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Publication numberUS2304369 A
Publication typeGrant
Publication dateDec 8, 1942
Filing dateAug 3, 1940
Priority dateAug 3, 1940
Publication numberUS 2304369 A, US 2304369A, US-A-2304369, US2304369 A, US2304369A
InventorsDavis Mcleod Earle, Morgan Willard L
Original AssigneeArnold Hoffman & Co Inc
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Condensation product
US 2304369 A
Abstract  available in
Images(7)
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Claims  available in
Description  (OCR text may contain errors)

Patented Dec. 8, 1942 CONDENSATION PRODUCT Willard L. Morgan, Edgewood, and Earle Davis McLeod, Rumford, R. 1., assignors to Arnold, Hofiman & Co. Incorporated, a corporation of Rhode Island No Drawing. Application August 3, 1940,

' Serial No. 351,200

24 Claims.

This invention relates to new condensation products which are suitable as assistants for the modification of the properties of textile fibers. 1 Many materials have been used as textile assistants for altering the softness, the easy wet= ting or the water repellency of textile fibers, but each has been subject to some fault; thus, tallows, oils, and sulphonated oils have long been used in the finishing of textiles for softening effacts, but these effects are not permanent and are lost the first time the goods are washed. These materials also suffer from rancidity or ob-, jectionable odor development in the goods on standing. Fatty alcohols have also been used as textile softeners, but these also wash out. Fatty amides and the quaternary salts of these, as well as fatty quaternaries produced from pyridine or the betaines, and fatty imidazoles, have been suggested as textile modifying agentsand in particular as textile softeners. While these materials are mostly fairly expensive and dark in col r,

these substances have shownthe advantage of being somewhat resistant to washing. The.

quaternary salts or fatty acid condensations with aliphatic polyamines have also been used, particularly as these have shown a maximum resistance to washing up to this time. However, each of these types of materials has left considerable to be desired with regards to resistance to washing and as each of these materials has been unstable with respect to heat and oxidation, their use has been attended with the serious difficulty of the cloth being yellowed either by reason of the initially dark color of the product, or

by its decomposition due to the heat used in drying the fabric. Furthermore, goods which have been finished with these materials have frequently during a few months storage become seriously yellow due to the softener being sensitive to oxidation.

It is an object of this invention to provide a new class of textile assistants such as wettin softening, lubricating, waterproofing and mothproofing agents having improved properties.

It is a further object to produce textile assistants which are resistant to heat and to oxidation which permit the finishing and storage of the finished goods for long periods without any yellowing or without any odor development.

As further objects of our invention, we describe condensation products which may be easily appliedfrom aqueous solutions to give finishes on cloth of a maximum softness, which effects are completely permanent to washing and to dry cleaning.

A still further object of our invention is to describe condensation products which maybe used to lubricate either yarns or fabric so as to make the mechanical flow of these in weaving or sewing proceed smoothly.

The condensationrproducts proposed by this invention are substituted ureas, thioureas, guanidines, biurets, guanyl ureas, or diguanidines of high molecular weight in which each of the terminal carbamyl nitrogens has been substituted through linkage with a polyamino acid amide.

These compounds are readily prepared by reacting the carbamyl derivatives, such as, urea,

thiourea, guanidine salts, biuret, diguanidine, or guanyl urea with the condensation products secured from aliphatic polyamines and acids or acid esters or acid chlorides.

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 chlorostearic, or the cycloaliphatic, aromatic, or resin acids may also be used such as naphthenic, benzoic, creositinic, and abieticor 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- 1,3,diamino propane, 1,3,diamino iso propanol, beta beta diamino diethyl ether, and beta beta diamino diethyl thioether.

The condensation products of this invention are substituted ureas, thioureas, biurets, guanidines, diguanidines, or guanyl ureas of high molecular weight of the following general formula:

also represent other hydrocarbon radicals of 6 or more carbons such as a cyclo alkyl, an unsaturated hydrocarbon, an aryl radical, or a residue from a terpene acid, or R1 may carry other substituting groupssuch as hydroxyl, carboxyl or chlorine. In each case the corresponding acid, 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 diflerent acid.

In the formula R2, R3, R4, and Rs may represent either hydrogen, a simple alkyl 01' less than five carbons, or a similar hydroxy alkyl radical such as a beta ethanol group. R3 and R4 may also represent alternatively a second acid amide chain derived from an acid and a polyamine.

The chemical groups indicated by Di and Da may be oxygen in the case of the ureas, sulphur :8 with the thioureas, or imido (=NH) with the guanidines. The letter g represents a small whole number ranging from 0 to 3 and while D1 and D2 may be the same as in the biurets they may be different as in the guanyl ureas.

Depending upon the nature of the aliphatic polyamine used in the condensation with the acids, the letter A is used to represent either an amino -(NH) group, a simple alkyl or alkylol substituted amino of less than flve carbons, such as, -(NC2H5) or -(NC2H4OH), or oxygen, or sulphur. The figures f. 1, e, l, m, and t represent small whole integers, ,f and a varying from 1 to 6, e and I from 0 to 6, and m and t from 1 to 6, and any of the hydrogens in the CH: groups may be substituted by a simple alkyl or a hydroxy group.

The condensation products of this invention are in many cases directly water soluble or water dispersible. In all cases the condensations are readily dissolved aftertreatment with acids, such as, acetic, lactic, boric, oxalic, benzoic, salicylic, iuroic, citric, tartaric, formic, phthalic, succinic, or alkyl naphthalene sulphonlc acids or after reaction with an alkylating agent, such as, ethyl chloride, benzyl chloride, ethylene oxide, ethylene chlorohydrin, or dimethyl sulphate. The salts or alkylated products of our substituted urea condensates are indicated in the general formula given where B represents the acid hydrogen or alkyl groups and X the acid radical or halogen group, while for our primary urea, etc., condensations B and X disappear from the formula.

The condensation products of this invention are readily prepared by heating equimolal quantitles of the acid and polyamine at temperatures from 130 C. 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 C. and one half mol or more of the urea'or other carbamyl derivative added. Ammonia is rapidly liberated as the urea becomes substituted, the temperature being held between 170 C. and 200 C. The product may be cooled and used directly or at temperatures of 80 C. to 140", the various solubilizing acid or alkylating agents may be added in quantities of .2 to .5 mol or more.

The linking by urea or other carbamyl compounds of two or more acid polyamine amide groups results in products of very large molecular weight which are found to show high substantivity to the 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 from the presence of the urea or other similar carbamyl groups in such high molecular weight products. The urea group also increases the solubility in water which is very important since such large molecules which are desirable for substantivity are poorly soluble. Thus, our substituted ureas, although of double the molecular weight, are more soluble than the acid polyamine amide condensations from which they are produced.

We have found that the sensitiveness to oxidation and to heat or light of the acid polyamine 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 or 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 difficulties 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 sumcient urea or other carbamyl compound to combine with all the primary and the 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.

Inasmuch as urea, thiourea, and guanidine are each decomposed readily at temperatures below 180 C. or the reaction temperatures employed, it was impossible to forsee that the large molecule substituted urea condensations would be stable at these temperatures or could be formed. Thus, the heating of urea and fatty acids at C. does not lead to substituted ureas, but decompositions occur yielding only fatty amides as shown in U. S. 1,989,968 and U. S. 2,109,941. In a similar way we have been unable to react urea with simple fatty amides or fatty ethanol amides and we flndthat it is only when we use the amide of an acid and a polyamine containing either or both a primary or secondary amino group that reaction to our substituted ureas can be secured. The condensations go readily and are free of side reactions, thus, leading to full yields of products which do not need to be purified.

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 during which time ammonia was evolved. The

product obtained was 9. buff colored, hard wax melting at 130 C. and was acid soluble. The

product was not heat sensitive and had the following formula:

To 92.25 (2 mols) parts of a polyalkyl amino acid amide of formula stearic acid and diethylene triamine, was added 1 mol (7.5 parts) of urea at 185 C.'and the temperature raised to 190 C., during which time the acid amide further condensed with the evolution of ammonia to give a light colored product melting at 58 C., soluble in water after treatment with benzyl chloride or an acid and of the following formula:

C|1Hu -NHCH|CHz-NHCIhCIh-NH =0 CnHu--NH-CflgCHz-NHCILCHHI IH a This product was somewhat heat sensitive, but

by increasing the urea to 15.0 parts (2 mols) in the above case a product was obtained which was very heat resistant, giving no yellowing under hot ironing of treated cloth and possessed the following formula:

. 0 C 7H35( :NHCHzCHzN-CHCHNH (3:0 (3:0 C11Hss( i-NHCH:CHzI ICHzCHr-I TH 200 parts of lauric'acid may be substituted in either of the above compositions for every 284 parts of stearic acid represented.

Example 3 60 parts (1 mol) of the condensate of sebacic acid and diethylene triamine of formula 0 (J-NBCECBNHCHrCENH, 01

C-NHCHzCHrNHCHzCHrNH:

were further condensed by slowly adding 9.68 parts (1 mol) of urea at 185 C. and the temperature raised to 190 C. during which time ammonia is evolved. The product was asoft mass and was not heat resistant. Further addition of urea so that 2 mols and even three mols were condensed, thus eliminating all secondary and primary amino groups gave a product which was heat resistant and soluble in various acids, such as, acetic or oxalic in equimolal proportion. The quantity of ammonia evolved was the theoretical amounts for reaction with the various amino groups and the amounts of urea used.

meme 4' 333 parts of abietic acid and 192 parts of tetraethylene pentamine were heated under a reflux condenser until 1 mol of water had been distilled off. The product contained a primary amino and several secondary groups as shown in the formula:

and yellowed cloth very badly when ironed with a hot iron. 60 parts (2 mol) of the above condensate were then further condensed with 14.1 parts (4 mols) of urea by slowly adding the urea at 185 C. and raising the temperature to 190 C. The product had a melting point of 70-75" C. and

was acid soluble and gave no discoloration under heat on the cloth.

Example 5 One mol of the condensate of rincinoleic acid and hydroxyethyl ethylene diamine is further condensed with mol of urea at 185 C. with the temperature then being raised to 190 C.

i The product is a dark brown solid melting at -'75 C. which is soluble in water after treatment with an acid.

Example 6 parts (2 mols) of the condensate of stearic acid and hydroxyethyl ethylene diamine of formula:

is further condensed with 32.7 parts (1 mol) of guanidine carbonate by slowly adding the carbonate at C. and raising the temperature to C. The product obtained melted at 68-73 C., was soluble in water after adding acetic acid and applied to cloth at a strength of 2 lbs.in 50 gallons; it gave a very soft handle which was resistant to washing and dry cleaning and the goods would not discolor or take on any odors either when heated, exposed to light, or stored for months. The formula of the product was:

Example 7 143 parts (1 mol) of the condensate of lauric acid and hydroxyethyl ethylene diamine were further condensed with 19 parts /2 mol) of thiourea by addition of the thiourea at 185 C. and raising the temperature to 190 C. The product was a heavy viscous brown liquid which was water soluble directly or after adding acids and had the following formula:

If 38 parts (1 mol) of thiourea is added in the above example, a thiobiuret linkage is formed,

5 which product is a viscous amber colored liquid,

water and acid soluble and has the followin formular.

Both of the products are good mothproofers when applied 12 to 25 lbs. in 50 gallons of water to animal or protein fibers and may be used as such or as their salts such as the acetate fluoride, fluoborate furoate or fluosilicate.

Example 8 8.1 mol) parts of urea are introduced into 100 parts of a polyalkyl amino acid amide made by condensing 284 parts of stearic acid and 104 parts hydroxyethyl ethylene diamine at a temperature of 160 C. with the following formula:

at 185 C. and the temperature raised to 190 C. The product obtained was a light yellow compound, soluble in water after treatment with acids and melting at 60-65 C. with a formula as follows:

If the urea is increased to 16.2 parts (1 mol), a similar compound is obtained except that a biuret linkage l NH is substituted for the Example 9 16.6 parts mol) of biuret are slowly added at 185 C. to the same polyalkyl amino acid amide as in Example 8 and the temperature raised to 190 C. The product was light amber colored melted at 65-70 and was identical with the just previously described product. It has the following formula:

0 CnHaa-kB-NHCHzCHr-N-OHK] HnOH O +=O Cl1 S5 NHCHRCHP'NCHICHIOH By increasing the amount of biuret to 33.2 parts (1 mol) the biuret linkage between the secondary amino groups is lengthened and yields a product which is acid soluble, light in color, melts at -100 and apparently has a similar structure, except that biuret linkage is extended to:

i ..N Both compounds are light and heat resistant.

Example 10 284 parts (1 mol) of stearic acid is mixed with 90 parts (1 mol) of 1,3 diamino iso propanol and the mixture heated to C. at which point 1 mol of water is split out. The temperature is then raised to C. and 30 parts mol) of urea is slowly added and the batch raised to C during which time A; mol of ammonia is split off. The product obtained melts at 80-85 C., is soluble after treatment with acetic acid and is heat resistant. The acetate has the following formula:

This product when applied to fabric imparts in addition to a marked softening value, a lubricating value which permits easy passage of the It has the following formula:

The product is very stable to heat treatment when impregnated on cloth and gives a soft handle.

Example '12 142 parts (2 mols) of stearic acid were mixed with 58% parts (1 mol) of a condensate of hy droxyethyl ethylene diamine and urea, having the formula:

HN-CHaCHzNHCHKJHrOH HN-CHzCHsNHCHiCHrOH This gave a soft handle on cloth and did notdis color under heat on the cloth.

Example 13 30.8 parts (2 mols) of the condensate of two mols of stearic acid and 1 mol of diethylene triamine having the formula:

were heated to 180 C. and 1.4 parts (1 mol) of urea were slowly added and the temperature raised to 200 C., during which time ammonia was evolved:

The product apparently had the following formula:

Two mols of the compound were further condensed with one mol of thiourea at 180 C., during which time ammonia was evolved and a linkage introduced. The product obtained was water soluble after treatment with acids, such as, furoic, hydrofluoroboric, hydrofluoric. Applied to wool or casein fibers, it possessed good mothprooflng qualities and was resistant to washing and dry cleaning.

The ijluosillcate salt had the following'formula:

H HSlFt As many widely different 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 and its acid salts of the following general formula:

wherein R1 and Re represent a hydrocarbon radical of at least six carbons and selected from the group consisting of a saturated alkyl group, an unsaturated alkyl group, a cycloalkyl group, an aryl group, and a terpene acid residue, and in which R2, R3, R4, and R5 represent a material selected from the group consisting of hydrogen, a simple alkyl of less than five carbons, and an alkylol of less than five carbons, and in which R:

and R4 may further represent a second acid polyamide chain, and in which general formula the carbamyl groups D1 and D2 represent a material selected-from, the group consisting of oxygen, sulfur, and imido groups, the number of such 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 amino(NH)-, a

simple alkyl substituted amino of less than five carbons, an alkylol substituted amino of less than five carbons, oxygen, and sulfur; and the integers f and :f vary from 1 to 6, while e and l vary from 0 to 6, and m and t vary from 1 to 6.

2. The reaction product of the carbamyl compounds described in claim 1 with alkylating agents selected from the group consisting of ethyl chloride, ethylene chlorohydrin, ethylene oxide, benzyl chloride, and'dimethyl sulphate.

3. A polyakyl amino acid amide substituted carbamyl compound of the general formula as described in claim 1 which is free of primary amino (NH2) and secondary (NH) amino groups.

4. A process for forming a substituted urea compound in which the condensation product of an organic acid of at least six carbon atomsand a polyamine, said condensation product containing a free primary amino group is chemically combined with urea at C. to 200 C.

5. A process for forming a substituted 8118.111? dine compound in which the condensation product of an organic acid of at least six carbon atoms and a polyamine, said condensation prodnot containing a free primary amino group is chemically combined with a guanidine salt at 170 C. to 200 C.

6. A process for forming a substituted biuret compound in which the condensation product of an organic acid of at least six carbon atoms and a polyamine, said condensation product containing a free primary amino group is chemically combined with a biuret at 170 C. to 200 C..

7. A process for forming a substituted biuret compound in which the condensation product of an organic acid of at least six carbon atoms and a polyamine, said condensation product containing a free primary amino group is chemically combined with urea at 170 C. to 200 C.

8. A process for forming a substituted carbamyl compound in which the condensation product of an organic acid of at least six carbon atoms and a polyamine, said condensation product containing a free primary amino group is chemically combined at 170 C. to 200 C. with sufiicient of a material selected from the group consisting of urea, thiourea, biuret, and guanidine carbonate to chemically combine with all the amino groups and give a product free of a primary amino group.

9. A 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 C. to 200 C. to form an amide condensation product containing free amino groups, and thereafter chemically com-' bining at 170 C. to 200 C. with urea.

10. A 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 C. to 200 C. to form an amide condensation product containing :free amino groups, and thereafter chemically combining at 170 C. to 200 C. with urea, and thereafter solubilizing by adding an acid.

11. A process for forming a substituted carbamyl compound which comprises heating a carbamyl substance which is substituted in each of the terminal nitrogens by alkyl chains carrying amino groups, with acids at 130 C. to 200 C. to form amide linkages at the amino groups on such chains.

12. A new chemical compound having the for- 13. A new chemical compound having the formula:

14. A new chemical compound having the formula:

15. A polyalkyl amino acid amide substituted urea and its acid salts of the following general type:

wherein R1 and Re represent a hydrocarbon radical of at least six carbon atoms and selected from the group consisting of a saturated alkyl group, an unsaturated alkyl group, a cycloalkyl group, an aryl group, and a terpene acid residue, and in which R2, R3, R4 and R5 represent a material selected from the group consisting of hydrogen, a simple alkyl of less than five carbon atoms, and an alkylol of less than five carbon atoms, and in which Ba and R4 may further represent a second acid polyamide chain, while in the side chains the letter A represents a material selected from the group consisting of amino (NH) a simple alkyl substituted amino of less than five carbon atoms, an alkylol substituted amino of less than five carbon atoms, oxygen, and sulfur; and the integers f and 7 vary from 1 to 6, while e and l vary from 0 to 6. and m and t vary from 1 to 6.

16. A polyalkyl amino acid amide substituted biuret and its acid salts of the following general type:

wherein R1 and Rs represent a hydrocarbon radical of at least six carbon atoms and selected from the group consisting of a saturated alkyl group, an unsaturated alkyl group, a cycloalkyl group, an aryl group, and a terpene acid residue, and in which R2, R3, R4 and R5 represent a material selected from the group consisting of hydrogen, a simple alkyl of less than five carbon atoms, and an alkylol of less than five carbon atoms, and in which R3 and R4 may further represent a second acid polyamide chain, while in the side chains the letter A represents a material selected from the group consisting of amino (NH)-, 9. simple alkyl substituted amino of less than'five carbon atoms, an alkylol substituted amino of less than five carbon atoms, oxygen, and the integers I and 7 vary from 1 to 6, while e and Z vary from 0 to 6, and m and t vary from 1 t0 6.

1'7. A polyalkyl amino acid amide ,substituted guanidine and its acid salts of the following general type:

R4 wherein R1 and Rs represent a hydrocarbon radical of at least six carbon atoms and selected from the group consisting of a saturated alkyl group, an unsaturated alkyl group, a cycloalkyl group, an aryl group, and a terpene acid residue, and in which R2, R3, R4 and Rs represent a material selected from the hydrogen, a simply alkyl of less than five carbon atoms, and an alkylol of less than five carbon atoms, and in which R3 and R4 may further represent a second acid polyamide chain, while in the side chains the letter A represents a material selected from the group consisting of amino (NH), a simplealkyl substituted amino of less than flvecarbon atoms, an alkylol substituted amino of less than five carbon atoms, oxygen,

and sulfur;

group consisting of and sulfur; andthe integers j and a vary from 1 to 6, while e and lvary from 0 to 6, and m and t vary from 1. to 6.

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

n CIB(I!I+I) CNH CHICHINHCHICHZ-NH in which the substituting groups are derived from the polyalkyl amino acid amides secured by chemically combining diethylenetriamine and a saturated fatty acid of over six carbon atoms as indicated by the letter 11. in this formula, and

wherein the carbamyl groups D1 and D: represent a material selected from the group consisting of oxygen, sulfur, and imido groups, the number of such groups being as 9 ranges from0 to 3.

19. The substituted carbamyl compounds of the following general formula: 1

carbon atoms as indicated by the letter n in this formula, andwherein the carbamyl groups D1 and D: represent a material selected from the 40 group consisting of oxygen, sulfur, and imido groups, the number of such groups being as g ranges from 0 to 3.

20. A 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, said condensation product containing a. free secondary'amino group is chemically combined with urea at 170 to 200 C.

21. A process for forming a substituted guanidine compound in which the condensation product of an organic acid of at least six carbon atoms and a polyamine, said condensation product containing a free secondary amino group is chemically combined with a guanidine salt at 170 C. to 200 C. y

22. A process for forming a substituted biuret compound in which the condensation product of an organic acid of at least six carbon atoms and a polyamine, said condensation product containing a free secondary amino group is chemically combined with a biuret at 170 C. to 200 C.

23. A process for forming a substituted biuret compound in which the condensation product of an organic acid of at least six carbon atoms and a polyamine, said condensation product containinga free secondary amino group is chemically combined with urea at 170 C. to 200 C.

24. A process for forming a substituted carbamyl compound in which the condensation product of an organic acid of at least six carbon atoms and a polyamine, said condensation product containing a free secondary amino group is chemically combined at 170 C. to 200 C. with suflicient of a material selected from the roup consisting of urea, thiourea, biuret, and guanidine carbonate to chemically combine with all the amino groups and give a product free of a secondary amino group.

WILLARD L. MORGAN. EARLE DAVIS McLEOD.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2461918 *Aug 14, 1945Feb 15, 1949Sterling Drug IncPolyamine resinous composition and an ink made therefrom
US2713066 *Oct 13, 1951Jul 12, 1955Shell DevBeta-carbonyl-substituted ureides
US2750366 *Feb 16, 1952Jun 12, 1956Armour & CoMono-acyl derivatives of alkylene diamines and process for preparing same
US2764601 *Feb 24, 1953Sep 25, 1956Arnold Hoffman & Co IncTextile assistants
US2772966 *Jul 28, 1954Dec 4, 1956American Cyanamid CoCationic rosin sizes
US2785092 *Aug 2, 1954Mar 12, 1957Ciba LtdCondensation product and textile material softened therewith
US2847399 *Oct 8, 1954Aug 12, 1958Rohm & HaasVinyl ethers of substituted biurets, their polymers, and their preparation
US2925781 *Oct 21, 1957Feb 23, 1960Union Oil CoCorrosion prevention
US2992195 *Nov 29, 1957Jul 11, 1961Swift & CoPreparing modified polyamide resins
US3240664 *Feb 3, 1964Mar 15, 1966Hercules Powder Co LtdPolyaminoureylene- epichlorohydrin resins and use in forming wet strength paper
US3298993 *Dec 10, 1962Jan 17, 1967Montedison SpaPolyoxymethylene compositions stabilized with biurets and phenols or amines
US3445408 *Sep 6, 1966May 20, 1969Liaison SaPolyamide resins
US3956350 *Apr 8, 1974May 11, 1976Ciba-Geigy CorporationProcess for the production of textile softeners
US3959323 *May 22, 1975May 25, 1976Continental Oil CompanyOil soluble mercury compound for an analytical standard
US5298618 *Nov 23, 1992Mar 29, 1994Texaco Chemical CompanyMacrocyclic oxamides
DE2453386A1 *Nov 11, 1974May 22, 1975Sandoz AgVerwendung von verbindungen zum ausruesten von materialien
Classifications
U.S. Classification540/460, 564/160, 564/38, 554/53, 252/8.63, 564/159, 554/42, 554/39, 530/221, 564/22, 554/57, 564/30, 564/59, 564/188