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Publication numberUS2470081 A
Publication typeGrant
Publication dateMay 10, 1949
Filing dateJun 18, 1946
Priority dateJun 18, 1946
Publication numberUS 2470081 A, US 2470081A, US-A-2470081, US2470081 A, US2470081A
InventorsThurston Jack T, Warner Ruth B
Original AssigneeAmerican Cyanamid Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Alkylene oxide condensation products of dimerized fatty acid alylol amides
US 2470081 A
Abstract  available in
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Description  (OCR text may contain errors)

Q Patented May 10, 1949 UNITED STATES PATENT OFFICE ALKYLENE OXIDE CONDENSATION PROD- UCTS F DIMERIZED FATTY ACID AL- KYLOL AMIDES Jack '1. Thurston, Riverside, and Ruth B. Warner,

Stamford, Conn., assignors to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application June 18, 1946,

Serial No. 677,524

'12 Claims. (01. zoo-4045i This invention relates to water-soluble alkylene oxide condensation products of bis-alkylol amides of heat-polymerized or dimerized polyunsaturated fatty acids of approximately 18 carbon atoms, and to their methods of preparation. Objects of the invention are to obtain non-ionic surfaceactive agents having good dispersing and emulsimonoor dialkylolamines containing alkylene radicals of 2-4 carbon atoms they are converted into diamides of the formula RI RI I HO.C,.HQ,..I1I.OC .B.CQ.N.C,,H2...OH in which R is the residue of the dimerized polyunsaturated fatty acid, n is 2, 3 or 4, and R is are essentially organic dicarboxylic acids of the cycloaliphatic series. The most probable structural formulas for these dimerized fatty acids are given in volume 32 of Industrial Engineering Chemistry, page 808, as follows:

Di-merization of octadecadienic acids and their esters by 1,4-diene addition leads to compounds of the following structure, or isomers thereof:

1 1 H o o=conl 1c/ CH (CH2)aC HC-(CH2)7C onucmn- H H OH Conjugated and unconjugated octadecatrienic acids and their esters polymerize by a bimolecular addition involving and additional intramolecular ring'closure, forming a compound of the following structure, or isomers thereof:

In our copending application Serial No. 677,525 filed concurrently herewith we have shown that by heating these compounds or their lower alkyl esters such as the methyl or ethyl esters with either hydrogen or the I'adiCa1?CnH2n.OH depending on whether the mono or dialkylolamine was used. These diamides, which vary in appearance from dark, viscous liquids to non-crystalline solids, are soluble in alcohols and in arcmatic hydrocarbon solvents but are insoluble in water and are not surface-active.

Our present invention is based on the discovery that these bis-alkylol amides can be converted into water-soluble non-ionic agents by condensing them with sufiicient quantities of alkylene oxides of 2-4 carbon atoms to render the product water-soluble. The invention therefore consists in the production of watersoluble derivaties of bis-alkylol amides of dimerized polyunsaturated fatty acids of approximately 18 carbon atoms, in which the alkylol radicals contain 2-4 carbon atoms, by condensing them with ethylene, propylene or butylene oxide or similar compounds such as epichlorhydrin which contain a water-solubilizing lower alkylene oxide ring.

' Any polyunsaturated fatty acid of approximately 18 carbon atoms may be used as a starting material in preparing the compositions of the present invention. Fatty acid mixtures containing polyunsaturated fatty acids of approximately 18 carbon atoms are employed in preparing the dimerized .fatty acids because they are readily obtainable by the hydrolysis of natural oils of vegetable and animal origin, and it will be understood that the expression dimerized polyunsaturated fatty acids of approximately 18 carbon atoms refers to the monomeric fatty acids from which the dimerized acids are prepared by heat treatment rather than to the resulting dimers, which contain approximately 36 carbon atoms. The dimer acids may be used either in the form of the free acids or as the lower alkyl esters thereof, such as the methyl, ethyl or propyl esters, in preparing the alkylol amides employed in the process of our invention.

Any monoor diahyloloamine in which the alkylene radical or radicals contain 2-4 carbon atoms may be condensed with the dimerized higher fatty acids described above, or with their methyl, ethyl or propyl esters, to form diakylol surface-active 3 amides. Typical dialkyloloamines which may be used are monoethanolamine, diethanolamine, monopropanolamine, dipropanolamine, monobutanolamine, dibutanolamine or mixed dialkylolamines containing one ethanol and one propanol substituent, or one ethanol and one butanol substituent, etc. These and other similar amines may be condensed with the dimerized higher fatty acids by refluxing a solution containing about one mol of the dimerized acid and two mols of the amine in an organic solvent such as toluene, xylene and the like while distilling oi! the water produced by the amide formation. when esters of the dimerized fatty acid are employed the organic solvent may be omitted, the two reagents being simply mixed and heated at about 150-200 C. in an inert atmosphere for several hours. The liberated alcohol may then be removed, together with any excess amine, by distillation at reduced pressures.

The alkylene oxide condensation can be carried out in the absence of solvents by heating the dimer acid diamides with ethylene, propylene or butylene oxide in an autoclave under pressures up to 4-5 atmospheres, preferably in the presence of a small quantity of a catalyst such as sodium alcoholate at temperatures of l-160 C. We have found, however, as another important feature of the invention that the condensation reaction can be carried out at considerably lower pressures and temperatures, and in most cases at atmospheric pressures, by the use of polar solvents such as isopropyl alcohol, tertiary butyl alcohol and the like, preferably with the addition of a lower alkyl amine such as diethylamine or trlethylamine as catalyst. Under these conditions, solubilizing amounts of lower alkylene oxides can be condensed with the dimer acid diamides simply by passing the alkylene oxide compound into the solution under a reflux condenser, and at approximately the .boiling point of the solvent used.

The quantity of allwlene oxide to be condensed with the dimer acid diamides to obtain the proper degree of water-solubility for optimum dispersing, emulsifying or dye-assistant properties may vary throughout a wide range. With diamides of relatively low molecular weight, such as the bis-monoethano'lamides, as little as 8 mols of ethylene oxide or 10-15 mols of propylene oxide or -25 mols of butylene oxide for each mol of the dimer acid diamide will produce adequate water-solubility. As shown in Example 4, as much as 175 mols of alkylene oxide for each mol of the dimer acid can'easily be combined if desired.

The invention will be further illustrated by the following specific examples. It should be understood, however, that although these examples may describe in detail certain specific features of the invention, they are given primarily for purposes of illustration and the invention in its broader aspects is not limited thereto.

Example 1 tend to distill off with the water.

For example, 56 parts by weight of dimerized Example 2 t-Butanol, 300 cc., 190 grams of the N,N'-di-2- hydroxyethylamide of the dimer acid of Example 1 and 20 cc. of triethylamine were heated together in a flask provided with stirrer, inlet tube, thermometer, and spiral coil reflux condenser. Ethylene oxide was bubbled through the resulting solution, maintained under atmospheric pressure, at 70-80 C. until 244 grams were absorbed. This required about 12 hours. During the reaction ice water was circulated through the reflux condenser to prevent escape of the unreacted ethylene oxide. When the addition was complete the reaction mixture was allowed to reflux for 2 or 3 hours or until the temperature reached -95 C. after which the solvent and volatile material were stripped at reduced pressure (20-30 mm). The product was 418 grams of dark, viscous liquid.

Example 3 The ethanolamide of the dimer acid of Example l, 192 grams, 225 cc. of t-butanol, and 15 cc. of triethylamine were heated at atmospheric pressure with agitation to 70-80 C., and ethylene oxide was bubbled through the solution as in Example 2. After 4'77 rams of gas had been absorbed (about 24 hours), the solution was refluxed for 3 hours- The t-butanol and triethylamine were then removed by distillation at reduced pressure. The product was 655 grams of thick, dark brown liquid which was soluble in water to form clear foaming solutions.-

Example 4 A mixture of 21 grams of the dimer acid ethanolamine of Example 1, cc. of t-butanol and 15 cc. of triethylamine were heated with agitation to 7040 C. as in Example 3 and 266 grams of ethylene oxide were absorbed. The yield was 271 grams of a product containing ethenoxy units per molecule.

Example 5 A solution of 840 grams (1.5 mols) of dimer- Example 6 A 250-gram portion of the product of Example 5 was mixed with 200 cc. of t-butanol and 10 cc. of triethylamine in a flask fitted with stirrer, thermometer, gas inlet tube, and a coil condenser open to the atmosphere through which ice a clear yellow, foaming solution.

8 water was circulated. Ethylene oxide was passed into the solution at -85 C. for 7 hours at the end of which time 243 grams were absorbed. Re-

fluxing was continued for 2 hours, and the vola-' i Example 7 A mixture .of 200 grams (.342 mol) of the dimethyl ester of dimerized linseed acid (prepared according to Bradley, Industrial & Engi-- neering Chemistry 32, 802 (1940)), and 57 grams (.684 mol plus 20% excess of ethanolamine) was heated with stirring at 130-180 C. for two hours in a, nitrogen atmosphere. At the end of this time the excess ethanolamine and the methyl alcohol were distilled off under waterpump pressure up to a temperature of 160 C. The product was a dark red oil. Yield 200 grams, of theory.

Example 8 A mixture of 200 grams (0.36 mol) of dimerized soya bean fatty acid and 60 grams (0.72 mol plus 10% excess of normal propanolamine) and ml. of xylene was refluxed with stirring, stripping oil the water in a trap as it formed. The reaction required 12% hours at -148 C. When the reaction was complete, as shown by the fact that no more water formed. the xylene and excess normal propanolamine were stripped off by distillation under water-pump pressure up to a temperature of C. The product was a viscous greenish-black oil. Yield 243 grams, 100% of theory.

Example 9 A mixture of 200 grams (0.36 mol) of dimerized soya beam fatty acid, 80 grams (0.72 mol plus 10% excess of z-amino-l-butanol) and 150 ml. of xylene was refluxed at a temperature of 145?- C. for 20 hours. Thewater was stripped out in a trap as it formed. When the reaction was complete the xylene and excess butanolamine were stripped off under water-pump pressure up to a temperature of C. The product was a dark green viscous oil. Yield 250 grams, 99% of theory.

Example 10 A mixture of 228 grams (0.39 moi) of the dimethyl ester of dimerized tung oil fatty acid (prepared according to Industrial 8: Engineering Chemistry 32, 802 (1940)) and 60 grams (0.78 mol plus 20% excess) of 95% ethanolamine was heated for two hours at 1'70-180" C. in a nitrogen atmosphere. The excess ethanolamine and the methanol were distilled off under water-pump pressure up to a temperature of 190 C. The product was an amber colored viscous oil. Yield 253 grams, 100% of theory.

Example 11 a solution of 97' grams (0.151 mol) of the bis-monoethanolamide of dimerized linseed fatty acid prepared as described in Example '7, 100 ml.

during 3% hours. At the end of this time 125 grams (2.84 mols) had been absorbed. The reaction mixture was heated for another three hours during which time the reflux temperature rose to 96 C. The solvent and volatile material were distilled off under water-pump pressure up to a temperature of 130 C. The product was a dark red oil, yield 217 grams.

Example 12 A solution of 100 grams (0.156 mol) of the bis-monoethanolamide of dimerized linseed fatty acid, 100 ml. of tertiary butyl alcohol and 10 ml. of triethylamine was placed in the apparatus described in the preceding example. Ethylene oxide was passed into the solution during 5 hours at a temperature of 6888 C. During this time 217 grams (4.93 mols) were absorbed. The reaction mixture was heated for an additional three hours and the "reflux temperature rose to 95 C. The solvent and volatile materials were distilled oil under water-pump pressure up' to 130 C. The product was a dark red oil, yield 310 grams.

Example 13 A solution of 100 grams (0.156 mol) of the bis-monoethanolamide of dimerized tung fatty acid, 100 ml. of tertiary butyl alcohol and 10 ml.

of triethylamine was-placed in the apparatus described above. Ethylene oxide was passed into the solution during 4 hours at a temperature of 75-84 C. During this time 129 grams (2.93 mols) were absorbed. The mixture was heated for an additional four hours at 92-95 C. to complete the reaction. The solvent and volatile materials were distilled off as in the preceding examples. The product was a brown viscous oil, yield 224 grams. I

Example 14 A solution of '100 grams (0.149 moi) of the bis-monopropanolamide of dimerized cottenseed fatty acid, 100 ml. of tertiary butyl alcohol and 10 ml. of triethylamine was placed in the apparatus described above. Ethylene oxide was passed into the flask during seven hours at 80-86 C. During this time grams (3.86 mols) were absorbed. The mixture was heated at 95-105 C. for an additional three hours to complete the reaction. The solvent and volatile materials were distilled oi! as before. The product was-a brown viscous oil, yield 263 grams.

Example 16 solution of the product of Example 2 were then added and the bath brought slowly to the boil and maintained there at the boil for sufficient time to complete dyeing. The yarn was then removed, well rinsed, and dried. The dyeing was bright, level, and of excellent color value.

A dye bath was made up having the same composition as before but without the surface-active agent. The resulting dyeing was definitely inferior in brightness, levelness and strength of shade.

Example 17 A dye bath was made up of 4000 parts of water heated to 100 F. and 100 parts of wool fabric gradually introduced and maintained for a sufficient time .to assure thorough wetting. parts of concentrated sulfuric acid was diluted, added to the dye bath, and allowed to penetrate the wool. Thereupon the solutions of. the following dyes were introduced and allowed to disperse:

1 part of the chromium complex of the azo dyestuif obtained from diazotized anthranilic acid and 1-(4'-sulfophenyl)-3-methy1 5 pyrazolone.

part diazotized 1-amino-2-hydroxy-naphthalene-4-sulfonic acid coupled to 1-pheny1-3- methyl-5-pyrazolone I part diazotized 1-amino-2-hydroxy-naphthalene-4-sulfonic acid coupled to l-hydroxynaphthalene-8-sulfonic acid Two parts of the product of 'Example 2 dissolved in warm water were then added, the temperature of the dye bath raised to the boil gradually, and boiled for a sufficient time to complete dyeing. Thereupon the dye bath was run off, the wool fabric rinsed in cold water, and dried.

The goods dyed were level, free of skitteriness, and showed no oil blotches. The shade of the fabric was strong, approximately 20% stronger than the same dyeing effected under identical conditions and without surface-active agent.

Example 18 A dye bath was made up of 300 parts of water and 0.4 part of the chromium complex of the azo dyestuff obtainedfrom-diazotized 1-amino-2- hydroxy-6-nitro-naphthalene 4 sulfonic acid coupled to 2-naphthol. 0.5 part of calcined Glaubers salt and 0.1 part of 56% acetic acid were then added, whereupon 5 parts of thoroughly wet out wool yarn were introduced into the dyebath. parts of a 1% solution of the product of Example 2 were introduced and the temperature raised to 180 F., whereupon 0.075 part of formic acid was added, the temperature raised to the boil, the bath boiled for a short time, 0.1 part sulfuric acid added and the boil continued for about twice the length of time until dyeing was complete.

Example 19 A dye bath was made up of 300 parts of water and 0.1 part of well dissolved chromium complex of the azo dyestuif obtainedfromdiazotized 4 nitro-2-amino-phenol coupled to 1-(4'-sulfophenyl)-3-methyl-5-pyrazolone. 3 parts of 10% ammonium sulfate solution were then added with 4 parts of calcined Glaubers salt. Thereupon 7.5 parts of a 1% solution of the product of Example 11 were added and 5 parts of thoroughly wet out wool yarnthen introduced. The bath was slowly brought to the boil, boiled for a short time, 0.5 part of 56% acetic acid added, boiling continued for about the same length of time, followed by an addition of another 0.1 part of 56% acetic and the boiling then continued for the same time until the dyeing was complete. The yarn was removed, rinsed and dried, and presented a bright dyeing which was level and of excellent color value.

A similar dyeing procedure was followed with no surf ace-active agent added but all other factors kept the same. The resulting dye was quite inferior in brightness, levelness and strength of shade.

' What we claim is:

1. Water-soluble condensation products of lower alkylene oxides of '2-4 carbon atoms with dialkylolamides of dimerized polyunsaturated fatty acids of the formula Ii R! Ho.c.H1...N.oo.R.co.1 I.c,H:.on wherein R is the residue of dimerized polyunsaturated fatty acids of approximately 18 carbon atoms, 11. is a whole number from 2 to 4 inclusive and R. is a member of the group consisting of hydrogen and 'CnH21|.-OH said condensation products having from 8 to 175 mols of said lower alkylene oxide condensed therein.

2. Water-soluble condensation products of ethylene oxide with dialkylolamides of dimerized polyunsaturated fatty acids of the formula wherein R is the residue of dimerized polyunsaturated fatty acids of approximately 18 carbon atoms, 11 is a whole number from 2 to 4 inclusive and R is a member of the group consisting of hydrogen and CnH2n.OH, said condensation products having from 8 to 1'15 mols of ethylene oxide condensed therein.

3. Water-soluble condensation products of lower alkylene oxides of 2-4 carbon atoms with bis-monoethanolamides of dimerized polyunsaturated fatty acids of approximately 18 carbon atoms, said condensation products having from 8 to mols of said lower alkylene oxide condensed therein.

4. Water-soluble condensation products of lower alkylene oxides of 2-4 carbon atoms with bis-diethanolamides of dimerized polyunsaturated fatty acids of approximately 18 carbon atoms, said condensation products having from 8 to 1'75 mols .of said alkylene oxide condensed therein.

5. Water-soluble condensation products of ethylene oxide with bis-monoethanolamides of dimerized polyunsaturated fatty acids of approximately 18 carbon atoms, said condensation products having from 8 to 175 mols of ethylene oxide condenser therein. l

6. Water-soluble condensation products of ethylene oxide with bis-diethanolamides of dimerized polyunsaturated fatty acids of approximately 18 carbon atoms, said condensation products having from 8 to 1'75 mols of ethylene oxide condensed therein.

'I. A method of producing water-soluble derivatives of dialkylolamides of dimerized polyunsaturated fatty acids of the formula urated fatty acids of approximately 18 carbon atoms, 1: is awhole number from 2 to 4 inclusive and R is a member of the group consisting of hydrogen and C1rH-.m.0H which comprises condensing therewith a sumcient quantityof an alkylene oxide of 2-4 carbon atoms to render the product water-soluble, said quantity being from 8 to 175 mols of the alkylene oxide for each mol of the dimer acid diamide.

' alkylene oxide is ethylene oxide.

11. A method of producing water-soluble derivatives of bis-diethanoiamides of dimerized polyunsaturated fatty acids of approximately 18 carbon atoms which comprises condensing therewith a sufiicient quantity of an alkylene oxide of 2-4 carbon atoms to render the product watersoluble, said quantity being from 8 to 175 mols of the alkylene oxide for each mol of the dimer acid diamide.

12. A method according to claim 11 in which the alkylene oxide is ethylene oxide.

JACK T. THURSTON.

RUTH B. WARNER.

REFERENCES crrnn The following references are of record in the 15 file of this patent:

' UNITED STATES PATENTS Number Name Date 2,243,329 De Groote et a1 May 27, 1941 20 2,344,977 De Groote et a1 Mar. 28, 1944 2,379,413 Bradley July 3, 194,5

FOREIGN PATENTS Number Country Date 337,368 Great Britain Oct. 27, 1940 364,104 Great Britain Dec. 28, 1931 380,431 Great Britain 1932 802 to 809 by Bradley et a1.

Patent Citations
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US2243329 *Jun 27, 1940May 27, 1941Petrolite CorpProcess for breaking petroleum emulsions
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US2379413 *Jun 28, 1940Jul 3, 1945American Cyanamid CoAmides of high molecular weight carboxylic acids
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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2718478 *Jan 27, 1954Sep 20, 1955American Cyanamid CoAntistatic treatment of fibrous materials
US2803607 *May 27, 1953Aug 20, 1957Bayer AgNu-substituted polyacrylamide sizing material composition and method
US2808397 *Feb 16, 1953Oct 1, 1957Bayer AgProduction of hydroxyether amides of polyacrylic acid
US5184992 *May 27, 1992Feb 9, 1993Banks Gary SMulti-station physical exercise apparatus
Classifications
U.S. Classification564/152
International ClassificationC08G59/50
Cooperative ClassificationC08G59/50
European ClassificationC08G59/50