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US2530147A - Alkylene polyamine derivatives - Google Patents

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US2530147A
US2530147A US73772547A US2530147A US 2530147 A US2530147 A US 2530147A US 73772547 A US73772547 A US 73772547A US 2530147 A US2530147 A US 2530147A
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Frederick C Bersworth
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Frederick C Bersworth
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/33Amino carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/04Carboxylic acids or salts thereof
    • C11D1/10Amino-carboxylic acids; Imino-carboxylic acids; Fatty acid condensates thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00Compositions of detergents, not provided for by one single preceding group
    • C11D10/04Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00Compositions of detergents based essentially on soap
    • C11D9/04Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22Organic compounds, e.g. vitamins
    • C11D9/30Organic compounds, e.g. vitamins containing nitrogen

Description

Patented Nov. 14, 1950 UNITED ALKYLENE POLYAMINE DERIVATIVES Frederick C. Bersworth, Verona, N. J.

No Drawing. Application March 27, 1947, Serial No. 737,725

8 Claims.

This invention relates to derivatives of alkylene poiyamines, and more particularly to such compounds which combine the properties of soap compatibility, detergent and wetting action, and ability to sequester metal ions. Still more particularly it relates to carboxylic and hydrocarbon derivatives of such alkylene polyamines. The synthetic detergents and wetting agents hitherto known fail to combine these properties in the ef-. fective manner of the compounds of the present invention.

It is, therefore, an object of this invention to prepare alkylene polyamine carboxylic and hydrocarbon 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 more than very small amounts. In my 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 formula:

A l v oom M 00M wherein Alk is an alkylene radical of the group consisting of ethylene and propylene, n is a positive integer not greater than 2, m is zero or a positive integer, M is selected from the group consisting of hydrogen and alkali metal, and A and amine, diethylene triamine, triethylene tetramine, etc., with two mols of a, chloro derivative of the substituent desired in the A and 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 U. S. Patent 2,407,645. Other methods may be used if desired.

A second method for preparing these compounds consists of reacting one mol of the alpha beta dichloro derivative of ethylene with two mols of an alpha amine of the substituent desired in the A and A positions. This compound is then reacted in either of the two general ways de-' scribed above to provide the proper substituents in the secondary (imino) positions.

It is essential that either two or three (-CH2) groups be present separating the nitrogen atoms. Consequently, the alkylene radicals separating the nitrogen atoms must be either ethylene or propylene radicals, and if propylene, they may be either (CH2) 3- groups or -omoH- groups.

It is further necessary for the purposes of this invention that the groups replacing the secondary hydrogen atoms be either acetic acid or propionic 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 fewer ,carbon atoms than those specified in these alkylene and (CH-2)" groups of the foregoing formula seriously reduces or eliminates this sequestering action.

The following is believed to be an explanation of the physical characteristics of the compounds A are hydrocarbon groups containing together 40 briefly described abOVe- The ps in e Seea total of at least ten carbon atoms and having not more than two of their hydrogen atoms replaced by a carboxyl radical of the group consisting of -COOH, -COOR and -COOM', M

ondary (imino) positions give the various compounds water solubility (or colloidal dispersal properties) as well as the property of sequestering polyvalent metal ions such as calcium withbeing an alkali metal and R being the radical of 5 out ad cal y al eri the so ub y of he coman alcohol ROH. The term alkali metal as used above, and in th claims, is intended to include particularly sodium, potassium, and ammonium. The term hydrocarbon group includes carbocyclic groups, both alicyclic and aromatic.

The compounds of this invention may be prepared in several ways. One of these methods consists in reacting one moi of a suitable alkylene or polyalkylene polyamine, such as ethylene pound. Groups in the A and A positions ending in the radical --COOM, where M is an alkali metal such as ammonium, sodium or potassium, also influence the characteristics of the product. More than three per cent of compounds such as described by Munz in U. S. Patent 2,240,957 salt" out soap, making them undesirable for some purposes. The reason for this efiect is believed to be .due to the fact that the group CH2COOM is an diamine, trimethyiene diamine, propylene 1,2 dielectrolyte. When the total number of "hydros,cso,147

carbon" carbon atoms in the A and A groups together (i. e. exclusive of those in any carboxyl groups) is increased to ten or greater, the product loses its electrolyte character and assumes a soaplike character which becomes, more pronounced as the number of hydrocarbon" carbon atoms increases, Such compounds, e. g. those having a total of from 10 to 20 "hydrocarbon" carbon atoms in the A and A positions, appear to have little electrolyte efiect and may be mixed with soap freely. When a total of 12 or more "hydrocarbon" carbon atoms are present in the A and A positions, it is found that the compound is completely miscible with soap and is itself a good detergent. Those compounds having 14 or more such carbon atoms are oil soluble and such solubility is particularly marked in the case of the ammonium salts or the complex metal salt. In all cases the compounds, because of the groups in the secondary (imino) positions, appear to have the power of sequestering calcium or other metal ions without precipitation from solution. As these compounds become quite soap-like in character, i. e. wher the total number of "hydrocarbon carbon atoms in the A and A positions exceeds 12, the compound is soluble in water in much the same manner as is soap.

Ordinarily the groups A and A will be identical, merely because it is usually easier to manutacture such products than to make those wherein A and A are different. When A and A are the same, each will, of course, contain at least ilve "hydrocarbon carbon atoms. However, A and A maynot only have diflerent numbers oi "hydrocarbon carbon atoms, but neither, or both, or only one, may be provided with one or two carboxyl substituents of the group hereinbefore defined-see for instance Examples 6 and '7, below.

The group COH gives to the compounds oi this invention fatty acid characteristics, while the group COOM (M being alkali metal) provides soap-like properties in these compounds.

The esters of these compounds are not generally soluble in water, but are oil soluble.

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

Example 1 A preferred type of compound of this invention is the derivative of ethylene .diamine in which an undecylenic acid derivative is substituted in the A and A positions. Two compounds using undecylenic acid are of particular interest and the method of making them is described below.

1 The methyl ester of the acid is first produced by any conventional esterification procedure. The ester is in turn reacted with hydrobromic acid. This halogenation is carried out in wet" ligroin, i. e. containing a small amount of water, in the presence of air and at a temperature of 0 C. The hydrobromic acid is forced into a saturated solution or the acid in ligroin in the form 0! hydrogen bromide gas. Under the conditions as carried out, the gas causes suiiicient agitation. The resulting brominated methyl ester is soluble in ligroin and does not crystallize out, but is recovered by evaporation. 558 grams oi the brominated ester (two mois) are dissolved in methyl alcohol to form a substantially saturated solution. 100 grams of ethylene diamine (70%) is added slowly with agitation to the ester solution while a pH of about 8.0 is maintained by the addition of dry caustic soda. In the course of the reaction there is some foaming because of the mide, the mixture is dehydrated with benzene,

thus precipitating the sodium bromide and making vacuum distillation trouble free. There is no appreciable hydrolysis oi the methyl ester during the reaction. After removing the alcohol by distillation a yield of 452grams yield) is obtained, in the form of a yellowish, semi-crystalline mass which is soluble in organic solvents and miscible with water to form a milky solution. The compound is not very soluble in acids, but forms a slurry similar to semi-precipitated calcium soap.

The product of the above reaction is re-dissolved in methyl alcohol and the alcoholic solution added to a, slurry oi chloracetic acid sodium salt in methyl alcohol. Two mols of such salt is added for each mol equivalent or the reaction product with good agitation. Considerable heat of reaction is developed and is allowed to run its course for two hours. Using 2000 cc. of methyl alcohol and flve molar equivalents of the diamineester reaction product and ten molar equivalents of the sodium salt of chloracetic acid, the temperature oi the reaction is 60 C. At the end of two hours, heat is applied and the temperature maintained at the reflux temperature of methyl alcohol for about 6 to 8 hours. Sodium carbonate is added i'rom time to time to maintain the pH between 7.5 to 8.5. The formed sodium chloride is removed by filtration.

The product thus produced by the above reaction is highly eiIective as a cleaner and foams and cleans in any type of water. It is not precipitated by any amount of electrolyte, and is a powerful wetting agent in water or 400 P. P. M. hardness and in salt water. Soap added to a solution 01' the compound is not precipitated in hard water nor is the soap salted out.

It is believed that the formula of the hydrolysis product oi the above compound may be written as inflows:

Unsaturated acids of the acrylic acid series having live or more carbon atoms in the hydrocarbon" chain when halogenated may be reacted similarly to undecylenic acid to give the compounds 01 this invention. Oi such acids. hexenic and teracrylic in the lower range of chain lengths, and oieic in the higher range serve to complete the understanding as described above or the eflect 01' chain length in the A and A positions on the characteristics of the final compound.

A product similar to that shown above may be formed by employing HCl as the halogenating agent. In such case it is believed that the chlorine adds to the double bond according to Markownikofls rule in contrast to the addition of HBr. Consequently the carbon chain separating the the carboxyl group from the amino group is one less when HCl is employed (although the total number of carbon atoms in the compound is of course the same).

Example 2 141 grams oi oleic acid is dissolved in 500 cc. of methyl alcohol, and placed in an apparatus equipped with a reflux condenser. Carrying out the reaction at 50 0., dry HCl is introduced into the alcohol solution of acid until a saturated solution of hydrochloric acid is formed. In A of an hour the chlor ester has formed, and separates from the alcohol solution. The ester is then water present. To separate all the sodium bro- 7s washed with dilute caustic soda. dried, and puri- NAOOC(CH1)1 CHDICOONB H CH-N-CHa-OHa-N-C GHQ-(C a): H: H: OHDhCHr OONa oom This compound is a very powerful emulsifying agent, imbibes water freely and forms gels similar to lecithin. It is oil soluble and forms emulsions when a solution of it and oil is let out with water; such emulsions are not broken by the presence of electrolytes or metal ions. The product is miscible with soap and no precipitate is formed on the addition of the usual precipitating agents such as lime. If diethylene triamine is substituted for ethylene diamine in Example 2, a product is obtained having increased solubility in water due to the presence of an added acetate group on the additional nitrogen atom. Other properties of the compound are substantially the same.

Example 3 Maleic anhydride and butadiene react according to well-known procedures, to form the compound:

Such a reaction is known as the Diels-Alder condensation.

The condensation product is then hydrochlorinated according to the procedure outlined in the above examples, being first esterifled. The chlorinated product is crystalline and soluble in methanol and has the following structure:

CH: C CH-COOCH:

C1 H H-COOCHI This chloroester may then be reacted in the ratio of two mols oi ester to one of ethylene diamine to form the symmetrical di-substituted compound. This di-substituted compound may then be reacted according to the process shown by my U. S. Patent 2,407,645. Such reaction takes place between the secondary hydrogen atoms and formaldehyde and sodium cyanide in an alkaline medium. The product is believed to conform to the following formula:

HrCOONl 35 groups.

Similar compounds may be prepared by reactin: in the same manner, any of thechloro esters resulting from the Dials-Alder condensation with suitable triamines, or tetramines. As with the other compounds described above, the secondary hydrogens attached to the nitrogen groups are reacted to substitute acetic acid or propionic acid radicals. These products are compatible with soap and are excellent cleaning agents.

l0 In the above examples a method of forming the compounds is disclosed which consists of reacting the halogenated derivative of the group to be placed in the A or A positions with a polyamine. This invention is not confined to a particular method and any suitable variation may be employed. The polyamine may be reacted with an unsaturated acid directly as in the following equation:

An amino acid may be esterified and reacted with a suitable halide such as ethylene dichloride. If desired a saturated fatty acid may be halogenated directly and the resulting product reacted with of oleic and undecylenic acids may be reacted with ethylene diamine to give such a product, for example.

The above discussion and examples relate to compounds containing at least four carboxylic Compounds included by this invention are those having both the A positions substituted by alkyl groups, and compounds having one of the A positions substituted by an alkyl group and one substituted by a fatty acid group. But in all such compounds the total number of hydrocarbon carbon atoms in the A and A positions must be ten or more.

E ramp l6 4 the reaction solution at a pH of 8 to 8.5 by the gradual addition of sodium hydroxide. 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 oiT. The product is a semi-solid paste with an appearance somewhat like stearic acid and is soluble in alkalies and acids, compatible with soap and has the power of sequestering metal ions. It

80 is believed that this compound has the following formula CH: CH H2) 1 /Hz) 1 N-C H2-C H2-N H1 HI 5 O 0N8 C O 0N8,

The sodium, potassium, and ammonium salts of the above compound and those shown in the subsequent examples may be prepared by conventional methods from the corresponding acids.

If the A an A groups are oil soluble, the calcium complexes of the compound are oil soluble. 76 An example of such a compound is given below.

Example Two mols oi toluidine, MeCcmNl-h. are reacted by known procedures with one mol of ethylene dichloride to form a symmetrical disubstituted product. The secondary hydrogen atoms are then reacted to substitute acetic acidgroups or propionic acid groups as described in the previous examples.

The formula for the compound resulting when acetic acid groups are sugtituted may be represented as follows QEQMFPEQQ L H: .oom cooNn Example 6 For example, one mol of octyl chloride and one mol of the hydro-chlorinated undecylenic acid described in Example 1 are heated with one mol of propylene 1,2-diamine until the reaction is complete. The secondary hydrogen atoms in the notrogen atoms are then replaced by CH:COONa groups or --(CH:)2COONa groups as described above. The resulting product, when the latter group is the replacing group. has the following probable formula:

on. 000m ($111): CH; Him

N-CH:-- H H1): ((81 1):

OONa OONa Example 7 One mol of lauryl chloride is heated to boiling with one mol of ethylene diamine until the reaction is complete. The resulting product is then reacted with three mols oi chloracetic acid to yield a product which may be represented by the formula 0 nnu-N-cm-c nHm-c-m-o o om H1 H1 lOONa JOONa The product has excellent detergent properties, is soluble in water, is compatible with soap, and is capable of sequestering metal ions.

A product having properties similar to those of this lauryl-trisodium-acetate-substituted ethylene diarnine results when one mol of ethylene diamine is reacted with one mol of hydrochlorinated undecylenic acid ester and the resulting product reacted with three mols of chloraoetic acid. Chlorpropionic acid may be used with satisfactory results, both as to operating procedure and characteristics of products, in either case-in place of chloracetic acid.

While most of the foregoing examples show the -(CH :)CO0M groups to be acetic acid groups or alkali metal salts thereof, these groups may be propionic acid groups instead, without 8 pounds. To add the propionic acid groups. wever, I find it best to use chlorpropionic acid, whereasto add the acetic acid groups I may use either chloroacetic acid, or the process oi my U. 8. Patent 2,407,645 above mentioned, to good advantage.

Most of the compound shown in the ioregoing examples are ethylene diamine derivatives as ethylene diamine is the most readily available of, and is typical of, the alkylene or polyalkylene polyamines embraced by the present invention. However, other polyamines which tall within the definitions herein given may be used in the same manner, following the same procedures given in the ioregoing examples-as has already been stated in Example 2, for instance, where diethylene triamine is referred to. Obviously, it these polyamines contain more than two nitrogen atoms, a correspondingly larger number of acetic or propionic acid radicals must be added to provide the final compound. Thus, whereas in making the products of this invention two mols oi CH:6OOH or (CH=):COOH (or their alkali metal salts) are required per mol Of ethylene diamine (or propylene 1,2 diamine, or trimethylene diamine) radical. three mols are required per mol of diethylene triamine (or dipropylene triamine, etc.) radical, and tour per mol of triethylene tetramine (or tripropylene tetramine, etc.) radical-and so on.

As has already been indicated in Example 2, an increase in the number of amino nitrogen atoms-and consequentl in the number of (CH:) a-COOM groups mentioned in the basic formula given at the beginning of this specification-results in increased water-solubility oi the corresponding alkali-metal salt compounds. For example, the diethylene triamine derivatives are more water-soluble than the ethylene diamine derivatives, and the triethylene tetrarnine derivatives are still more water-soluble.

The compounds shown in the above examples as the sodium salts may be as readily prepared as the iree acid or the potassium or ammonium salts. The free acid is obtained by adding hydrochloric acid, or other strong mineral acid, to a solution of the sodium salt until a pH of 2.0 to 2.5 is obtained. The precipitated acid may then be separated from the liquid present by filtration. Ammonium salts are readily prepared by dissolving the acid in aqueous ammonia. Potassium salts may be formed either by following the procedure of the examples using potassium coinpounds in place of the sodium compounds deany marked change in the prop rties oi the com- 15 scribed, or by dissolving the acid in aqueous potassium hydroxide.

For the sake of clarity a definition of terms radical and "group" used in the claims will be given. A "radical is attached to the rest oi the molecule and has at least one valence which is satisfied by a "group." Thus the radical may be an acetic acid radical CH2COO- attached through the bond on the -CH: carbon to the main part oi the molecule, and through the bond on the CO0- portion to a group." This group as pointed out hereinabove, may be hydrogen or an alkali metal such as sodium or potassium, and hence a member or group I of the periodic table of atomic weight less than 40.

The usefulness of the compounds produced in accordance with the present invention is apparent from their properties. Used alone they are excellent detergent agents and/or metal ion sequestering agents. They may be incorporated with soap in sufiicient quantity to prevent the precipitation of calcium, magnesium 'or other hard water soaps. They may be incorporated with soap. rubber. gasoline or other such material in small quantities to prevent the undesirable effects induced by traces of copper and other metal ion oxidation catalysts. The oil soluble compounds, particularly the long chain acid substituted products such as that shown in Example 2 are useful for making oil emulsions of the type known in the trade as soluble oils. These and other uses make the compounds valuable commercially.

The usefulness of such compounds is also enhanced by the fact that they may be made soluble in oils, organic solvents, or water by selecting an ester, metal salt, or acid of a compound having appropriate groups in the A and A positions. Qualities such as the foaming power may be regulated since the more hydrocarbon" carbon atoms in the A and A positions, the greater the foaming power.

I claim:

1. A compound having the formula wherein Alk is an alkylene radical of the group consisting of ethyleneand propylene, n is a positive integer not greater than 2, m is one of the group consisting of zero and a positive integer, M is selected from the group consisting of hydrogen and alkali metal, and A and A are hydrocarbon radicals containin together at least 10 carbon atoms and having not more than two of their hydrogen atoms replaced by a carboxylic radical of the group consisting of -COOH, COOM' and COOR, 11' being an alkali metal and R being the radical of an esterifiable alcohol ROI-I.

2. A compound according to claim 1 wherein n is 1.

3. A compound according to claim 1 wherein m is zero.

5. A compound according to claim 1 wherein I A and A are cyclic hydrocarbon radicals con- 5 taining together at least carbon atoms and having not more than two of their hydrogen atoms replaced by a carboxylic radical of the group consisting of -COOH, COOM', and -COOR, M? being an alkali metal and B being the radical of an esteriilable alcohol ROH.

6. A compound having the formula CH: Cg: n'ooc-c cm on, cn-cooa' R'OOC- 11 H-NCH:-QHQN H n-coon' \C 1 H: H: C a

wherein R is one of the group consisting of hydrogen and an alkyl group and M is selected from the group consisting of hydrogen and alkali metal.

7. A compound having the formula:

Na00C--(CH:)1 cum-000m H-NCHs.CHr-N H REFERENCES CITED The following references are of record in the 0 file of this patent:

UNITED STATES PATENTS Number Name Date 2,164,781 Platz et a1. 'Ju1y4, 1939 2,384,816 Curme et al Sept. 18. 1945 mamas Bersworth Oct. so. 1945

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Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2840600A (en) * 1955-02-02 1958-06-24 Armour & Co Nu-substituted trimethylene diamine-n'alkanoic acids, salts, and esters
US3485736A (en) * 1964-08-26 1969-12-23 Olof Alfred Yngve Vesterberg Method of isoelectric fractionation
DE2246907A1 (en) * 1972-09-14 1974-04-11 Tukovy Prumysl Oborove Rschedi containing a surfactant aktivierungsfaehigkeiten detergent agent with
US4352751A (en) * 1979-09-10 1982-10-05 Analytical Radiation Corporation Species-linked diamine triacetic acids and their chelates
US4432907A (en) * 1979-09-10 1984-02-21 Analytical Radiation Corporation Diamine acid fluorescent chelates
US4965211A (en) * 1979-09-10 1990-10-23 Irwin Wieder Fluorometric analysis method
US5656586A (en) * 1994-08-19 1997-08-12 Rhone-Poulenc Inc. Amphoteric surfactants having multiple hydrophobic and hydrophilic groups
US5789371A (en) * 1997-04-22 1998-08-04 Rhodia Inc. Amphoteric surfactants having multiple hydrophobic and hydrophilic groups
US5846926A (en) * 1997-06-09 1998-12-08 Rhodia Inc. Nonionic gemini surfactants with three hydrophilic heads and two lipophilic tails
US5922663A (en) * 1996-10-04 1999-07-13 Rhodia Inc. Enhancement of soil release with gemini surfactants
US6030938A (en) * 1996-12-31 2000-02-29 Rhodia Inc. Process for making salt-free amphoterics with high mono amphopropionate content
US6040288A (en) * 1997-02-21 2000-03-21 Rhodia Inc. Fabric color protection compositions and methods
US6121222A (en) * 1996-12-27 2000-09-19 Rhodia Inc. Anionic surfactants having multiple hydrophobic and hydrophilic groups
US6183550B1 (en) 1998-04-22 2001-02-06 Hercules Incorporated Paper size dispersions
US7524808B2 (en) 2007-06-12 2009-04-28 Rhodia Inc. Hard surface cleaning composition with hydrophilizing agent and method for cleaning hard surfaces
US7524800B2 (en) 2007-06-12 2009-04-28 Rhodia Inc. Mono-, di- and polyol phosphate esters in personal care formulations
US7550419B2 (en) 2007-06-12 2009-06-23 Rhodia Inc. Mono-, di- and polyol alkoxylate phosphate esters in oral care formulations and methods for using same
US7557072B2 (en) 2007-06-12 2009-07-07 Rhodia Inc. Detergent composition with hydrophilizing soil-release agent and methods for using same
US7608571B2 (en) 2007-07-20 2009-10-27 Rhodia Inc. Method for recovering crude oil from a subterranean formation utilizing a polyphosphate ester
US8993506B2 (en) 2006-06-12 2015-03-31 Rhodia Operations Hydrophilized substrate and method for hydrophilizing a hydrophobic surface of a substrate
WO2015125734A1 (en) * 2014-02-24 2015-08-27 マナック株式会社 Halohexahydrophthalic acid derivative
US9181282B2 (en) 2011-12-23 2015-11-10 Universiteit Gent Organosilica compounds

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2164781A (en) * 1934-07-26 1939-07-04 Gen Aniline Works Inc Amino-carboxylic acids and a process of preparing them
US2384816A (en) * 1941-12-20 1945-09-18 Carbide & Carbon Chem Corp Preparation of amino carboxylic acids and their salts
US2387735A (en) * 1941-07-03 1945-10-30 Martin Dennis Company Method of forming carboxylic amino acids

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2164781A (en) * 1934-07-26 1939-07-04 Gen Aniline Works Inc Amino-carboxylic acids and a process of preparing them
US2387735A (en) * 1941-07-03 1945-10-30 Martin Dennis Company Method of forming carboxylic amino acids
US2384816A (en) * 1941-12-20 1945-09-18 Carbide & Carbon Chem Corp Preparation of amino carboxylic acids and their salts

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2840600A (en) * 1955-02-02 1958-06-24 Armour & Co Nu-substituted trimethylene diamine-n'alkanoic acids, salts, and esters
US3485736A (en) * 1964-08-26 1969-12-23 Olof Alfred Yngve Vesterberg Method of isoelectric fractionation
DE2246907A1 (en) * 1972-09-14 1974-04-11 Tukovy Prumysl Oborove Rschedi containing a surfactant aktivierungsfaehigkeiten detergent agent with
US4352751A (en) * 1979-09-10 1982-10-05 Analytical Radiation Corporation Species-linked diamine triacetic acids and their chelates
US4432907A (en) * 1979-09-10 1984-02-21 Analytical Radiation Corporation Diamine acid fluorescent chelates
US4965211A (en) * 1979-09-10 1990-10-23 Irwin Wieder Fluorometric analysis method
US5656586A (en) * 1994-08-19 1997-08-12 Rhone-Poulenc Inc. Amphoteric surfactants having multiple hydrophobic and hydrophilic groups
US5922663A (en) * 1996-10-04 1999-07-13 Rhodia Inc. Enhancement of soil release with gemini surfactants
US6121222A (en) * 1996-12-27 2000-09-19 Rhodia Inc. Anionic surfactants having multiple hydrophobic and hydrophilic groups
US6030938A (en) * 1996-12-31 2000-02-29 Rhodia Inc. Process for making salt-free amphoterics with high mono amphopropionate content
US6040288A (en) * 1997-02-21 2000-03-21 Rhodia Inc. Fabric color protection compositions and methods
US5789371A (en) * 1997-04-22 1998-08-04 Rhodia Inc. Amphoteric surfactants having multiple hydrophobic and hydrophilic groups
US5846926A (en) * 1997-06-09 1998-12-08 Rhodia Inc. Nonionic gemini surfactants with three hydrophilic heads and two lipophilic tails
US6183550B1 (en) 1998-04-22 2001-02-06 Hercules Incorporated Paper size dispersions
US8993506B2 (en) 2006-06-12 2015-03-31 Rhodia Operations Hydrophilized substrate and method for hydrophilizing a hydrophobic surface of a substrate
US7524808B2 (en) 2007-06-12 2009-04-28 Rhodia Inc. Hard surface cleaning composition with hydrophilizing agent and method for cleaning hard surfaces
US7550419B2 (en) 2007-06-12 2009-06-23 Rhodia Inc. Mono-, di- and polyol alkoxylate phosphate esters in oral care formulations and methods for using same
US7557072B2 (en) 2007-06-12 2009-07-07 Rhodia Inc. Detergent composition with hydrophilizing soil-release agent and methods for using same
US7524800B2 (en) 2007-06-12 2009-04-28 Rhodia Inc. Mono-, di- and polyol phosphate esters in personal care formulations
US7867963B2 (en) 2007-06-12 2011-01-11 Rhodia Inc. Mono-, di- and polyol phosphate esters in personal care formulations
US7919073B2 (en) 2007-06-12 2011-04-05 Rhodia Operations Mono-, di- and polyol alkoxylate phosphate esters in oral care formulations and methods for using same
US7919449B2 (en) 2007-06-12 2011-04-05 Rhodia Operations Detergent composition with hydrophilizing soil-release agent and methods for using same
US8268765B2 (en) 2007-06-12 2012-09-18 Rhodia Operations Mono-, di- and polyol phosphate esters in personal care formulations
US8293699B2 (en) 2007-06-12 2012-10-23 Rhodia Operations Hard surface cleaning composition with hydrophilizing agent and method for cleaning hard surfaces
US7608571B2 (en) 2007-07-20 2009-10-27 Rhodia Inc. Method for recovering crude oil from a subterranean formation utilizing a polyphosphate ester
US9181282B2 (en) 2011-12-23 2015-11-10 Universiteit Gent Organosilica compounds
WO2015125734A1 (en) * 2014-02-24 2015-08-27 マナック株式会社 Halohexahydrophthalic acid derivative
JPWO2015125734A1 (en) * 2014-02-24 2017-03-30 マナック株式会社 Halo hexahydrophthalic acid derivatives

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