US3742045A - Detergency builders - Google Patents

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US3742045A
US3742045A US00158539A US3742045DA US3742045A US 3742045 A US3742045 A US 3742045A US 00158539 A US00158539 A US 00158539A US 3742045D A US3742045D A US 3742045DA US 3742045 A US3742045 A US 3742045A
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compounds
detergency builders
sodium
methyl
ammonium
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US00158539A
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K Lannert
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Monsanto Co
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Monsanto Co
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2089—Ether acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/235—Saturated compounds containing more than one carboxyl group
    • C07C59/305—Saturated compounds containing more than one carboxyl group containing ether groups, groups, groups, or groups

Definitions

  • ABSTRACT Compounds having the formula wherein M is an alkali metal or ammonium and R and R are hydrogen or methyl are useful sequestrants and detergency builders. Lower alkyl esters and acids of such compounds are useful intermediates for this production.
  • detergency builders 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 sequenstrants, 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.
  • novel compounds of this invention are represented by the formula wherein R is hydrogen, methyl, ethyl, alkali metal or ammonium and R and R are hydrgen or methyl.
  • the compounds are readily prepared reacting the appropriate alkyl bromomalonate with the sodium salt of the appropriate a-hydroxy ester in an inert solvent such as 1,2-dimethoxyethane.
  • 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.
  • R is sodium and R and R are both methyl or hydrogen. 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 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 carbonate, borates, phosphates, polyphosphate, bic'arbonates and silicates or organic builders such as salts of phytic acid, sodium citrate, water soluble polymeric polyc'arboxylates 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.
  • 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.
  • 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 U.S. Pat. application Ser. No. 707,480 filed Feb. 23, 1968 and copending herewith; condensates of monohydroxy or polyhydroxy alcohols such as oleyl alcohol or l-tridecanol with from 9 to 15 molecular proportions of ethylene oxides; alkyl internal vicinal dialkoxy or hydroxy alkoxy compounds as described in U.S. Pat. application Ser. No. 852,898 filed Aug. 25, 1969, now abandoned; and condensates of alkylene oxides with organo amines, for example, ethylene diamine and amides such as N-octadecyl diethanol amide.
  • organo amines for example, ethylene diamine and amides such as N-octadecyl diethanol amide.
  • cationic surfactants include octadecyl ammonium chloride; straight chain fatty amines having 8 to 18 carbon atoms; and quaternary ammonium compounds such as octadecyl trimethyl ammonium chloride.
  • 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-cyclo 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-3dodecyl amino propionate and sodium-S-dodecyl amino propane sulfonate.
  • amido alkene sulfonates such as sodium C-pentadecyl, N- methyl amido. ethyl sulfonate potassium C-octyl N- napthal
  • zwitterionic surfactants include derivatives of quaternary ammonium phosphonium and sulfonium compounds such as 3-(N,N-dirnethyl-N- hexadecyl ammonio) propane-l-sulfonate and 3-(N,N-diemthyl-N-hexadecyl ammonio-Z-hydroxy propanel -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 due to recognized problems of precipitation of insoluble products.
  • the ratio of the detergency building components to the surfactant components will be in the range of from 1:2 to about 12:] by weight.
  • the detergent formulstions may contain fillers such as so dium sulfate and minor amounts of bleaches, dyes, optical brighteners, soil anti-redeposition agents, perfumes and similar conventional detergent formulation additives.
  • 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 Ill EXAMPLE IV
  • Neodole 45-1 1 a nonionic surfactant which is an aduct of a modified oxo type C -C alcohol with an average of l 1 moles of ethylene oxide is substituted for the alkylbenzene sulfonate. Comparable results are obtained.
  • Example V EXAMPLE V The tests of Example Ill are repeated with a detergent formulation wherein sodium hydroxyalkyl (C -C alkyl chain length) N-methyl taurate, 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 cocodimethylsulfopropylbetaine, a zwitterionic surfactant is substituted for the alkylbenzene sulfonate. Comparable results are ob tained.
  • R is selected from the group consisting of hydrogen, methyl, ethyl, alkali metal and ammonium and R and R are each selected from the group consisting of hydrogen and methyl.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Compounds having the formula

WHEREIN M is an alkali metal or ammonium and R1 and R2 are hydrogen or methyl are useful sequestrants and detergency builders. Lower alkyl esters and acids of such compounds are useful intermediates for this production.

Description

United States Patent [1 1 Lannert [52] US. Cl. 260/535 P, 252/DIG. ll, 252/135, 252/180, 252/539, 200/484 P [51] Int. Cl. C07c 59/22 [58] Field of Search 260/535, 484 P [56] References Cited UNITED STATES PATENTS 2,377,246 5/1945 Kyrides 260/535 P June 26, 1973 Primary Examiner-Lorraine A. Weinberger Assistant Examiner-Paul J. Killos Attorney-Herbert B. Roberts, Thomas N. Wallin et al.
[57] ABSTRACT Compounds having the formula wherein M is an alkali metal or ammonium and R and R are hydrogen or methyl are useful sequestrants and detergency builders. Lower alkyl esters and acids of such compounds are useful intermediates for this production.
4 Claims, No Drawings DETERGENCY BUILDERS BACKGROUND OF THE INVENTION This invention relates to novel compounds and precursors thereof useful as sequestrants and detergency builders.
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 sequenstrants, 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 compounds 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 phosphorous.
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 and formulations 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 wherein R is hydrogen, methyl, ethyl, alkali metal or ammonium and R and R are hydrgen or methyl.
The compounds are readily prepared reacting the appropriate alkyl bromomalonate with the sodium salt of the appropriate a-hydroxy ester in an inert solvent such as 1,2-dimethoxyethane.
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.
In preferred embodiments of the invention, R is sodium and R and R are both methyl or hydrogen. 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 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 carbonate, borates, phosphates, polyphosphate, bic'arbonates and silicates or organic builders such as salts of phytic acid, sodium citrate, water soluble polymeric polyc'arboxylates 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 ofa 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 U.S. Pat. application Ser. No. 707,480 filed Feb. 23, 1968 and copending herewith; condensates of monohydroxy or polyhydroxy alcohols such as oleyl alcohol or l-tridecanol with from 9 to 15 molecular proportions of ethylene oxides; alkyl internal vicinal dialkoxy or hydroxy alkoxy compounds as described in U.S. Pat. application Ser. No. 852,898 filed Aug. 25, 1969, now abandoned; and condensates of alkylene oxides with organo amines, for example, ethylene diamine and amides such as N-octadecyl diethanol amide.
Examples of cationic surfactants include octadecyl ammonium chloride; straight chain fatty amines having 8 to 18 carbon atoms; and quaternary ammonium compounds such as octadecyl trimethyl ammonium chloride.
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-cyclo 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-3dodecyl amino propionate and sodium-S-dodecyl amino propane sulfonate.
Examples of zwitterionic surfactants include derivatives of quaternary ammonium phosphonium and sulfonium compounds such as 3-(N,N-dirnethyl-N- hexadecyl ammonio) propane-l-sulfonate and 3-(N,N-diemthyl-N-hexadecyl ammonio-Z-hydroxy propanel -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 due to recognized problems of precipitation of insoluble products.
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:] by weight.
In addition to surfactant and builder components, the detergent formulstions may contain fillers such as so dium sulfate and minor amounts of bleaches, dyes, optical brighteners, soil anti-redeposition agents, perfumes and similar conventional detergent formulation additives.
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 68 grams sodium ethyl glycolate in 400 ml 1,2-dimethoxyethane is added 120 grams diethyl bromomalonate, the temperature being maintained below C. The mixture is allowed to stir for 16 hours at 25 C. Solids are separated by filtration and solvent .removed under reduced pressure. The residue is vacuum fractionally distilled, product being collected at 149-l 5 l C, 0.07 mm Hg. The product is identified by nuclear magnetic resonance and elemental analyses as tetraethyl 2,4-dioxal ,3 ,3 ,5-pentane-tetracarboxylate. The product is saponified in an aqueous ethanol solution of NaOH at 25 C. The salt is precipitated by addition of excess ethanol and isolated by filtration and drying. Acidification of the salt with H 80 yields the acid form of the product.
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 Ill EXAMPLE IV The tests of Example Ill above are repeated using a detergent formulation in which Neodole 45-1 1 (a nonionic surfactant which is an aduct of a modified oxo type C -C alcohol with an average of l 1 moles of ethylene oxide is substituted for the alkylbenzene sulfonate. Comparable results are obtained.
, EXAMPLE V The tests of Example Ill are repeated with a detergent formulation wherein sodium hydroxyalkyl (C -C alkyl chain length) N-methyl taurate, 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 cocodimethylsulfopropylbetaine, a zwitterionic surfactant is substituted for the alkylbenzene sulfonate. Comparable results are ob tained.
What is claimed is:
1. Compounds having the formula o It it,
wherein R is selected from the group consisting of hydrogen, methyl, ethyl, alkali metal and ammonium and R and R are each selected from the group consisting of hydrogen and methyl.
2. A compound according to claim 1 wherein R is sodium.
3. A compound according to claim 2 wherein R is hydrogen and R is a methyl substituent.
4. A compound according to claim 2 wherein R and R are hydrogen.

Claims (3)

  1. 2. A compound according to claim 1 wherein R is sodium.
  2. 3. A compound according to claim 2 wherein R1 is hydrogen and R2 is a methyl substituent.
  3. 4. A compound according to claim 2 wherein R1 and R2 are hydrogen.
US00158539A 1971-06-30 1971-06-30 Detergency builders Expired - Lifetime US3742045A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4125485A (en) * 1976-03-25 1978-11-14 Monsanto Company Detergent formulation containing novel ether carboxylates
US4146495A (en) * 1977-08-22 1979-03-27 Monsanto Company Detergent compositions comprising polyacetal carboxylates
US4169934A (en) * 1978-04-03 1979-10-02 Monsanto Company Copolymers of keto dicarboxylates
US4174306A (en) * 1977-02-28 1979-11-13 Montedison S.P.A. Detergent compositions containing self-sequestering surfactants
US4182684A (en) * 1974-05-17 1980-01-08 Monsanto Company Machine dishwashing composition
US4219437A (en) * 1979-02-02 1980-08-26 Monsanto Company Copolymers of keto dicarboxylates

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2377246A (en) * 1942-03-02 1945-05-29 Monsanto Chemicals Alkoxy-substituted aliphatic carboxylic acid compounds

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2377246A (en) * 1942-03-02 1945-05-29 Monsanto Chemicals Alkoxy-substituted aliphatic carboxylic acid compounds

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4182684A (en) * 1974-05-17 1980-01-08 Monsanto Company Machine dishwashing composition
US4125485A (en) * 1976-03-25 1978-11-14 Monsanto Company Detergent formulation containing novel ether carboxylates
US4174306A (en) * 1977-02-28 1979-11-13 Montedison S.P.A. Detergent compositions containing self-sequestering surfactants
US4146495A (en) * 1977-08-22 1979-03-27 Monsanto Company Detergent compositions comprising polyacetal carboxylates
US4169934A (en) * 1978-04-03 1979-10-02 Monsanto Company Copolymers of keto dicarboxylates
US4219437A (en) * 1979-02-02 1980-08-26 Monsanto Company Copolymers of keto dicarboxylates

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