US3865755A - Detergent composition - Google Patents

Abstract

WHEREIN M is an alkali metal or ammonium, R1 and R2 are hydrogen, methyl or ethyl and R3 is hydrogen, methyl, ethyl or COOM are useful sequestrants and detergency builders. Lower alkyl esters and acids of such compounds are useful intermediates for their production. This is a division, of application Ser. No. 253,357, filed May 15, 1972 which is a continuation-in-part of U.S. applications, Ser. Nos. 158,577 and 158,540, filed June 30, 1971 and June 30, 1971, and now abandoned.

Compounds having the formula

Description

United States Patent Lannert 1 Feb. 11, 1975 DETERGENT COMPOSITION Primary Examiner-Stephen J. Lechert, Jr. [75] Inventor Kent Lannert Freeburg Attorney, Agent, or Firm-Thomas N. Wallin; J. E. [73] Assignee: Monsanto Company, St. Louis, Mo. M Neal E, Willi [22] Filed: Sept. 13, 1973 211 Appl. No.: 396,928 [571 ABSTRACT Related US. Application Data Compounds having the formula [60] Division of Ser. No. 253,357, May I5, 1972, which is a continuation-in-part of Ser. Nos. l58,577, June COOM 000M 30, 1971, and Ser. No. 158,540, June 30, 1971. 1;

1 2 abandoned.

[52] US. Cl 252/558, 252/89, 252/121,

252/539, ZSZ/DIG- 11 wherein M is an alkali metal or ammonium, R and R [51] Int. Cl Clld 1/12 are hydrogen, methyl or ethyl and R is hydrogen, Field Of Search 5 methyl, ethyl or COOM are useful sequestrants and 252/539, 5 5 DIG. 1 1 260/553 detergency builders. Lower alkyl esters and acids of such compounds are useful intermediates for their [56] References Cited production,

UNITED STATES PATENTS ll/l972 Lannert 252/558 X 12 Claims, No Drawings DETERGENT COMPOSITION This is a division, of application Ser. No. 253,357, filed May 15, 1972 which is a continuation-in-part of U5. applications, Ser. Nos. 158,577 and 158,540, filed June 30, 1971 and June 30, 1971, and now abandoned.

BACKGROUND OF THE INVENTION This invention relates to novel compounds and precursors thereof useful in sequestrants and detergency builders and to detergent formulations containing such compounds. Numerous materials are known which, by virtue of sequestering characteristics and/or capability to enhance the cleansing ability of detergent formulations in combination with various surfactants are useful in water treating applications, or as adjuvants, reenforcers, supplements, augmentors, potentiators and/or benefactors in detergent formulations wherein such materials are usually referred to as detergency builders. It is noted that although many detergency builders are also sequestrants, the determination of materials which are effective detergency builders is a complex matter emperical in nature and not accurately predictable from known characteristics of the materials.

Many materials of the foregoing type are characterized by high phosphorous content such as the alkali metal tripolyphosphates widely employed as detergency builders. It has recently been suggested by some researchers that such eompounds may contribute to the acceleration of eutrophication processes. Accordingly, particularly in the detergent builder field, extensive efforts have been exerted to provide alternate functional compounds free of phosphorus.

SUMMARY OF THE INVENTION It is an object of this invention to provide novel compounds and intermediates useful for the production of such compounds which are useful as sequestrants and as detergency builders.

The novel compounds of this invention and their manufacture and utility will be understood from the following description of the preferred embodiments.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The novel compounds of this invention are represented by the formula COOR CODE wherein R is hydrogen, methyl, ethyl, alkali metal or ammonium and R and R are hydrogen, methyl, or ethyl and R is hydrogen, methyl, ethyl or COOR.

The compounds (except those in which R, and R are hydrogen and R is COOR) can be prepared by reacting the appropriate halomalonate,

C O 0 (methyl or ethyl) 0 0 (methyl or ethyl) (X being Cl when R is hydrogen and being Cl or Br when R, is methyl) with the sodium salt of the appropriate a-hydroxy ester C 0 0 (methyl or ethyl) NB,O- I Re in an inert solvent such as l,2-dimethoxyethane or tetrahydrofuran.

This reaction yields the ester forms of the compounds of this invention which are saponified by conventional techniques to yield the desired ammonium or alkali metal salts. The acid forms of the compounds of this invention are obtained by acidifying the salts. The acids can be crystallized by conventional techniques to provide useful precursors for high purity salts. It is noted that when R, is hydrogen, the acid is relatively unstable due to a tendency to undergo rapid decarboxylation.

Those compounds in which R is COOR, including those in which R and R are hydrogen can be prepared by adding a solution (preferably about 1 molar) of compounds represented by the formula 000(methyl or, ethyl) COO(methyl or ethyl) Ri J---O R2 II III in tetrahydrofuran to two equivalents of lithium diisopropylamide in tetrahydrofuran solution (preferably about 1 molar) at a temperature of about 78C.

It is believed that this procedure results in formation of a lithium salt represented by the formula C O 0 (methyl or ethyl) C O 0 (methyl or ethyl) R1 I--O Rz Li Li Gaseous CO is then introduced to form 000(methyl or ethyl) 000(methyl or ethyl) OOLi The dilithium salt is converted to a half-ester halfacid C00(methyl or ethyl) 000(rnethyl or ethyl) R1- --0 Rz by treatment with an organic strong acid cation exchange resin, for example, a sulfonated polystyrene resin such as marketed by Fischer Scietific Co., under the trademark Rexyn 101(H). The ester forms can be obtained by conventional esterification procedures. The salt forms are obtained by saponification of the half-ester half-acid.

In one preferred embodiment of the invention, R is sodium and R R and R are hydrogen. In aother preferred embodiment, R is sodium, R, is methyl and R and R are hydrogen. In another preferred embodiment, R is sodium, R and R are hydrogen and R is COONa. These embodiments are preferred by virtue of availability of raw materials for their manufacture and their excellent performance as detergency builders.

Both the acid and salt forms of the compounds of this invention are useful as metal ion sequestrants and as detergency builders, the use of the salt form being preferred.

The detergent formulations utilizing the compounds of this invention will contain from 1 to 75 percent by weight, preferably from 5 to 50 percent by weight of the salt, preferably sodium salt forms of the compounds of this invention. Such compounds can be utilized as the sole detergency builder in the compositions or in combination with other known detergency builders such as water soluble inorganic builder salts, for example, alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates or organic builders such as salts of phytic acid, sodium citrate, water soluble polymeric polycarboxylates as described in U.S. Pat. No. 3,308,067 and the like.

The detergent formulations will additionally contain at least 8 percent by weight of a surfactant. Any of the numerous well known anionic, nonionic, zwitterionic or ampholytic surfactants can be employed.

Examples of suitable anionic surfactants include alkyl ethyl sulfonates, alkyl sulfates, acyl sarcosinates; acyl esters of isocyanates, acyl N-methyl taurides, and alkyl aryl sulfonates. The foregoing materials are used in the form of their water-soluble sodium, potassium, ammonium and alkyl ammonium salts. Specific examples include sodium laryl sulfate; sodium N-methyl aluryll tauride; sodium dodecyl benzene sulfonate; and triethanol amine undecanol benzene sulfonate.

Examples of suitable nonionic detergents include alkyl phenol and alcohol alkoxylates including condensates of l-decanol or l-undecanol with from 3 to 5 molecular proportions of ethylene oxide such as described in US. Pat. application Ser. No. 707,480 filed Feb. 23, 1968 and now abandoned; condensates of monohydroxy or polyhydroxy alcohols such as oleyl alcohol or l-tridecanol with from 9 to molecular proportions of ethylene oxides; alkyl internal vicinal dialkoxy or hydroxy alkoxy compounds as described in US. Pat. application Ser. No. 852,898 filed Aug. 25, 1969 and now abandoned; and condensates of alkylene oxides with organo amines, for example, ethylene diamine and amides such as N-octadecyl diethanol amide.

Suitable ampholitic surfactants include the amido alkene sulfonates such as sodium C-pentadecyl, N- methyl amido ethyl sulfonate potassium C-octyl N- napthalene amido propyl sulfonate; ammonium C- decyl, N-cycle propyl amido butyl sulfonate and aliphatic amine derivatives in which the aliphatic substituent contains an anionic water-solubilizing substituent such as a carboxy, sulfo, phosphato, or phosphino group, for example, sodium-3-dodecyl amino propionate and sodium-3-dodecyl amino propane sulfonate.

Examples of zwitterionic surfactants include derivatives'of quaternary ammonium phosphonium and sulfonium compounds such as 3-(N,N-dimethyl-N- hexadecyl ammonio) propane-l-sulfonate and 3-(N,N-dimethyl-N-hexadecyl ammonio-2-hydroxy propane-l-sulfonate).

It will be understood that the above examples of supplementary surfactants are by no means comprehensive. Numerous other surfactants are known to those skilled in the art and are set forth in such familiar references as Surface Active Agents by A. M. Schwarz and James W. Perry. It will be further understood that the use of such surfactants will be in accordance with conventional, well-understood practices of detergent formulation. For example, cationic and anionic detergents will not normally be employed in combination clue to recognized problems of precipitation of insoluble products. 1

In accordance with general practice, the ratio of the detergency building components to the surfactant components will be in the range of from 1:2 to about 12:1 by weight.

In addition to surfactant and builder components, the detergent formulations may contain fillers such as sodium sulfate and minor amounts of bleaches, dyes, optical brighteners, soil anti-redeposition agents, perfumes and similar conventional detergent formulation additives.

It is further expected that the compounds of this invention will function effectively in machine dishwashing formulations as total or partial replacements for sodium tripolyphosphate.

The invention is further illustrated by the following Examples wherein all parts and percentages are by weight unless otherwise indicated.

EXAMPLE I To a slurry of 34 grams sodium ethyl glycolate in 300 ml of 1,2-dimethoxyethane is added with stirring to a solution of 63 grams diethyl 2-bromo-2- methylmalonate in 100 ml of 1,2-dimethyoxyethane precooled to 5C. During slurry addition, the temperature is maintained below 10C. The reaction mixture is maintained at 25C for 16 hours and at 65C for 2 hours with stirring. Solids are recovered by filtration and solvent removed under reduced pressure. The residue is dissolved in CHCl and the solution is washed, in succession, with 0.5 normal HCl, saturated Na CO and water. The solution is then dried over anhydrous MgSO, and the Cl-lCl removed under reduced pressure. The residue is fractionally distilled with product being collected at -97C, 0,04 mm Hg.

The product is identified as triethyl 2-oxa-1,3,3- butane tricarboxylate by nuclear magnetic resonance and elemental analysis.

The ester is saponified in an aqueous ethanol solution of sodium hydroxide at room temperature. Acidifying the solution with H 50 yields the acid which is extracted with ether and cystallized therefrom.

Pouring the saponified solution into excess methanol precipitates the salt.

EXAMPLE II The salt and acid produced according to Example I are tested for sequestration characteristics and are found to effectively sequester Ca ions.

EXAMPLE lIl Detergent formulations containing 12 percent alkylbenzene sulfonate having an average alkyl chain length of about 12 carbon atoms from 5 to 75 percent trisodium 2-oxa-1,3,3-butanetricarboxylate; 12 percent sodium silicate having an SiO to Na O ratio of about 2.4; and a quantity of sodium sulfate sufficient to equal percent are found, in conventional laundry operations, to clean soiled samples of cotton and polyester cotton broadcloth substantially better than otherwise identical formulations containing no trisodium 2-oxa-l ,3,3,- butanetricarboxylate. These tests demonstrate that this material is an effective detergency builder material.

EXAMPLE IV The tests of Example III above are repeated using a detergent formulation in which Neodol 45-11 (a non- -ionic surfactant which is an aduct of a modified oxo type C, C, alcohol with an average of 11 moles of ethylene oxide is substituted for the alkylbenzene sulfonate. Comparable results are obtained.

EXAMPLE V The tests of Example III are repeated with a detergent formulation wherein sodium hydroxyalkyl (C -C alkyl chain length) N-methyl laurate, and ampholytic surfactant, is substituted for the alkylbenzene sulfonate. Comparable results are obtained.

EXAMPLE VI The tests of Example III are repeated with a detergent formulation wherein cocodimethysulfopropylbetaine, a zwitterionic surfactant is substituted for the alkylbenzene sulfonate. Comparable results are obtained.

EXAM PLE VII To a slurry of 72 grams of sodium ethyl glycolate in 350 ml of 1,2-dimethoxyethane at 50-65C is added 97 grams of diethyl chlorom alonate over a two hour period. The resulting solution is refluxed until a neutral pH is obtained. The reaction mix is then stirred for 16 hours at 25C and reaction product isolated as in Example I, the product being collected at ll9-l20C, 0.05 mm Hg. The product is identified as triethyl 2-oxal,1,3-propanetricarboxylate. Salts and acid forms of the product are prepared as in Example I and are found to be effective sequestrant for Ca ions.

EXAMPLE VIII Detergent formulations containing from 5 percent-75 percent trisodium 2-oxa-1 ,1 ,3- propanetricarboxylate are prepared and tested as in Examples llI-Vl. Comparable results are obtained.

EXAMPLE IX A solution of 63 gms diethyl 2-bromo-2- ethylmalonate in 25 ml tetrahydrofuran is added to a slurry of 59 gms sodium diethylmethyltartronate in 300 ml tetrahydrofuran at 65C. The mixture is refluxed for 18 hours after which the tetrahydrofuran is removed under vacuum and the residue diluted with ethyl ether. The ethereal solution is washed with water to remove NaBr, dried over anhydrous CaSO and distilled to remove the ether.

The residue is fractionally distilled, product being collected at l30-135C (0.06 mm Hg). The product is identified as tetraethyl 3-oxa-2,2,4,4-hexanetetracarboxylate by nuclear magnetic resonance and elemental analysis.

The sodium salt is obtained by saponitication in a methanol solution of sodium hydroxide at room temperature and recovered by filtration.

EXAMPLE X To a slurry of 34 grams sodium ethyl glycolate in 300 ml tetrahydrofuran cooled to about 3C is added a solution of 63 grams diethyl 2-bromo-2-ethylmalonate in 25 ml tetrahydrofuran at about 3C. The mixture is maintained at -5C with stirring for 2 hours, warmed to and maintained at about 25C for 16 hours and then refluxed for 2 hours.

The tetrahydrofuran is removed under vacuum and the residue treated as in Example llX, the ester product triethyl-Z-oxa-l,3,3-pentanetricarboxylate being collected at 101C 107C (0.05 mm Hg) and converted to the salt form as described in Example IX.

EXAMPLE XI Sodium ethyl lactate (38 gms) and diethyl 2-bromo-2-ethylmalonate are reacted according to the procedure of Example X to yield an ester product triethyl-3-oxa-2,4,4-hexanetricarboxylate being collected at 92C96C (0.04 mm Hg) which is converted to the salt form as described in Example X.

EXAMPLE Xll To a slurry of 98 grams of sodium ethyl lactate in 400 ml 1,3-dimethoxyethane at R.T. is added 136 grams diethyl chloromalonate. The mixture is heated at C for 8 hours and then maintained at 25C for 48 hours. The 1,2-dimethoxyethane is evaporated and the residue dissolved in chloroform, washed with water to remove NaCl, dried over MgSOQ, and the CHCl evaporated. Fractional distillation of the residue gives a product (b.p. 94C 96C at 0.03 mm Hg) analytically identified as triethyl 2-oxa-l,1,3butanetricarboxylate. Saponification of the ester with NaOH yields trisodium 2-oxal ,1 ,3-butanetricarboxylate.

EXAMPLE XIllI To a slurry of 77 grams of sodium ethyl lactate in 300 ml 1,2-dimethoxyethane at 45C is: added a solution of 127 gms diethyl 2-bromo-2-methylmalonate in 1,2 dimethoxyethane and the temperature is allowed to rise to about 65C. The mixture is refluxed until the pH of a water solution of the mixture is about 7. The 1,2- dimethoxyethane is evaporated, the residue washed with water to remove NaBr. Distillation of the dried residue yields a product (coolected at 82C, 0.05 mm Hg) analytically identified as triethyl 3-oxa-2,2,4-pentanetricarboxylate. Saponification of the ester with NaOH yields trisodium 3-oxa-2,2,4-pentanetricarboxylate.

EXAMPLE XIV A 1 liter flask is purged with nitrogen, charged with 400 ml tetrahydrofuran and cooled to 30C in a dryice acetone bath. 1 15 ml 2.3 molar solution of nbutyllithium in tetrahydrofuran is added and the solution cooled to -C. A solution of 21 gms diethyl glycolate in 100 ml tetrahydrofuran is added, the temperature being maintained below 70C. CO is then bubbled into the mixture for about an hour and the mixture warmed to room temperature, the tetrahydrofuran is evaporated leaving a yellow powder. The powder is dissolved in water and 100 ml of Rexyn 101(H) ion exchange resin added. An insoluble gum separates and is removed. The remaining solution is then passed through a column packed with sufficient resin to complete the conversion to the half-ester half-acid.

The water solution of half-acid half ester product is dried to a syrup. This material is dissolved in 25 ml eth- 7 orated and the residue distilled. Product collected at 141C 141C (0.05 0.1 mm Hg) is identified as tetraethyl 2-oxa-1,1 ,3 ,3-propanetetracarboxylate.

Alternatively, saponification of the half-acid halfester with sodium hydroxide yields tetrasodium 2-oxal ,1 ,3 ,3-propanetetracarboxylate.

EXAMPLE XV EXAMPLE XVI Detergent formulations containing 5 percent 75 percent of the salt forms of the compounds produced according to Examples lXXV are prepared and tested as in Examples lIl-VI. Comparable results are obtained.

What is claimed is:

1. A detergent composition comprising at least 8 percent by weight of a surfactant selected from the group consisting of anionic, nonionic, zwitterionic, ampholytic and amphoteric surfactants and from 1 percent to 75 percent by weight of a detergency builder compound having the formula 000M CO OM Rr- O- I R2 00M Ra wherein M is selected from the group consisting of alkali metals and ammonium and R, and R are each selected from the group consisting of hydrogen, methyl and ethyl and R is selected from the group consisting of hydrogen, methyl, ethyl and COOM.

2. A composition according to claim 1 wherein said detergency builder constitutes from 5 percent to 50 percent of the weight of the composition.

3. A composition according to claim 1 wherein the surfactant is a linear alkylbenzene sulfonate surfactant.

4. A composition according to claim 1 wherein M is sodium.

5. A composition according to claim 4 wherein R and R are hydrogen and R, is a methyl substituent.

6. A composition according to claim 4 wherein R,, R and R are hydrogen.

7. A composition according to claim 4 wherein R, and R are methyl substituents and R is hydrogen.

8. A composition according to claim 4 wherein R, and R are hydrogen and R is a methyl substituent.

9. A composition according to claim 1 wherein R is COOM.

10. A composition according to claim 9 wherein R, and R are hydrogen.

11. A composition according to claim 9 wherein R, and R are methyl.

12. A composition according to claim 9 wherein R,

is methyl and R is hydrogen.

Claims (12)

1. A DETERGENT COMPOSITION COMPRISING AT LEAST 8 PERCENT BY WEIGHT OF A SURFACTANT SELECTED FROM THE GROUP CONSISTING OF ANIONIC, NONIONIC, ZWITTERIONIC, AMPHOLYTIC AND AMPHOTERIC SURFACTANTS AND FROM 1 PERCENT TO 75 PERCENT BY WEIGHT OF A DETERGENCY BUILDER COMPOUND HAVING THE FORMULA

2. A composition according to claim 1 wherein said detergency builder constitutes from 5 percent to 50 percent of the weight of the composition.

3. A composition according to claim 1 wherein the surfactant is a linear alkylbenzene sulfonate surfactant.

4. A composition according to claim 1 wherein M is sodium.

5. A composition according to claim 4 wherein R2 and R3 are hydrogen and R1 is a methyl substituent.

6. A composition according to claim 4 wherein R1, R2 and R3 are hydrogen.

7. A composition according to claim 4 wherein R1 and R2 are methyl substituents and R3 is hydrogen.

8. A composition according to claim 4 wherein R1 and R3 are hydrogen and R2 is a methyl substituent.

9. A composition according to claim 1 wherein R3 is COOM.

10. A composition according to claim 9 wherein R1 and R2 are hydrogen.

11. A composition according to claim 9 wherein R1 and R2 are methyl.

12. A composition according to claim 9 wherein R1 is methyl and R2 is hydrogen.