Classifications

• • 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

Definitions

• 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.
• 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.
• 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 COOR
• R and R are hydrogen
• a solution preferably about 1 molar
• two equivalents of lithium diisopropylamide in tetrahydrofuran solution preferably about 1 molar
• R is sodium and R R and R are hydrogen.
• R is sodium, R, is methyl and R and R are hydrogen.
• R is sodium, R and R are hydrogen and R is COONa.
• 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.
• 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 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.
• 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.
• amido alkene sulfonates such as sodium C-pentadecyl, N- methyl amido ethyl sulfonate potassium C-octyl N- napthalene amido
• 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).
• 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.
• 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.
• 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.
• EXAMPLE II The salt and acid produced according to Example I are tested for sequestration characteristics and are found to effectively sequester Ca ions.
• 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.
• Example llX 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 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.
• 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.
• 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.
• 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
• a composition according to claim 1 wherein said detergency builder constitutes from 5 percent to 50 percent of the weight of the composition.
• composition according to claim 1 wherein the surfactant is a linear alkylbenzene sulfonate surfactant.
• R is hydrogen

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Citations (1)

• 1972
  • 1972-06-27 NL NL727208864A patent/NL149226B/xx not_active IP Right Cessation
  • 1972-06-29 DE DE2231927A patent/DE2231927A1/de active Pending
  • 1972-06-29 AT AT561772A patent/AT322076B/de not_active IP Right Cessation
  • 1972-06-29 FR FR727223601A patent/FR2143886B1/fr not_active Expired
  • 1972-06-29 CH CH973872A patent/CH575005A5/xx not_active IP Right Cessation
  • 1972-06-29 CA CA146,087A patent/CA1002531A/en not_active Expired
  • 1972-06-29 GB GB3037372A patent/GB1387447A/en not_active Expired
  • 1972-06-29 AU AU44060/72A patent/AU458711B2/en not_active Expired
  • 1972-06-29 DE DE19722265058 patent/DE2265058A1/de active Pending
• 1973
  • 1973-09-13 US US396928A patent/US3865755A/en not_active Expired - Lifetime

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