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Publication numberUS2524218 A
Publication typeGrant
Publication dateOct 3, 1950
Filing dateMar 28, 1946
Priority dateMar 28, 1946
Publication numberUS 2524218 A, US 2524218A, US-A-2524218, US2524218 A, US2524218A
InventorsBersworth Frederick C
Original AssigneeBersworth Frederick C
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Washing composition
US 2524218 A
Abstract  available in
Previous page
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Claims  available in
Description  (OCR text may contain errors)

Patented Oct. 3, 1950 UNITED WASHING COMPOSITION Frederick C. Bersworth, Verona, N. J.

No Drawing. Application March 28, 1946, Serial No. 657,893

3 Claims. 1

. This invention relates to derivatives of alkylene polyamines, and more particularly to such compounds which combine the properties of soap fcompatibility, detergent and wetting action, and ability to sequester metal ions. The synthetic detergents and wetting agents hitherto known fail to combine these properties in the effective manner of the compounds of the present invention.

It is, therefore, an object of this invention to prepare alkylene polyamine derivatives which are detergents and wetting agents, are capable of sequestering metal ions, and are compatible with soap. Other objects will appear in the following disclosure.

It has been shown by Munz, in U. S. Patent 2,240,957, that acetic acid derivatives of amines and diamines are useful for treating hard water. The compounds shown by Munz are not, however, compatible with soap. In my copendng application, Serial Number 491,669, filed June 21, 1943, now U. S. Patent 2,407,645, a method of preparing these acetic acid derivatives is shown. Various other methods are known.

The alkylene polyamine derivatives of the present invention are represented by the following formulaf N- o 11:) ,.-(-N- Hi) .)-N D t D wherein n is either 2 or 3 and m is either zero or a positive integer and wherein D is a member 01' the group consisting of and their alkali metal salts, and wherein A is a hydrocarbon group containing at least two carbon atoms and having not more than two hydrogen atoms replaced by a member of the group consisting of (CHz)2COOR, --(CH2):COOM, -SO3H, SO3M, OR and --OR0R wherein R is alkyl or hydrogen, M is an alkali metal, and R is alkylene, said groups being spaced at least two carbon atoms from the nitrogen atoms.

The compounds of this invention may be prepared in several ways. One of these methods consists in reacting one mol of a suitable polyamine, such as ethylene diamine, trimethylene diamine, diethylene triamine, etc., with two mols of a chloro derivative of the substituent desired in the A positions. The secondary (imino) hydrogens are then substituted either by the chloracetic acid method shown below, or by my process as set forth in my copending application Serial No. 491,669 filed June 21, 1943, now U. S. Patent 2,407,645,

to provide the proper substituents in the D positions.

It is essential that either two or three (CH:)

groups be present separating the nitrogen atoms and it is further necessary for the purposes of this invention that the groups in the D positions be either acetic acid or proplonic acid radicals or their alkali metal salts. These conditions insure sequestering action of the compound and tend to make the compound water miscible. The presence of more or less than the specified number of (CHz) groups seriously reduces or' eliminates this sequestering action.

It has been discovered that in general the longer the hydrocarbon chain in the A positions the more soap-like the entire compound becomes. It has been further found that when this chain is four carbon units in length or longer it is water dispersible, and when it is more than seven carbon units in length the calcium complex is soluble in water, foams strongly, cleans well and is compatible with soap.

Another requirement of these compounds is that any hydrophyllic groups attached to the hydrocarbon chain must be at least two carbon atoms removed from the nitrogen atoms. The substitution of a relatively long alkyl chain in the primary nitrogen position also destroys any electrolyte effect of the compound. It becomes possible, therefore, with proper substitutions in the A positions to prepare compounds which are miscible with materials such as soap without causing any deleterious effects to the soap, and form emulsions with liquid hydrocarbons, and other water insoluble organic compounds.

In order to understand this invention more clearly the following examples are given:

Example 1 One mol of ethylene diamine added to two mole of octyl chloride is heated under atmospheric pressure until the reaction is substantially complete. The resulting compound is reacted with chloracetic acid in methyl alcohol keeping the reaction solution at a pH of 8 to 8.5. The mixture is heated and held to a gentle refluxing of the methyl alcohol for a period of six to eight hours. The material is filtered from the formed sodium chloride and the methyl alcohol is distilled oil. The product is a semi-solid paste with an appearance somewhat like stearic acid and is soluble Hz JOONa Example 2 such as calcium ions.

Acrylic type unsaturated acids may be used advantageously in the preparation of compounds included within the scope of this invention. Several methods of employing those unsaturated acids are possible. In general they are first esterified to form a stable ester. Two mols of the ester may then be reacted directly with a diamine, such as ethylene diamine, according to the following equation:

It is noted that the ester group is sufficiently stable so that the hydrogen of the primary amino group acts as a hydrogen donor saturating the double bond. The remaining hydrogen of the amino groups is then reacted according to either of the methods described above. R in the case just described may be(CHz) n(NH(CH2) n) mwhere n is 2 or 3 and m is 0, 1 or 2. A second general method of utilizing an unsaturated ester is hydro-halogenation in the presence of methyl alcohol using dry HCl to form the chloride ester. The halogen ester is then reacted with a polyamine in methyl alcohol in the ratio of two mols of ester to one of the polyamine as in the previous cases. It will be noted that only the primary hydrogens are treated as being in the A positions.

In addition to the compounds described above derivatives using the condensation products from the Diels-Alder reaction may be used. A preferred compound of this series is produced from maleic anhydride and butadiene and is represented by the following formula:

The dicarboxylic acid resulting from the condensation of the butadiene and maleic anhydride is condensed with ethylene diamine in the same manner that the unsaturated acids described above are condensed, that is, the di-acid is esterifled and is reacted with hydrochloric acid and the hydrochloride is in turn reacted with ethylene diamine or other suitable diamines, triamines or tetramines. As in the other compounds described, the secondary hydrogens attached to the nitrogen groups are reacted to substitute acetic acid or propionic acid radicals. The product is compatible with soap and is an excellent cleaning agent. If desired, the ester may be saponified to yield the alkali metal salt, and if the acid is preferred, the salt is treated with an acid in the conventional manner.

Still other types of compounds may be produced by reacting 2 amino, 2 methyl, 1-3 propane diol, the formula of which is with ethylene dichloride. The compound 2 amino, 2 methyl, 1-3 propane diol is dispersed in methyl alcohol. To this well dispersed, well agitated suspension two mols of ethylene dichloride are added to each ten mols of the amine. The mixture is refluxed for about 1 hour. Sodium carbonate is added from time to time to maintain the pH between 8.0 and 8.5. The reaction is over in approximately 5 hours and requires about two mols of sodium carbonate and 1500 cc. of methyl alcohol. Sodium chloride formed is removed by filtration and the alcohol is removed by distillation. Secondary hydrogen atoms on each of the nitrogen atoms are reacted according to my application Serial Number 491,669 filed June 21, 1943, now U. S. Patent 2,407,645 and are substituted by the radical Cl-IzCOONa. The formula of the resulting product is believed to be as follows:

J)Na Na The product as produced is a yellow-white solid. It has been discovered that if the amine diol is reacted according to the chloracetic acid method some of the hydroxyl groups are involv d to form ether acids. The compound forms a lear calcium complex and is an excellent detergent. While it increases the foam of soap solutions it, by itself, is not a foaming agent as are the other compounds described above.

A preferred type of compound of this invention is the derivative of ethylene diamine in which a long chain acid such as undecylenic acid is substituted in the A positions. Two compounds using undecylenic acid are of particular interest and the method of making them is described below.

The methyl ester of the acid is first produced. This is in turn reacted with hydrobromic acid. This halogenation is carried out in ligroin in the presence of air and at a temperature of 0 0. Two mols of the bromide ester react readily with ethylene diamine in the presence of methyl alcohol as a solvent. The reaction is carried out at a pH of 8.0 which is regulated by the addition of dry caustic soda. Sodium bromide is precipitated and may be filtered off. When 70% ethylene diamine is used some foaming will be experienced due to the water present. It has been found that the best procedure is to dehydrate the entire reaction mixture, after the reaction is completed, with benzene. There is no appreciable hydrolysis of the methyl ester during this reaction. After removing the alcohol by distillation, a compound is obtained of a yellowish semi-crystalline mass, soluble in organic solvents and miscible with water to form a milky solution. To react the secondary hydrogen atoms on the nitrogen atoms, the product produced above is redissolved in methyl alcohol and the alcohol solution added to a slurry of chloracetic acid sodium salt in methyl alcohol. Two mols of such salts are used per mol equivalent of the reaction product. There is considerable heat of reaction but if this is permitted to run its course using 200 cc. of methyl alcohol for each mol of chloracetic acid sodium salt, the heat of reaction is 60 C. After two hours sodium bromide begins to precipitate and heat is applied to maintain the reflux temperature of methyl alcohol for about six to eight hours. Sodium carbonate is added from time to time to regulate the pH between 7.5 and 8.5. Provision must be made to allow liberated carbon dioxide to escape. When the reaction is completed the water that is pres ent due to the hydrous dia-mine is removed before filtering.

When the undecylenic acid used in the preparation of the foregoing product is of the usual type, CH3CH2=CH2-(CH2) v-COOH (Q-hendecenoic acid), the formula of that product is as follows:


. It is obvious that the lengths of the two alkyl chains on either side of the carbon atom of the undecylenic acid ester radical attached to the nitrogen atoms will depend upon the location of.

the double bond in the undecylenic acid, as well as upon which carbon atom the halogen atom is attached. Hence a more general formula for these compounds, using the methyl ester of any undecylenic acid, will be represented by the fol lowing radical in the A positions:

H2 )a-= CH;OOO(CHz),- H-

wherein, conformably with'the requirements of the compounds of this invention, a: is not less than 3--and is, of course, not greater than 8.

The above product is illustrative of these high ly effective compounds. They act as cleaners and foam in any type of water. They are not precipitated or salted out by any amount of electrolyte and are powerful wetting agents even in water of 400 parts per million hardness and in sea water. They are compatible with soap and are not precipitated in the form of lime soap nor is the soap salted out. They have a unique dual action in that they will form highly soluble filtrable calcium complexes. They also have the property of dispersing lime salts in an amount far greater than that calculated to form the clear complex. The calcium complex itself is soluble in alcohol. It may be noted that the compounds of this invention are both anionic and cationic in nature. For these reasons, and because these compounds are extremely stable in both alkaline and acid solutions, they have wide usefulness.

A second, and slightly different type of compound from that described above may be prepared from omega undecylenic acid by reacting the acid ester with hypochlorous acid, HOCl. This acid acts much the same way as does hy- 6 drochloric acid in its addition to the double bond of undecylenic acid. The addition product is reacted with ethylene diamine and the secondary hydrogen atoms are reacted as described above;

upon hydrolysis of the ester groups with alkali a compound oi the following formula results:

CHzOH GHgOH N800C-(CH:)l-J3H H(CH:)r-COONB -cm-cm-N H: H; -O =0 Na Na This compound is very similar in nature to the compound described above except that it is more soluble in water. Likewise, the lengths of the two alkyl chains of the undecylenic acid radical will depend upon conditions as set forth above.

When the hydrochloric acid derivative of undecylenic acid ester is reacted with diethylene triamine, and the secondary hydrogen atoms on the three nitrogen atoms are reacted with chlorpropionic acid sodium salt, there is produced a compound similar to the ethylene diamine dethe calcium complex precipitates in water. However, if this benzene nucleus is sulfonated the sodium sulfonate calcium complex is soluble and is useful for the purpose of this invention. If not sulfonated the compound is quite oil soluble, while the sulfonated compound (sodium salt) is quite water soluble. The compounds described above may Fne illustrated by the following formula:

Hf 08 H:

O: -O 0- =0 (Oil soluble) NBSO CH N-OH CH N-CH S a 3 l e Q Hz Ca H1 0: O OC=O (Water soluble) This compound illustrates the fact that materials particularly suitable for cleaning action and sequestering ability in oil may be secured, by substituting suitable oil soluble groups in the A positions.

The introduction of a (-SO3Na) group into the compounds of this invention may be readily accomplished by reacting two mols of a compound such as taurine, NHz(CH2)zSOaH, with each one mol of dichloro ethylene, CI(CH2)2C1. The reaction follows the general procedure outlined for that described of reacting 2 amino, 2 methyl, 1-3 propane diol with ethylene dichloride described above. The resulting product is then reacted according to my application Serial Number 491,669, new U. S. Patent 2,407,645, to sub- The product may be crystallized from methyl alcohol solutions.

It is excellent as a detergent and for sequestering metal ions, and is completely miscible with soap.

Other types of radicals in the A positions are also advantageous for some cleaning purposes; for example, compounds prepared by reacting an hydroxylated ether with a diamine. The reaction between diethylene glycol and anhydrous et vlene diamine may be carried out merely by boi ing the two together. Xylene or a dehydration catalyst may be added but such precaution is not essential. As in the previous examples, the secondary hydrogen atoms on the nitrogen atoms are substituted with CHzCOONa or CH2CH2COONa groups, and by the same method. The final compound may be represented by the formula:

This compound is an excellent detergent and sequestering agent and is completely miscible with soap.

A summary of the properties of the compounds herein described will serve to point out obvious uses for them.

As prepared, the compounds have no deleterious electrolytic properties to soap. Accordingly as they are compatible with soap when incorporated with soap in which electrolytes are present, the electrolytes do not adversely afiect the soap. They are of themselves good wetting agents and detergents but do not defat the skin. Being completely stable in both alkali and acid solutions, they may be incorporated in media of either type. The effectiveness of these compounds may be due, in part, to the fact that they are both cationic and. anionic in action as well as the fact that they sequester metal ions, such as calcium ions, thus preventing the precipitation of calcium soaps. It can be seen from the above description that the compounds may be varied to make them soluble in oils, organic solvents, or water. The foaming power of the compound may be adjusted, as the longer the aliphatic chain in the A positions, the greater the foaming power, while the heterocylic compound shown has very little foaming action (although it is a good detergent). More than six carbon atoms in the hydrocarbon chain insures the compound of having good wetting action, particularly if carboxyl groups or hydroxyl groups are present.

In the above discussion of this invention wherein alkali metal salts are disclosed, and. in the claims, the term alkali metal is intended to include the group consisting of sodium, potassium, and ammonium (NH4) Although any desired amount of these compounds may be added to a water-soluble soap to form a washing compound, it has been found that from 1% to 5% by weight prevents the precipitation of calcium or magnesium soaps in any commonly used water, and yields a good detergent soap.

I claim:

1. A detergent composition consisting of a water soluble alkali metal-fatty acid soap and an alkylene polyamine derivative, the amount of said alkylene polyamine derivative in the said mixture being from 1% to 5% by weight of the mixture, said alkylene polyamine derivative being one conforming to the formula:

and OR'OR wherein R is one of the group consisting of alkyl and hydrogen, M is an alkali metal, and R is an alkylene group, said replacing groups being spaced from the N atoms of the compound by at least two carbon atoms of the hydrocarbon group containing the same.

2. The detergent composition of claim 1, wherein said alkylene polyamine derivative comprises the compound:

3. The detergent composition of claim 1, wherein said alkylene polyamine derivative comprises the compound:

CH2 on? on, CH-COOR 5 11000-0 CH1 g f n-Coon ROOC n H-N-CH:OHN 0H2 C 1 H2 H2 v=0 AR wherein R is one of the group consisting of hydrogen and alkyl and R, is one of the group consisting of hydrogen and alkali metal.


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

UNITED STATES PATENTS Number Name Date 2,240,957 Munz May 6, 1941 2,387,976 Bersworth Oct. 30, 1945 2,407,645 Bersworth Sept. 17, 1946 2,412,945 Bersworth Dec. 24, 1946

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Referenced by
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US2983684 *Nov 28, 1956May 9, 1961Wyandotte Chemicals CorpSoap composition containing lime soap dispersant
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US6040288 *Feb 20, 1998Mar 21, 2000Rhodia Inc.Fabric color protection compositions and methods
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US6183550Apr 16, 1999Feb 6, 2001Hercules IncorporatedPaper size dispersions
US7524800Jun 12, 2008Apr 28, 2009Rhodia Inc.Mono-, di- and polyol phosphate esters in personal care formulations
US7524808Jun 12, 2008Apr 28, 2009Rhodia Inc.Hard surface cleaning composition with hydrophilizing agent and method for cleaning hard surfaces
US7531490 *Sep 29, 2005May 12, 2009Kao CorporationDetergent composition comprising calcium gluconate and a mixture of calcium ion sequestering agents
US7550419Jun 12, 2008Jun 23, 2009Rhodia Inc.Mono-, di- and polyol alkoxylate phosphate esters in oral care formulations and methods for using same
US7557072Jun 12, 2008Jul 7, 2009Rhodia Inc.Detergent composition with hydrophilizing soil-release agent and methods for using same
US7608571Jun 12, 2008Oct 27, 2009Rhodia Inc.Method for recovering crude oil from a subterranean formation utilizing a polyphosphate ester
US7867963Jan 6, 2009Jan 11, 2011Rhodia Inc.Mono-, di- and polyol phosphate esters in personal care formulations
US7919073May 25, 2009Apr 5, 2011Rhodia OperationsMono-, di- and polyol alkoxylate phosphate esters in oral care formulations and methods for using same
US7919449May 25, 2009Apr 5, 2011Rhodia OperationsDetergent composition with hydrophilizing soil-release agent and methods for using same
US8268765Nov 30, 2010Sep 18, 2012Rhodia OperationsMono-, di- and polyol phosphate esters in personal care formulations
US8293699Jan 6, 2009Oct 23, 2012Rhodia OperationsHard surface cleaning composition with hydrophilizing agent and method for cleaning hard surfaces
US8993506Jun 12, 2007Mar 31, 2015Rhodia OperationsHydrophilized substrate and method for hydrophilizing a hydrophobic surface of a substrate
US9181282Dec 21, 2012Nov 10, 2015Universiteit GentOrganosilica compounds
US20060079437 *Sep 29, 2005Apr 13, 2006Kao CorporationDetergent composition
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U.S. Classification510/481, 562/564, 510/484, 562/500, 562/565
International ClassificationC11D9/04, C11D9/30, C11D10/00, C11D10/04
Cooperative ClassificationC11D9/30, C11D10/04
European ClassificationC11D9/30, C11D10/04