US3927073A

US3927073A - Esters of dicarboxylic acids and polyhydroxy tertiary amines as new detergent softener compounds

Info

Publication number: US3927073A
Application number: US409027A
Authority: US
Inventors: Bjorn Sundby
Original assignee: Colgate Palmolive Co
Current assignee: Colgate Palmolive Co
Priority date: 1971-12-06
Filing date: 1973-10-24
Publication date: 1975-12-16
Anticipated expiration: 1992-12-16
Also published as: DE2258564A1; US3893930A; US3928422A; FR2166982A5; GB1420209A; US3803036A; AU4956372A; CH576944A5

Abstract

Novel esters of dicarboxylic acids and polyhydroxy tertiary amines having the structural formula:

wherein R1 is a monovalent hydrocarbon radical of 8 to 24, preferably 10 to 20 carbon atoms; R2 is an C1-C6 alkyl or alkylol radical containing 2 to 6 carbon atoms, and R3 is an alkylol radical containing 2 to 6 carbon atoms. The reaction mixture consists of mono-, di-, and/or tri-esters depending on the number of reactive hydroxyl groups in the alcoholamine and the amount of dicarboxylic acid utilized. These novel esters and salts thereof uniquely possess both detergency and softening properties.

Description

United States Patent [191 Sundby 11] 1 3,927,073 Dec. 16, 1975 ESTERS OF DICARBOXYLIC ACIDS AND POLYHYDROXY TERTIARY AMINES AS NEW DETERGENT SOFTENER COMPOUNDS Inventor: Bjorn Sundby, Piscataway, NJ.

Colgate-Palmolive Company, New York, N.Y.

Filed: Oct. 24, 1973 Appl. No.: 409,027

Related US. Application Data Assignee:

References Cited FOREIGN PATENTS OR APPLICATIONS 5/1967 France 260/475 P Primary ExaminerLorraine A. Weinberger Assistant ExaminerE. Jane Skelly Attorney, Agent, or FirmSteven J. Baron; Norman Blumenkopf; Herbert S. Sylvester [57] ABSTRACT Novel esters of dicarboxylic acids and polyhydroxy tertiary amines having the structural formula:

wherein R is a monovalent hydrocarbon radical of 8 to 24, preferably 10 to 20 carbon atoms; R is an C -C alkyl or alkylol radical containing 2 to 6 carbon atoms, and R is an alkylol radical containing 2 to 6 carbon atoms. The reaction mixture consists of mono-, di-, and/or tri-esters depending on the number of reactive hydroxyl groups in the alcoholamine and the amount of dicarboxylic acid utilized. These novel esters and salts thereof uniquely possess both detergency and softening properties.

3 Claims, No Drawings pounds are useful surface active agents and are sub- 1 stantive to a variety of fibrous materials. Thus, they may be used as emulsifiers, solubilizing agents for lipophilic materials, wetting agents, detergents and softeners for textiles and hair.

Since the introduction of commercial synthetic organic detergents and emulsifiers to replace the conventional watersoluble higher fatty acid soaps, much research work has been performed in an effort to improve such compounds and compositions including them, with the object of obtaining better and more convenient laundering of textiles. As a result, a wide variety of types of surface active agents and detergents have been produced and many such compositions have been manufactured commercially and have been introduced to the market place. As better products were made, the goals set for researchers on detergency were increased and the properties of the desired products were such as to have been thought impossible of attainment only a few years before. Although the cleaning function of surface active materials is still very important and products which clean better than competitive compounds are always in demand, additional attributes of cleaning compounds were desired. For example, with the increasing importance of cold water washing, detergent compositions were desired which would be capable of successfully cleaning and whitening textiles and laundry in cold water, as well as in hot water. Such washing capability is of importance in making a product acceptable for the washing of wool and other shrink-sensitive materials. In addition, softening agents have been found to be a desirable and in some instances, a necessary ingredient in the washing of textiles. However, because of the incompatibility of softeners and detergents, it has been necessary to utilize the textile softener in the final rinse as a separate step in a washing cycle. The objections to this procedure are obvious; one must be present during the washing cycle and few washing machines include devices for the addition of softeners in the final rinse.

Therefore, it has been the long desire of the detergent industry to provide a single compound possessing the foaming and detergency characteristics of conventional detergents yet, uniquely possessing fabric softening ability. Such a single compound uniquely possessing both detergency and fabric softening ability would of course eliminate the disadvantages of employing two separate materials and in addition, would completely eliminate the disadvantages associated with the incompatibility of conventional anionic detergents and cationis fabric softeners.

The present invented compounds have the combined properties of detergency and textile softening. They possess detergent activity in both hard and soft waters and at both elevated and lower temperatures. In addition, these compounds are excellent in textile softening activity. Such an activity evidences a high degree of substantivity, which is unexpected in a surface active 2 material which itself functions to release adsorbed and absorbed substances from materials being washed.

In accordance with the present invention, there are provided novel esters of dicarboxylic acids and 2- hydroxyalkyl tertiary alcohol amines and salts thereof consisting predominantly of the mono-ester having the formula:

which are effective detergents and which also serve to soften fibrous materials when applied to them, as in aqueous solution. In the formula, R is a monovalent hydrocarbon radical of 8 to 24 and preferably 10 to 20 carbon atoms, R is an C -C alkyl or alkylol radical of 2 to 6 carbon atoms, R, is a divalent hydrocarbon radical of 2 to 6 carbon atoms (R =R OH); R is a saturated, unsaturated, aliphatic or aromatic divalent -hydrocarbon radical (residue of the dicarboxylic acid), X is hydrogen or a salt-forming element or radical. If X is an element it is preferred that it should be an alkali metal such as potassium, sodium and lithium or other suitable salt-forming metal, capable of making the compounds water soluble. If X is a radical it is preferred that such be ammonium, alkylamine or alkanolamine, either mono-, di-, or tri-alkylamine or mono-, dior tri-alkanolamine, in which the alkyl and alkanol groups of the salt-forming amines are of 1 to 4 carbon atoms, preferably 2 to 3 carbon atoms.

The novel esters of the present invention are prepared by reacting the dicarboxylic acid or preferably the anhydride thereof with a polyhydroxy tertiary amine having the structure:

wherein R is a monovalent hydrocarbon radical of 8 to 24 and preferably 10 to 20 carbon atoms, R is an C -C alkyl or hydroxyalkyl radical containing 2 to 6 carbon atoms, R is a hydroxy alkyl radical containing 2 to 6 carbon atoms. Examples of radicals of this class are:

and related compounds in which the radicals contain more carbon atoms than in the formula shown above, e.g., radicals of di(isopropanol)amine, N-methyl-N-iso- OH H CH OH heat ' CH CH OH ca, HN

The dicarboxylic acid may be saturated, unsaturated, substituted or unsubstituted aliphatic or aromatic and include phthalic, succinic, maleic, glutaric, tartaric, malic, adipic, diphenic, naphthalic, etc.

The reaction is predominently in accordance with the following equation:

wherein the R radicals are as aforedefined, and equimolar amounts of reactants are used. The alcoholamine has at least two hydroxyl groups, one in the long chain resulting from the epoxide ring opening and one or more from the original alcoholamine. When utilizing equimolar amounts of reactants, the primary hydroxyl is preferentially esterified into the mono-ester, since it is the least stearically hindered and therefor the most reactive group. However, when more than one mole of the acid anhydride is used, the other hydroxyl radicals react to form the di-ester, tri-ester, etc. and mixtures thereof. Similarly, the number of hydroxyl groups in the alcoholamine is determinative of the formation of the mono-, di-, or triesters.

4 The esters formed in accordance with instant invention have one free carboxyl group for every esterified carboxyl radical as shown by the following structural formulae:

mono-ester:

di-ester:

CH,CH2OH Ol' OCR5COOH R,- CH2NR4OOCR,,COOH

tri-ester:

OOCRSCOOH R, -CH2 R4-OOCR5COOH RZOOCRSCOOH The esterification of the 2-hydroxyalkylalcoholamines with the dicarboxylic acid anhydride is an exo-.-

thermic reaction which can be carried out in aprotic solvent, ether, chloroform or acetone, but it can also be carried out neat. The latter method is preferable as an industrial process, since no solvent is involved. The powdered acid anhydride (e.g. maleic anhydride) is added gradually to the liquid alcoholamine which is held at a temperature of about C. The product is obtained as a high viscosity melt, that rapidly solidifies upon cooling. The ester (e.g. maleate) may be con-. verted to the alkali metal salt (e.g. sodium) by neutralizing with a dilute aqueous solution of alkaliv metal hydroxide such as a 10% NaOH. When utilizing a sol vent, the reactants are first dissolved therein and the solution refluxed until the esterification has taken place. Evaporation of the solvent yields a resin-like waxy product, insoluble in water, but readily soluble in mono, di-, and

triesters mono-, di-esters monoand di-esters :0 a dilute aqueous sodium hydroxide solution.

When utilizing the dicarboxylic acid in lieu of the anhydride, the reaction is controlled so that only one mole of water is removed per mole of alcohol. Termination of the reaction at this point ensures the forma tion of the esters of instant invention and prevents the production of a polymeric linear ester. The reaction may be controlled by conventional methods of cooling or by other suitable means.

The products obtained are usually yellow or light yellow viscous mono, di, tri-esters and mixtures thereof, resin-like in appearance, insoluble in water, but readily soluble in alcohol, acetone, chloroform and in dilute aqueous sodium hydroxide wherein the sodium salt of the ester is formed. The mono-, diand tri-esters can be readily separated and purified by chromatographic techniques in the usual manner. The sodium salts of instant novel esters are homogeneous and very water soluble, whereas the sodium salts of the" esters of secondary amines and dicarboxylic acids are less homogeneous and less water-soluble. Consequently, instant esters and salts thereof have been found to be particularly useful as detergents, due to their combined property of detergency and fabric conditioning (softeningianti-static, etc.).

Examples of esters in accordance with the present invention include:

N-(Z-hydroxydodecyl)-methylethanolamine maleate N-(Z-hydroxyoctadecyl)-methylethanolamine maleate N-(Z-hydroxydodecyl) diisopropanolamine maleate N-( 2-hydroxyoctadecyl) diisopropanolamine malea te N- (2-hydroxydodecy1)-diethanolamine maleate N-(2-hydroxyoctadecyl) diethanolamine maleate v N-(2-hydroxydodecyl)-diglycolarnine maleate N-(Z-hydroxoctadecyl);diglycolamine maleate N-(2-hydroxypentadecyl)-diethanolamine phthalate N-(2-hydroxyoctadecyl) die'thanolamine phthalatel...

The novel esters of the present invention, in addition to possessing excellentdetergency and water softening properties, have been found to be-compatible with the various detergent builders and other additives conventionally employed in detergent compositions. Accordingly, it is possible to formulate a detergent composition based upon the tertiary alcohol amine-dicarboxylic acid ester as the detergent and water softener.

Various embodiments of the present invention will now be illustrated by reference to the following specific examples. It is to be understood however that such examples are presented for purposes of illustration only and the present invention is in no way to be deemed as limited thereby.

EXAMPLE 1 Preparation of N-(2-hydroxyhexadecyl)-diethanolamine maleate:

35 grams (0.1 mole) of N-(2-hydroxyhexadecyl)-diethanolamine was melted and heated to 100C. 1 1 grams (0.11 mole) powdered maleic anhydride was added gradually to the hot melt with vigorous agitation. The

6 reaction mixture became at once very viscous with a clear yellow color. The mix-ture was heated to the melting point and then cooled. The product solidified to a semi-solid yellow material with a pleasant odor, readily soluble in alcohol, acetone and chloroform.

EXAMPLE 2 1 Preparation of sodium maleate of N( 2.-hydroxyhexadecyl)-diethanolamine:

OH C H CH OH The maleate prepared in accordance with Example 1 is cooled to about C and then neutralized with 10% sodium hydroxide.

EXAMPLE-:3

Preparation of. N-( 2-hydroxyhexadecyl)-diethanola mine phthalatez 30 gr. of N( 2-hydroxyhexadecyl)-diethanolamine and 12.9 gr. phthali'c anhydride (0.087'moles of each) were dissolved in m1 acetone',and the solution was refluxed'for-two hours. The acetone was removed by evaporation, leaving a resin-like light yellow waxy material insoluble in'water. i

EXAMPLE 4 Preparation of sodium'phthalate of N-( 2 hydroxyhexadecyl)-diethanolamine:

on cH,cH,o|-i

COONa Three Spangler soil swatches were washed 10 minutes in Terg-O-Tometer, followed by a 5 minute rinse.

Similarly the test for softening effect on cotton materials is run using a terry cloth towel in three gallons of 100 ppm. hardness water. After washing in a miniature washing machine, the towel is rinsed in the normal manner and dried. The softness is rated on a scale of 1 to 10, with 1 indicating no softness and 10 representing maximum softness.

Table l ARd (Soil Removal) Softness 7 F I20F Compound NB-TAP SOOPPM NB-TAP 300 PPM 1. Ester of N-(Z- y y is-ui alkyl )-diethanol- 1 amine and maleic anhydride, Na-salt 14.2 12.0 15.6 9.8 2. Ester of N-(2- I hydroxy C alkyl )-diethanolamine and phthalic anhydride, Na-salt 17.6 1 1.5 16.8 12.5 9 3. Control-Linear tridecyl benzene sulfonate (LTBS) 17.0 11.0 19.2 13.1 1 4. Product of 18.0 1 1.7 20.4 12.8

Example 3 5. Control LTBS 16.2 9.9 21.0 12.2

and The results shown above lndlcate an unexpectedly excellent detergency in hard and soft water, both cold 0 and hot, as compared to commercial detergent linear AC fi tridecyl benzene sulfonate. In addition to possessing excellent detersive properties, instant esters exhibit (B) excellent fabric softening characteristics, not possessed by the control. Similar results are obtained with other 2-hydroxy alkyl tertiary alcohol aminedicarboxylic esters and salts thereof.

The present invention has been described, in conjunction with various illustrations and embodiments thereof set forth in the. specification. However, it is evident that equivalents may be substituted for the present compounds and procedural steps, without departing from the principles of this invention or the spirit thereof. Those of skill in the art will recognize what equivalents and substitutes are also within the scope of the present disclosure.

What is claimed is:

1. A compound having in the free acid form a formula selected from the groupconsisting of and mixtures of (A) and (B) wherein 1. R is C; to C alkyl, 2. R isC to C alkyl or C -C alkylol, 3. R and R are alkylene of C to C and 4. R represents the residue of a dicarboxylic acid and selected from the group consisting of maleic, succinic, glutaric, tartaric, malic, adipic, diphenic and naphthalic acids. 2. Compounds in accordance with claim 1, wherein the dicarboxylic acid is maleic acid. 3. A compound having the formula

Claims

1. A COMPOUND HAVING IN THE FREE ACID FORM A FORMULA SELECTED FROM THE GROUP CONSISTING OF

1. R1 IS C8 TO C24 ALKYL,

2. R2 IS C1 TO C6 ALKYL OR C2-C6 ALKYLOL,

2. R2 is C1 to C6 alkyl or C2-C6 alkylol,

2. Compounds in accordance with claim 1, wherein the dicarboxylic acid is maleic acid.

3. A compound having the formula

3. R3 and R5 are alkylene of C2 to C6, and

3. R3 AND R5 ARE ALKYLENE OF C2 TO C6, AND

4. R4 REPRESENTS THE RESIDUE OF A DICARBOXYLIC ACID AND SELECTED FROM THE GROUP CONSISTING OF MALEIC, SUSSINIC, GLUTARIC, TARTARIC, MALIC, ADIPIC, DIPHENIC AND NAPTHALIC, ACIDS.

4. R4 represents the residue of a dicarboxylic acid and selected from the group consisting of maleic, succinic, glutaric, tartaric, malic, adipic, diphenic and naphthalic acids.