are due to their reaction with the dyestuif and the formation of new dyestuffs of completely altered and practically invariably decreased fading resistance to light. New dyestuffs are formed by reaction of the quaternary nitrogen acid salts with dyestuffs carrying sulphonic acid groups, which is particularly true for most all direct dyestufls and acid type dyestuffs. In these dyestuifs the large color group carrying the sulphonic acid group forms a negative ion in water solution, and this negative ion reacts with the large positive substituted ammonium quaternary ion or cation formed from the quaternary compounds when they are dissolved in water. The cation carries practically all of the organic compound attached to the'pentavalent nitrogen, the entire group carrying a positive charge and only the acid radical coming from the solubilizing acid goes into the negative ion formed, thus, we may typify the reaction of the dyestuil' with a quaternary aliphatic amino acid salt by the following reactions, where D is the large organic dyestuff complex carrying the sulphonic acid group. The pentavalent nitrogen or quaternary compound is indicated as carrying three substituent organic radicals (R) and a hydrogen which latter arises from the solubilizing acid. The other radical indicated by A hooked to the pentavalent nitrogen arises from the solubilizing acid, which, for instance, may be acetic acid in which case A is an acetate radical.

- (DSOQ' Na+ That the last reaction does occur, can readily be seen when solutions of 'direct dyestuffs and of cation active materials are mixed as there is an immediate co-precipitation resulting in the formation of a new dyestulf which is oil soluble. Oil soluble dyes in general have always been noted for very poor light fastness.

The textile modifying agents proposed by this invention are new alkali salts of fatty carbamino compounds characterized by the fact that the fatty carbamino acid group forms in water a large negative ion. In these compounds nitroen is only found in a trivalent condition and there are no pentavalent or quaternary nitrogens resent. The new compounds which we propose to use as textile modifying agents and softening agents are further characterized by the presence of one or more groups of the following types:

As will be seen these are amide and amidine groups in which the acid hydrogen attached to the nitrogen has been replaced by an alkali base indicated by Me, such as, sodium or potassium. We have found that in fatty carbamide and fatty guanidine compounds which carry the respective 1 IH ..Q IIQ that the hydrogen is a weak acidic hydrogen which can readily be replaced by alkalies when these compounds are treated with strong alkalies. The fatty carbamide and fatty guanidine compounds may also contain other aliphatic amido groups which can be reacted in the same way with strong alkalies.

We may make our new alkali salts of fatty carbamides and guanidines by reacting a wide range of fatty carbamide and fatty guanidine types of substances with strong alkalies.

The condensation products proposed by this invention are the alkali salts of substituted ureas, guanidines, biurets, guanyl ureas, and diguanidines of high molecular weight, in which each of the terminal carbamyl nitrogens has been substituted through linkages with a polyamino acid amide.

These compounds ar readily prepared by reacting the carbamyl derivatives, such as, ureas,

- guanidine salts, biurets, diguanidines and guanyl ureas with the condensation products secured by reacting aliphatic polyamines and acids or acid esters or acid chlorides and thereafter reacting with strong alkalies.

As suitable acids for condensing with the polyamines, we prefer those containing six or more carbons and preferably saturated aliphatic acids. such as, lauric, stearic, palm oil acids, although we may use the unsaturated or substituted fatty acids, such as, rincinoleic, oleic, sebacic or chlorostearlc, or the cycloaliphatic, aromatic, Or resin acids may also be used, such as, naphthenic, benzoic, creositinic, and abietic or the resin acid secured from rosin and maleic anhydride. These acids may be condensed with any of the aliphatic polyamines or substituted polyamines, such as, ethylene diamine, diethylene triamine, triethylene tetramine, -tetraethylene pentamine, hexa methylene diamine, hydroxy ethyl ethylene diamine, ethyl ethylene diamine, 2,2,dimethyl-l,3,- diamino propane, 1,3,diamino iso propanol, beta beta diamino diethyl ether, and beta beta diamino diethyl thioether.

The alkali salts of the substituted ureas, biurets, guanidines, diguanidines or guanyl ureas of high molecular weight proposed by this invention are of the following general formula:

bility in water. In general we find the solubility acid chloride, or ester may be used as a source to introduce this radical into our condensation products as will be shown later. Re is used to indicate hydrocarbon groups of similar type to R1 and in a given compound may be identical with R1 or be secured from a differentacid.

In the formula Ra, Ra, B4, and Rs may, any-or all of them, represent an alkali such as sodium or potassium. Where one of these groups is occupied by a sodium or potassium atom, the remaining three may represent either hydrogen,

' a simple alkyl of less than five carbons or a similar hydroxy alkyl radical, such as, a beta ethanol group and Re and R4 may also represent alternatively a second acid amide group derived from an acid'and a polyamide.

The chemical groups represented by D1 and D2 may be oxygen in the case of the ureas, or imido (=NH) with the guanidines. The letter g represents a small whole number ranging from Oto 3 andwhileDi andDzmaybethesameas in the biurets they may be different as in the guanyl ureas.

Depending on the nature of the aliphatic polyamine used in the condensation with the organic acids, the letter A is used to represent either an amino (NH)- group, a simple alkyl or alkylol substituted amino of less than five caror oxygen or sulphur. The figures, f. .i, e, l, m, and t represent small whole integers, ,f and 1 varying from 1 to 6, e and l from O to 6, and m and it from 1 to 6 and any of the hydrogens in the CH1 groups may be substituted by a simple alkyl or a hydroxyl group.

The alkali salts of the fatty carbamino compounds of this invention are readily prepared by first condensing equivalent molal quantities of the organic acids and polyamines by heating at temperatures from 130 to 200 C. until the reaction is complete as shown by the loss of one molecule of water. The mix is then cooled back to 180 and /2 mol or more of the urea or other carbamyl derivative added. Ammonia is rapidly liberated as the urea becomes substituted, the temperatures being held between 170 and 200 C. The molten mass is cooled down to below 100 C. and while still molten is mixed with the strong alkali solution of caustic soda or potassium hydroxide. Further water is then immediately stirred in in order to secure soap-like pastes which can thereafter be diluted with further water at the time these materials have to be applied to the textiles. Other means of converting the basic organic fatty carbamino compounds into their alkali salts will be evident in the examples detailed hereafter.

The linking by urea or other carbamyl compounds of two or more acid polyamino amide groups results in products of very large molecular weight and the alkali salts of these compounds are found to show high substantivity to various textile fibers, such as, cotton, viscose, cellulose acetate, linen, jute, etc., and to give textile treatments which are permanent to washing and dry cleaning. This marked substantivity is found to arise largely from the presence of the urea 0! other similar carbamyl groups in such high molecular weight products. The formation of the alkali salts makes the basic organic compounds soluble in water. Such large molecules which are desirable for substantivity are inclined to be poorly soluble but by the formation of our alkali salts by treating the original condensates with strong alkalies we are able to increase their solupresent in the original fatty condensates are weak acids and in general the weak acidic hydrogen reacts readily only with the strong alkalies, such as, sodium and potassium hydroxide. However, where the organic acid group present is not too larg or, for instance, contains twelve carbons or less, such as, in the lauric compounds the water solubility of the initial organic condensates is considerable and in these cases we may form alkali salts between these bases and weaker alkalies, such as, ammonia or the various alkylol amines or alkyl polyamines such, for instance, as monoethanol amine or diethylene triamine. In general, then we may replace the sodium or potassium hydroxide by these materials and form the corresponding ammonium and amine salts, but, in general, we prefer to use the stronger sodium and potassium hydroxide. As the fatty carbamino compounds are all very weak acids, the alkali salts of these compounds all show an alkaline reaction in water solution. In some cases our alkaline salts of the fatty carbamino compounds can be made by mixing with strongly alkaline salts which provide free alkalies when dissolved in water. Examples of this type are soaps and the sodium salts of sulphonated alkylated biphenyl compounds.

It is apparent that by reason of the large molecular weight of our fatty carbamino compounds the actual amount of alkali needed to convert these into the alkali salts is a relatively small amount as would be apparent in the examples detailed hereafter. Our new alkali salts of fatty carbamino compounds possess marked emulsifying properties and it is possible to readily emulsify oils or waxes in pastes of these materials. These give very stable emulsions when diluted with water. In fact, we find that our alkali salts will frequently emulsify considerable quantities of the fatty carbamino compound bases which have not been converted into the alkali salts, thus, making it possible to use less than molal quantities for the securing of apparently water soluble or at least stable emulsions of these products. Any water soluble compounds, such as, hygroscopic agents, for example, diethylene glycol, dextrose, or urea can of course be added directly to the water pastes of our new alkali salts where it is desired to use these on textiles in conjunction with the new textile modifying agents.

As can be seen from the nature of our general formula, there are not present -in any of our new substantive textile treating agents any pentavalent or quaternary nitrogens and it is apparent that our new alkali salts when dissolved in water ionize in a completely different way from the quaternary or cation active materials in that our products ionize into a positive alkali cation and a large organic ion which is charged with a negative charge. Since the dyestufl ionizes in a similar way there is no tendency for negative ions of our textile treating agents to combine with the negative ions of the dyestuffs, and the nature of the original dyestufl is completely preserved;

'thus, it is found that when our new softeners and other textile modifying agents are put onto dyed cloth irrespective of whether the dyestuff used on the cloth is direct dyestuffs, acid dyestuffs,

vats, indigosols, rapidogens or other types of dyestuffs, the resistance to fading on exposure to light is found to be the same as that exhibited to yarns or textile constructions or we may apply them to increase the rewetting or absorbability of a cloth or conversely in some cases we may apply them for waterproofing effects, all of which will be apparent in the examples hereafter described. Many of our compounds are also useful as detergents inasmuch as many of the products show distinct soap-like characteristics in their physical natures and operate very satisfactorily as cleaning agents for the washing of textiles and other materials.

We have found that the sensitiveness to oxidation and to heat or light of the acid polyamino amide condensations and other proposed nitrogen containing textile assistants which results in yellowing either in processing, drying, storage, or use of the treated fabrics is mainly caused by the presence of primary amino or NH: groups in the compounds and to a much lesser extent by secondary amino (NH)-- groups. It is the primary amino group left in the acid polyamine amide condensations which is reacted upon by the urea or other carbamyl compound and removed during the formation of our substituted ureas, and we are thus able to secure compounds free of these difliculties which-had checked technical use. Likewise, the urea and other carbamyl compounds will react with and eliminate secondary amino groups and the yellowing arising from such groups and it is an alternative under this invention to use sufficient urea or other carbamyl compound to combine with all the primary and secondary amino groups in the acid polyamine amide, as well as merely the terminal groups as shown in the general formula already given. The resistance to scorching under heat is also found to be lowered to some degree by the use of unsaturated acids as the source of R1 and Re and while we may use them in many types of application, for products of maximum resistance we prefer the use of the saturated fatty acids.

The invention will be further illustrated, but is not limited by the following examples in which the quantities are stated in parts by weight:

Example 1 To 92.25 parts (2 mols) of a polyalkyl amin acid amide of formula,

made by condensing equimolal quantities of stearic acid and diethylene triamine, were added 7% parts (1 mol) of urea at 185 C. and thebelow 100 C. were added 40 parts (1 mol) of solid sodium hydroxide as a 50% solution. The mass was stirred well and hot water stirred in to form a creamy paste of about 20% SOULS. This stock paste may then be further diluted at the time of use to give solutions containing /8 to 1% solids and such solutions may be used for treating textile yarns' whereupon after drying the yarns will be found to be softened, that the softener is wash resistant, and further that the yarns will dye deeper and better shades. The dyed yarns show no greater tendency to fade on exposure to sunlight or ultraviolet light than similarly dyed yarns not treated with the softener.

The water soluble sodium salt of the fatty carbamino compound produced and used as a softener in this example is of the following formula. Its water solutions show an alkaline pH of 10.9.

0 CnHu- -N-CHaCPbNH-CHiCHr-NH Example 2 aqueous solutions of this product show a pH of We may also mix the'initial condensate of Example 2 with strong alkalinesalts which provide free alkali in water solution and utilize this free alkali to solubilize our condensates as the alkali salts, for example, salts of very weak acids. such as, the alkali salts of sulphonated alkylated biphenyl compounds, for example, the sodium salt of dibutyl-ortho-hydroxyl-biphenyl-disulphonic acid, to the extent of 10 parts may be mixed with 30 parts of the above condensate and 60 parts of water to make a stock paste of approximately pH 9.5. This paste may be diluted with further water at the time of use and applied'as a 1% solids solution to x 80 cotton cloth to give a very soft handle and a finish which ishighly water absorbent and suitable for further treatment in Sanforizing" and preshrinking operations.

Example 4 To 5'7 parts (2 mols) of a polyalkyl amino acid amide of formula,

made by condensing equimolal quantities of lauric acid and diethylene triamine were added six parts (1 mol) of urea at 185 C. and the temperature raised to 190' C., during which time the acid amide further condensed with the evolutionof ammonia to give a light colored condensate. To 596 parts (1 moi) of the above condensate, which at room temperatures is a heavy semiliquid material, were added 70 parts of ammonium hydroxide (2 mols) as a 28% solution. The

mass was stirred well and hot water added to form a creamy paste of 25% solids. This stock piste can then be further diluted at the time of use to give solutions containing. Y. of 1% solids and such solutions can be used for treating rayon yarns whereupon after drying the yarns will be found to be softened, that the softener is wash resistant, and further that the yarns dye deeper and better shades. The dyed yarns show no greater tendency to fade on exposure to sunlight.

or ultraviolet light than similarly dyed yarns not treated withthe softener. The alkali salts By reacting 57 parts (2 mols) of a poly aikyl amino acid amide used in Example 4 with 12 parts (2 mols) of urea, we are able to secure a product which is completely heat resistant and does notshow any yellowing tendency under hot ironing oftreated cloths. The semi-liquid condensate at rooms temperatures made in this way can be reacted with 121 parts (2 mols) of monoethanolamine to yield a water-soluble compound. The product may be used directly without dilution with water or may be used at suitable stren ths, such as. 5 or for the oiling or lubricating of rayon and cotton yarns. For such purposes it is found to be very satisfactory as it permits the easy flow of the yarns in the machines in the twisting and combing operations and at the same time prevents any development of static during these operations. The yarns also Show a very nice, pleasing, soft handle and in the case of colored yarns the fading resistance is uneflected by the use of this lubricant.

Example 6 60 parts ,u mol) of the condensate of sebacic acid and 'diethyiene triamine of formula,

urea so that two mols and even three mols were .condensed, thus eliminating all secondary and primary amino groups, gave a product'which was heat resistant and easily soluble in strong alkalies, such as, potassiumhydroxide by adding 56 parts (1 mol) of potassium hydroxide as a 45% solution to 398 parts of the above condensate at temperatures below 100 C. There was formed a watersoluble potash salt which could be further diluted with water to form any strength solution desired. Etrample 7 333 parts of abietic acid and 122 parts of tetraethylene pentamine were heated until one moi of water had been distilled ofl. The product contained a primary amino and several secondary amino groups as shown in the formula,

0 cuHa-JL-NmcnmNmcnmNnwmbNmcnomni While this product yellows cloth very badly when ironed with a hot iron, it was found that on treating it further by heating 60 parts (2 mols) with 14.1 parts (4 mols) of urea at 185 C. and raising the temperature to 190 C. that a new product was secured which showed a melting point of -75 C: An alkali salt of this new product may be considered to be of the following formula or a polymer of this formula,

i i cuHa-tL-N-(om)PN(cm)iN-(0m),-N (cm)|-N I x and is readily soluble in alkalies in that there are four acid hydrogens present. From one to four mols of potassium hydroxide may be reacted to form the alkali salts which are water soluble.

One mol of the condensate of rincinolelc acid and hydroxy ethyl ethylene diamine is further condensed with /2 mol of urea at 185 C. with the temperatures then being raised to 190 C. The condensate is a dark brown solid melting at 70 to 0., which is easily solubilized in water by treatment with strong alkalies, such as, potassium hydroxide using, for example, two molal quantities.

Example 9 (2 mols) of the condensate of stearic acid and hydroxy ethyl ethylene diamine of formula.

0 CnHu-(E-NH(CH:)r-NHCH:CH:OH are further condensed with 82.! parts (1 mol) of guanidine carbonate by slowly adding the I carbonate at C. and raising the temperature to C. The product obtained melted at 68-78 0., was soluble in water after treatment with strong alkalies, such as, sodium hydroxide, for example, 76.4 parts (1 mol) of the above guanidine condensate were stirred with 8 parts (2 mols) of solid sodium hydroxide as a 50% solution which was further diluted to give a white paste of approximately 25%. This paste when applied to dyed fabrics at a strength of 2 lbs. in 50 gallons gave a very soft handle which was resistant to washing, and the goods would not discolor or develop any odors either when heated, exposed to light or stored for months. The compound further had no effect on the light fastness of the dyestuff used on the cloth. The formula of the product formed by the reaction of two mols of caustic soda with the guanidine condensate was,

8.1 /2 mol) parts of urea are introduced into 100 parts of a polyalkyl amino acid amide made by condensing 284 parts of stearic acid in 104 parts hydroxy ethyl ethylene diamine at a temperature of 160 C. of the following formula,

at 185 C. and the temperature was raised to 190 C. The compound obtained was a light yellow product melting at 60-65 C. with a formula as follows:

3.parts (V2 mol) of glacial acetic acid were added to 76.6 (1 mol) of the above urea condensate at The acid salt was then diluted with hot water and to the heavy paste thus formed 8.4 parts (1.5 mols) of solid potassium hydroxide as a 14% solution were slowly added, during which addition the acid salt of the above urea condensate was decomposed and the insoluble base material precipitated and thereafter converted into the water soluble potassium salt of the following formula,

Example 11 16.2 parts (1 mol) of urea are introduced into 100 parts of a polyalkyl amino acid amide made by condensing 284 parts of stearic acid and 104 parts of hydroxy ethyl ethylene diamine at a temperature of C. The urea condensation was carried out ata temperature of C. and the temperature raised to C. The compound obtained was a light yellow, waxy solid melting at 65-'l0 C. and possessing the following formula;

The biuret condensate indicated in the above formula may be solubilized by forming the alkali salt by the addition of 2 parts by weight of potassium oleate soap to one part of the condensate, in which case the compound is made water'soluble by the alkali obtained from the soap by hydrolysis in water solutions. For exmile, 8 parts by weight of the molten condensate may be added to 32 parts of a 50% potassium oleate soap solution, and the mixture stirred at 70-80 C., during which time the biuret base will solubilize and the paste obtained may be further diluted with hot water to approximately 25% solids. This paste when used in A; to solids as a detergent will impart a permanent softness to the fabric, which is resistant to washing with no subsequent effect on the light fastness of any dyestufi which might be used. This detergent may be applied fort'hese purposes either to yarns or to cloth either in kiering operations or in washing operations during the finishing of textiles such as after printin Example 12 16.6 parts 0/: mol) of biuret were slowly added at 185 C. to the same polyalkyl amino acid amideas in Example 10 and the temperature raised to 190 C. The waxy compound obtained was light amber melting at 65-70 C. and was similar in characteristics to the biuret condensate obtained in Example 11 which was formed by the addition of one mol of urea. By adding 3 3.2 parts (1 mol) of biuret to the same polyalkyl amino acid amide as in Example 10, the biuret linkage between the secondary amino groups yields a light yellow compound melting at 95-100" C. with a similar structure except that the biuret linkage is extended to:

Both biuret compounds are light and heat resistant.

The biuret condensates thus formed may be easily solubilized by the addition of strong alkalies; for example, 80.9 parts (1 mol) of the simple biuret condensate may be solubilized by the addition of 4.0 parts (1 mol) of solid sodium hydroxide as a 50% solution and the heavy paste thus formed further diluted with water to approximately 30% strength. We may also emulsify with the alkali salt ofthe above condensate varied amounts of the non-soluble base. As. for example, to 8.48 parts of the alkali salt may be added as much as 32.36 parts (4 mols) of the non-soluble biuret base and after thorough stirring at a temperature of IO-80 C., the paste thus formed can be further diluted with water. In a similar way the alkali salt of this compound, or of the other compounds illustrated in the various examples, may be used to emulsify oils and waxes. It is used as a softener and $5 to 1% solids solution of the above compound will impart a permanent softness and a water repellency to 60 x 60 cotton cloth or hosiery, which will be resistant to washing, non-yellowing under storage and impart no effect on the light fastness of any dyestuffs which might be used.

Example 13 284 parts (1 mol) of stearic acid are mixed with 90 parts (1 mol) of 1,3 diamino iso propanol and the mixture heated to 160 0., at which point one mol of water is split out. .The temperature is then raised to 185 C. and parts (5% mol) of urea are slowly added and the batch raised to 190 0., during which time mol of ammonia is split off. The product obtained melts at 80-85 C. and when treated with one mol of solid potassium hydroxide becomes water soluble. The potash salt of the urea condensate has the fol,- lowing formula,

and this compound when applied to fabrics imparts a marked softening value and lubricating effect which permits easy passage of the needles in sewing machines. When applied to yarns, it gives a soft lofty handle and lubricates these through the spinning and weaving operations. In addition to this, no efiect on the light fastness of any dyestufl which might be used is obtained.

Emmple 14 74.2 parts of stearic acid were mixed with 27.7 parts diamino neo pentane and the temperature raised to 160 C., during which time one mol of water was distilled off. The temperature was then raised to 180 C. and 7.84 parts of urea was added slowly, during which time ammonia was evolved and the temperature was raised to 190 C. The compound obtained was light yellow and when solubilized by the addition of three mols of solid sodium hydroxide as a 50% solution possessed the following formula:

The heavy paste of the alkali salt thus formed may be diluted with hot water to a white paste containing approximately 30% solids. To 3 parts of this 30% solids paste is added one part by weight of diethylena glycol and the mixture thoroughly mixed. This paste when used in the ratio of 2 to 6lbs. per 50 gallons of water imparts 30.8 parts (2 mols) of the condensate of two mols of stearic acid and one mol of diethylene triamine having the following formula,

were heated to 0. and 1.4 parts 1 moli of urea. were slowly added and the temperature raised to 200 C., during which time ammonia was evolved. The urea condensate obtained was light yellow and was water soluble after treatment with four mols of solid sodium hydroxide as a 50% solution. This alkali salt possessing the formula,

(I) Na Na 0 C|7His--1 i'CH:CH:NCH:CH:-I I-EC"Has =0 0 Cl7n35C- CHSCHt-AI-CHZCHFN--C"H35 Na Na may be further diluted with hot water to give a white creamy paste approximately 35% solids. The above alkali salt when used in a Dyebeck in the ratio of 6 lbs. of this paste per 1200 gallons (02%) of solution imparts a soft handle to fabrics which is resistant to washing and aging, and has no efiect on the resistance to fading of any dyestufif which might be used.

As many apparently widely difl'erent embodiments of this invention may be made without departing from the spirit and scope thereof, it is understood that we do not limit ourselves to the specific embodiments thereof except as defined in the appended claims.

We claim:

1. A substituted carbamyl compound of the following general formula:

where R1 and Re represent hydrocarbon radicals of at least six carbons and in which the carbamyl groups D1 and D2 are selected from the group consisting of oxygen and imido groups, thenumber of which groups being as g ranges from 0 to 3; while in the side chains the letter A represents a material selected from the group consisting of an amino (NH), a simple alkyl or alkylol substituted amino of less than five carbons,

oxygen, and sulphur, and the integers ,f, 7', m,

2. A polyalkyl amino acid amide substituted urea of the following general formula: r R|C--N[(CHLO-r- AIF-(CUHI-N in which at least one of the group R2, R3, R4, and R5, is an alkali metal, and R1 and Rs represent hydrocarbon radicals containing at least six carbon atoms; while in the side chains the letter A represents a material selected from the group consisting of an amino (NH), a simple alkyl substituted amino of less than five carbon atoms, a simple alkylol substituted amino of less than five carbon atoms, oxygen and sulphur; and the integers e, I, m and t each vary from 2 to 6, while i varies from 1 to 6, and lvaries from 0 to 6.

3. The chemical compound having the formula,

CHEM-( JNHCHICHINHCHICHj-NH in which one of the hydrogens attached to an amide nitrogen is replaced by an alkali metal.

4. The chemical compound having the formula,

I in which one of the hydrogens attached to an 6. A polyalkyl amino acid amide substituted biuret of the following general type:

where R1 and Rs represent hydrocarbon radicals containing at least six carbon atoms and are selected from the group consisting of a saturated alkyl group, an unsaturated alkyl group, a cyclic alkyl group, an aryl radical, and a residue from a terpene acid; and in the side chains the letter A represents a material selected from the group consisting of an amino (NH)-, a simple alkyl substituted amino of less than five carbon atoms, a simple alkylol substituted amino of less than five carbon atoms, oxygen, and sulphur; and the integers a, f, m and 1: each vary from 2 to 6, and e and l vary from 0 to 6; and in which at least one of the groups R2, R3, R4 and R5 is an alkali group while the remainder of such groups are selected from the group consisting of hydrogen, a simple aikyl radical of less than five carbon atoms, and a similar hydroxy alkyl radical excepting that R3 and R4 also can be represented by a second acid amide chain derived from an acid and a polyamine.

'7. A polyalkyl amino acid amide substituted guanidlne of the following general type:

where R1 and Rs represent hydrocarbon radicals containing at least six carbon atoms and are selected from the group consisting of a saturated alkyl group, an unsaturated alkyl group, a cyclic alkyl group, an aryl radical, and a. residue from a terpene acid; and in the side chains the letter A represents a material selected from the group consisting of an amino -(NH), a simple alkyl substituted amino of less than five carbon atoms, a simple alkylol substituted amino of less than five carbon atoms, oxygen, and sulphur; and the integers 7', f, m and t each vary from 2 to 6, and e and l vary from 0 to 6; and in which at least one of the groups R2, R3, R4 and R5 is an alkali group while the remainder of such groups are selected from the group consisting of hydrogen, a simple alkyl radical of less than five carbon atoms, and a similar hydroxy alkyl radical excepting that R3 and R4 also can be represented by a second acid amide chain derived from an acid and a polyamine.

8. A substituted carbamyl compound of the following general formula, in which one of the hydrogens attached to an amide nitrogen is replaced by an alkali metal and in which the substituting groups are derived from the polyalkyl amino acid amide secured by reacting dlethylene triamine and a saturated fatty acid of the class CnH2n+1 where n is at least 6, the compound having the following formula:

where the carbamyl groups D1 and D2 are selected from the group consisting of oxygen and an amide, the number of carbamyl groups being as g ranges from 0 to 3.

9. A substituted carbamyl compound of 'the following general formula, in which one of the hydrogens attached to an amide nitrogen is replaced by an alkali metal and in which the substituted groups are derived from the polyalkyl amino acid amides secured by reacting a hydroxy ethyl ethylene diamine and a saturated fatty acid of the class C2H2n+1 where n is at least-6, the compound having the following formula:

where the carbamyl groups D1 and D: are selected from the group consisting of oxygen and an lmide, the number of carbamyl groups being as or ranges from to 3.

'. 10. -A polyalkyl amino acid amide substituted urea of the following type unaifecting the fading characteristics of dyestuffs carried by fabric:

where R1 and Rs represent hydrocarbon radicals containing at least six carbon atoms and are selected from the group consisting of a saturated alkyl group, an unsaturated alkyl group, a cyclic alkyl group, an aryl radical, and a residue from a terpene acid; and in the side chains the letter A represents a material selected from the group consisting of an amino (NH)--, a simple alkyl substituted amino of less than five carbon atoms, a simple alkylol substituted amino of less than five carbon atoms, oxygen, and sulphur; and the integers f, m and t each vary from 2 to 6, and e and l vary from 0 to 6; and in which at least one of the groups Ra, Ra, R4 and R5 is an alkali metal while the remainder of such groups are selected from the group consisting of hydrogen, a simple alkyl radical of less than five carbon atoms, and a similar hydroxy alkyl radical excepting that R: and R4 also can be represented by a second acid amide chain derived from an acid and a polyamine.

11. A polyalkyl amino acid amide substituted urea of the following general type imparting softness to fabrics and unaffecting the fading characteristics of dyestuffs:

where R1 and Rs represent hydrocarbon radicals containing at least six carbon atoms and are selected from the group consisting of a saturated alkyl group, an unsaturated alkyl group, a cyclic alkyl group, an aryl radical, and a residue from a terpene acid; and in the side chains the letter A represents a material selected from the group consisting of an amino (NH)-, a simple alkyl substituted amino of less than five carbon atoms, a simple alkylol substituted amino of less than five carbon atoms, oxygen, and sulphur; and the integers i, f, m and t each vary from 2 to 6, and e and l vary from 0 to 6; and in which at least one of the groups Ra, Ra, R4 and R5 is an alkali metal while the remainder of such groups are selected from the group consisting of hydrogen, a simple alkyl radical of less than five carbon atoms, and a similar hydroxy alkyl radical excepting that R: and R4 also can be represented by a second'acid amide chain derived from an acid and a polyamine.

12. The process for forming a substituted urea compound having the following formula:

CriHsz--NH-CH|CH:-l l'CHiCH;0l1 secured by heating hydroxy ethyl ethylene diamine with stearic acid at to 200 C. and thereafter further reacting at to 200 C. with urea, said substituted urea compound being thereafter reacted with an alkali metal hydroxide solution. v

13. A substituted carbamyl compound of the general formula as described in claim 1 which are free of primary amino (NH:) and sec ondary (NH)-- amino groups. I

14. A process for forming a substituted guanidine compound in which the condensation product of an acid of at least six carbon atoms and a polyamine, said condensation product containing a free primary amino group, is heated at 170 to 200 C. with a guanidine salt and thereafter reacted with an alkali metal hydroxide solution.

15. The process for forming a substituted urea, in which the condensation product of an organic acid of at least six carbon atoms and a polyamine containing a free secondary group is heated at 170 to 200 C. with urea and thereafter reacted with an alkali metal hydroxide solution.

16. The process for forming a substituted carbamyl compounds in which the condensation product of an acid of at least six carbon atoms and a polyamine containing a free secondary amino group is heated at 170 to 200 C. with sufficient of a material selected from the group consisting of urea, biuret, and guanidine carbonate to react with all the amino groups and give a product free of secondary amino groups, and thereafter reacted with an alkali metal hy- QIOXidE solution.

17. A process for forming a substituted biuret in which the condensation product of an acid of at least six carbon atoms and a polyamine, said condensation product containing a free secondary amino group, is heated at 170 to 200 C. with biuret and thereafter reacted with an alkali metal hydroxide solution.

18. A rocess for forming a substituted biuret in which the condensation product of an acid of at least six carbon atoms and a polyamine, said condensation product containing a free secondary amino group, is heated at 170 to 200 C. with .urea and thereafter reacted with an alkali metal hydroxide solution.

19. A process 101' forming a substituted guanidine compound in which the condensation product of an acid of at least six carbon atoms and a polyamine, said condensation product containing a free secondary amino group, is heated at 170 to 200 C. with a guanidine salt and thereafter reacted with an alkali metal hydroxide solution.

20. The process for forming a substituted urea compound, in which the condensation product of an organic acid of at least six carbon atoms and a polyamine containing a free primary group is heated at 1'10 to 200 C. with urea and thereafter reacted with an alkali metal hydroxide solution.

21. The process for forming a substituted urea compound which comprises heating an aliphatic polyamine with an organic acid of at least six carbon atoms at 130 to 200C. to form an amide condensation product containing free amino groups and thereafter reacted with an alkali metal hydroxide solution.

22. The process for forming a substituted-urea compound which comprises heating an aliphatic polyamine with a saturated fatty acid of at least six carbon atoms at 130 to 200 C. to form an amide condensation product containing free amino groups, and thereafter reacted further at 170 to 200 C. with urea, and thereafter reacted with an alkali metal hydroxide solution.

23. The alkali metal compound of a substituted urea of the general formula described in claim 2, in which all free primary amino -(NH2) and secondary --(NH) amino groups have been removed by reaction with urea.

24. The process for forming a substituted carbamyl compound in which the condensation product of an acid of at least six carbon atoms and a polyamine, said condensate product containing a free primary amino group, is heated at 170 to 200 C. with suflicient of a material selected from the group consisting of urea, biuret,

and guanidine carbonate to react with all the amino groups and give a product free of primary amino groups, and thereafter reacted with an alkali metal hydroxide solution.

' 25. A process for forming a substituted biuret in which the condensation product of an acid of

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2622075 *Dec 1, 1947Dec 16, 1952Sandoz LtdPolyamine-cyanamide resins
US2876141 *Nov 5, 1956Mar 3, 1959Atlantic Ind IncAnti-soiling treatment of carpet and rug backing yarns and fibers
US3198597 *Jun 25, 1962Aug 3, 1965Bohme Fettchemie GmbhProcess for bleaching cotton with aqueous alkaline bleaching baths and the products obtained thereby
US6696488Aug 10, 2001Feb 24, 2004The Brigham And Women's Hospital, Inc.Administering protease inhibitor
WO2002014264A2 *Aug 10, 2001Feb 21, 2002Brigham & Womens Hospital(hydroxyethyl)ureas as inhibitors of alzheimer's beta-amyloid production
Classifications
U.S. Classification540/460, 554/51, 564/160, 564/281, 564/38, 564/153, 554/53, 554/57, 564/159, 564/59
International ClassificationC07C275/14, C07C275/00
Cooperative ClassificationC07C275/14
European ClassificationC07C275/14