US3717616A - Polymers of 1-butene-2,3,4-tricarboxylic acid - Google Patents

Polymers of 1-butene-2,3,4-tricarboxylic acid Download PDF

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US3717616A
US3717616A US00063023A US3717616DA US3717616A US 3717616 A US3717616 A US 3717616A US 00063023 A US00063023 A US 00063023A US 3717616D A US3717616D A US 3717616DA US 3717616 A US3717616 A US 3717616A
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acid
butene
copoly
solution
builder
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G Volpp
P Chakrabarti
H Stange
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FMC Corp
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FMC Corp
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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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/12—Hydrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/911—Emulsifying agents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/933—Detergent property or lubricant additive

Definitions

  • TRICARBOXYLIC ACID [75] Inventors: Paritosh M. Chakrabarti, Highstown; Hugo Stange; Gert Paul Volpp, both of Princeton, all of NJ.
  • ABSTRACT A water soluble salt of an aliphatic polycarboxylic acid useful as a detergent builder, and having the formula:
  • each of m and n can be zero or a positive number, it being provided that the sum of m and n is always less than one;
  • p is an integer the upper limit of I which is determined by the solubility of the salts in an 6 Claims, No Drawings POLYMERS OF 1 BUTENE-2,3,4-TRICARBOXYLIC ACID BACKGROUND OF THE INVENTION A.
  • This invention relates to cleansing and laundering compositions. It is particularly concerned with such compositions containing a polyelectrolyte builder material which enhances the cleansing action of detergents.
  • builder compounds exhibit at least some effect in such areas as stabilization of solid soil suspension, emulsification of soil particles, the surface activity of aqueous detergent solutions, solubilization of water-insoluble materials, foaming or sudsproducing characteristics of the washing solution, peptization of soil agglomerates, neutralization of acid soil, and the inactivation of mineral constituents present in the washing solution.
  • any theoretical discussion of the boosting capacity of a builder compound should give due consideration to all the significant individual actions involved in the detergent process and must apply equally to all the usual conditions of soiling and washing.
  • a builder should preferably be white, inexpensive, nontoxic, stable to oxidizers in the dry state, non-corrosive, non-hygroscopic, stable to hot alkaline detergent solutions and stable during spray drying operations.
  • inorganic builder materials examples include the water-soluble, inorganic alkaline builder salts which can be used alone or in combination, including alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates.
  • organic builder materials are alkali metal, ammonium or substituted ammonium aminopolycarboxylates, e.g., sodium and potassium ethylenediaminetetraacetate, sodium and potassium N(2-hydroxyethyl)-ethylenediaminetriacetate, sodium and potassium and triethanolammonium N (2- hydroxyethyl) nitrilodiacetate.
  • Alkali metal salts of phytic acid e.g., sodium phytate, are also suitable as organic builders.
  • condensed inorganic polyphosphates find the widest commercial acceptance, these exhibit the undesirable property of hydrolyzing into less condensed phosphorus compounds which are essentially devoid of builder properties. Moreover, these hydrolytic derivatives often form undesirable precipitates in aqueous washing solutions. Such lower forms include orthophosphate.
  • polyelectrolyte builder materials which are highly polar polymers such as the water-soluble salts of aliphatic polycarboxylic acids.
  • these classes of builders are disclosed in U.S. Pat. No. 3,308,067 to Diehl and U.S. Pat. No. 3,463,734 to Carter Jr. et al. These new types of builders do not hydrolyze into undesirable by-products.
  • the polymeric builder compounds of the invention are polymers of l-butene-2,3,4-tricarboxylic acid or copolymers thereof with l or 2 monoethylenically unsaturated monomers.
  • the polymerization is carried out in the manner of preforming ethylenic polymerizations, details of which are given below.
  • such polymerization is effected under free radical producing conditions, commonly provided by the use of peroxides such as alkali metal persulfates or an organic peroxide such as benzoyl peroxide.
  • the polymerization may be solution polymerization or emulsion polymerization depending on the solubility of the monomer starting materials. In some instances bulk polymerization is preferred.
  • the ratio of l-butene- 2,3 ,4-tricarboxylic acid with other ethylenic monomers is governed by the requirement that the copolymer must form water soluble salts or at least be soluble in the cleansing composition. Accordingly, the copolymer must contain solubilizing groups. These are preferably carboxy groups which can come solely from the l-butene-2,3,4-tricarboxylic acid or from a combination of the latter with at least one of the ethylenic units. There is a tendency toward insolubility when the number of non-carboxy containing units greatly exceeds the carboxy containing units.
  • the minimal percent of carboxy carrying groups needed for water solubility will vary to some extent depending upon the polar character of the substituents attached to the ethylenic units.
  • the desired water solubility can be realized with a relatively small percentage of carboxy groups in the copolymer whereas more carboxy groups will be needed if the associated ethylenic groups carry non-polar substituents such as alkyl radicals.
  • Those skilled in the art will generally be able to adjust the ratio of monomer units to achieve the desired solubility.
  • Typical of the polymeric compounds described herein are the following: homopolymer of l-butene- 2,3,4-tricarboxylic acid; 1:1, 1:2, and 2:1 copolymers of l-butene-2,3,4-tricarboxylic acid and itaconic acid; 1:1, 1:2, and 2:1 copolymers of l-butene-2,3,4-tricarboxylic and methacrylic acid; 1:1, 1:2, and 2:1, copolymers of l-butene-2,3,4-tricarboxylic acid and acrylic acid; 1:1 copolymer of l-butene-2,3,4-tricarboxylic acid and maleic acid; 1:1 copolymer of l-butene-2,3,4-tricarboxylic acid and vinyl acetate, 1:1 copolymer of l-butene-2,3,4-tricarboxylic acid and vinyl alcohol; 5:2 copolymer of l-butene-2,3,4-'tricarboxylic acid and methyl vinyl
  • Preferred compounds are l:l:l copolymer of l-butene-2,3,4-tricarboxylic acid, itaconic acid, and acrylic acid; 1:], 1:2, and 2:1 copolymers of l-butene-2,3,4- tricarboxylic acid and itaconic acid; 1:1, 1:2, and 2:1 copolymers of 1-butene-2,3,4-tricarboxylic acid and acrylic acid.
  • the monomeric species employed can in many cases, be such derivatives or precursors of the designated acids as the anhydrides, the full or partial esters of such acids, amides, nitriles, etc., or mixtures of same, which after polymerization can be converted to the carboxylate salts by appropriate chemical reactions.
  • the degree of polymerization, p, of the novel polyelectrolyte builder compounds of this invention has a significant and practical bearing on the builder effectiveness of these compounds.
  • the lower limit for p has been established as three resulting in compounds having a molecular weight on the order of not less than about 350.
  • Builder properties of the compounds of this invention drop off substantially as the molecular weight goes below 350.
  • the higher builder concentrations on the order of 0.50 percent by weight may be found necessary under certain washing conditions such as a water hardness of 21 grains equivalent CaCO per gallon or higher.
  • any of the polyelectrolyte builder compounds of this invention could be selected whose solubility characteristics would allow a builder concentration in an aqueous solution to the necessary amount. in more general household situations, builder concentrations of 0.03 percent to about 0.06 percent are found to be adequate.
  • the degree of polymerization of these compounds can very within a very wide range.
  • the degree of polymerization, p can be within the ranges of 3 to about 5,000. This corresponds to a molecular weight range for the compounds of this invention from 350 to about 1,500,000.
  • a preferred range for the degree of polymerization, p is from about 4 to about 500. This represents a preferred molecular weight range for the polyelectrolyte builder compounds of this invention of about 500 to about 175,000.
  • the minimum molecular weight of 350 mentioned above was arrived at empirically and, to a great extent, is based on the knowledge and experience acquired from working with these polyelectrolytic polycarboxylic polymers.
  • Viscosity is a property more frequently used by polymer chemists than molecular weights in characterizing polymeric compounds. This is no doubt due to the comparatively easier and less complicated methods available for obtaining viscosity data. To make such data meaningful, it is necessary to also give the test conditions under which the measurements were run. Since there is a recognized correlation between the viscosity of polymeric compounds and their molecular weights and since such figures can be more meaningful and can frequently be more available than molecular weights, the polymeric builder compounds used in the examples of this invention are characterized in terms of specific viscosity. In all cases the viscosity characterization corresponds to a molecular weight substantially above 350.
  • the essential ingredients are (a) an organic water soluble detergent surface active material as defined and illustrated below and (b) a novel polyelectrolyte builder compound meeting the structural requirements specified and exemplified above.
  • the detergent compositions of this invention therefore, contain the essential ingredients in a ratio of polyelectrolyte builder to detergent surfactant in the range of about 1:3 to about :1 by weight, with such compositions providing in aqueous solution a pH of about 8 to about 12.
  • the preferred ratio of polyelectrolyte builder to detergent surfactant is about 1:2 to about 5:1 and the optimum pH range is 9.5 to about 11.5.
  • organic detergent compounds i.e. surface active agents
  • anionic, nonionic, ampholytic and'zwitterionic synthetic detergents and mixtures thereof are exemplified as follows:
  • Anionic synthetic non-soap detergents can be broadly described as the water-soluble salts, particularly the alkali metal salts, of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from about eight to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals.
  • the synthetic detergents are the sodium or potassium alkyl sulfates, sodium or potassium alkylbenzenesulfonates, in which the alkyl group contains from about nine to about carbon atoms (the alkyl radical can be a straight or branched aliphatic chain); alkyl (glycerylsulfate) ether; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts or sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol (e.g., tallow or coconut oil alcohols) and about 1 to 6 moles of ethylene oxide, sodium or potassium salts of alkyl phenol ethylene oxide ether sulfate with about 1 to about 10 units of ethylene oxide per molecule and in which the alkyl radicals contain from eight to about 12 carbon atoms: the reaction product of fatty acids esterified with isothionic acid and neutralized with sodium hydroxide, sodium or potassium salts of fatty radicals
  • Nonionic synthetic detergents One class can be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements. Another class has semi-polar characteristics. Preferred classes of nonionic synthetic detergents are as follows:
  • a class of nonionic synthetic detergents under the trade name of Pluronic are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol;
  • the polyethylene oxide condensates of alkyl phenols e.g., the condensation products of alkyl phenols having an alkyl group containing from about six to 12 carbon atoms in either a straight chain or branched chain configuration with ethylene oxide;
  • Long chain tertiary amine oxides such as dimethyldodecylamine oxide; cetyldimethylamine oxide; bis-(2-hydroxyethyl)-dodecylamine oxide; bis-(2- hydroxyethyl)-3 -dodecoxyl -hydroxypropylamine oxide;
  • Long chain sulfoxides such as dodecyl methyl sulfoxide; 3-hydroxytridecyl methyl sulfoxide; 3- methoxytridecyl methyl sulfoxide; 3-hydroxy-4- dodecoxybutyl methyl sulfoxide.
  • Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic secondary and tertiary amines, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about eight to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfo, sulfato, phosphate, or phosphono. Examples of compounds falling within this definition are sodium-3-dodecylaminoproprionate and sodiumi3-dodecylaminopropanesulfonate.
  • Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radical may be straight chain or branched, and wherein one of the aliphatic substituerrts contains from about eight to 18 carbon atoms and one contains an anionic water solubilizing group; e.g., carboxy, sulfo, sulfato, phosphato, or phosphono.
  • Examples of compounds falling within this definition are 3- (N ,N -dimethyl-N-hexadecylammonio)propane-1 -sulfonate and 3-(N,N-dimethyl-N-hexadecylammonio)-lhydroxy propanel -sulfonate.
  • the weight ratio of surface active agent to builder ranges from about 3:1 to 1:10. These two ingredients generally represent at least about 45 percent of the total detergent formulation.
  • novel builders herein are used either in the form of their alkali metal salts or in acid-form together with a sufficient quantity of an alkali metal base, such as the carbonate or hydroxide, in order to neutralize the carboxyl group and adjust the pH level of the final detergent solution to within the desired 9.5-1 1.5 range.
  • an alkali metal base such as the carbonate or hydroxide
  • the formulations may also contain minor amounts of optional additives in order to modify certain properties thereof.
  • optional additives include foam builders and stabilizers, antiredeposition agents such as sodium carboxymethylcellulose, corrosion in hibitors such as benzotriazole, optical brighteners, bactericides, perfumes, bleaches, enzymes, dyes, blueing agents, inorganic salts, solvents and the line,
  • foam builders and stabilizers antiredeposition agents such as sodium carboxymethylcellulose
  • corrosion in hibitors such as benzotriazole
  • optical brighteners such as benzotriazole
  • bactericides such as benzotriazole
  • perfumes bleaches
  • enzymes such as sodium carboxymethylcellulose
  • dyes such as sodium carboxymethylcellulose
  • blueing agents such as sodium carboxymethylcellulose
  • solvents and the line these total optional ingredients commonly range from about 30 percent to about 55 percent, by weight of the formulation.
  • detergent formulations are well known to those skilled in the art, a typical method involving drying the ingredients, forming them into an aqueous slurry and then spray drying.
  • the final detergent formulations may be a mixture of dry ingredients, a concentrated aqueous solution or a solid mix resulting from the drying thereof, or a combination of dry solids and dry ingredients as is common in the art.
  • the bottle was warmed to room temperature, filled with nitrogen and the contents stirred until a clear solution resulted (5 days).
  • the solution was concentrated to half its original volume in vacuo and the polymer precipitated by pour- Aciding the concentrated solutions into acetone (1 liter).
  • the white precipitate was filtered and washed five times with 20 ml portions of warm acetone and then dried at 65/.l mm for 2 hr. Yield: 6 g.
  • EMULSION POLYMERIZATION This procedure was used for homeand copolymerizing water insoluble oils, i.e., esters of alkenepolycarboxylic acids.
  • An emulsifier solution was first prepared by mixing the following:
  • the pH of the solution was then adjusted to 3-5 by adding 5 percent sodium bicarbonate solution.
  • the mixture was charged into a polymerization bottle fitted with a rubber septum, degassed as described under Example 1 and shaken for 24-150 hr., when a waxy lump of solid had formed.
  • the solid lump was removed, washed successively with water and then dried at 65/0.1 mm..
  • emulsifier solution (6.5 ml), 2.8 percent potassium persulfate solution (1.9 ml), 2.8 percent sodium metabisulfite solution (1.9 ml), and 5 percent sodium bicarbonate solution (0.4 ml) were charged, in the above order, into a polymerization bottle.
  • the bottle was closed with a rubber septum and the contents degassed by repeating freezing and evacuation as described before.
  • the bottle was mechanically shaken for six days and the white waxy solid that had separated was washed repeatedly with water and dried at 65/0.1 mm; yield, 6 g.
  • EXAMPLE 4 Homopoly(Trimethyl late)
  • a mixture of trimethyl l-butene-2,3,4-tricarboxylate (4.6 g) and acetyl peroxide (1 ml of a 25 percent solution in dimethyl phthalate) was placed in a 50 ml round bottomed flask fitted with a rubber septum, degassed as described under Example 1.
  • the flask was heated at 50 until a highly viscous material was obtained (24 hr.).
  • the rubber septum was replaced by an adapted l-Butene-2,3 ,4-Tricarboxytube and the latter connected through a dry-ice trap to a vacuum pump.
  • the flask was then heated to 180 with stirring and the low boiling fractions removed under a pressure of 0.1 mm. At room temperature residual mass was a tough plastic glass; Yield 3 g.
  • EXAMPLE 6 EXAMPLE 7 l-Butene-2,3,4-tricarb0xylic Acid and Itaconic Acid 1:1 Copolymer Trimethyl 1-butene-2 ,3 ,4-tricarboxylate was copolymerized with itaconic anhydride as described in Example 3. A suspension of l g of this polymer in 100 ml of 5 percent aqueous hydrochloric acid was stirred at until a clear solution resulted (12 hr.). The solution was evaporated to dryness under reduced pressure and the residual white solid washed with acetone and dried at 65/0.l mm. Yield: 0.7 g of the title compound.
  • EXAMPLE 9 Preparation of Sodium Salts of Polymeric Alkenepolycarboxylic Acids
  • the sodium salts for builder evaluation of the polymeric alkenepolycarboxylic acids were prepared by neutralizing a saturated aqueous solution of the poly-acid with 30 percent aqueous sodium hydroxide until a pH of 9.5 was reached. The solution was then concentrated to half the original volume and poured into a large quantity of acetone to precipitate the sodium salt. The salt was filtered and dried at 65/0. 1 mm.
  • EXAMPLE DETERGENT FORMULATION This example illustrates typical detergent formulations of this invention as well as the excellent laundering properties exhibited by these products.
  • the general detergent formulation which was utilized in this example is as follows:
  • the formulation was prepared by merely blending the various ingredients.
  • Reflectance readings on the washed swatches were then taken from a Hunter Reflectometer, Model Dl0. The results were expressed in terms of percent reflectance with the arbitrary standard of 100 percent reflectance being established for the reflectance value obtained on a cotton swatch which had been washed with the standard detergent formulation containing 50 percent sodium tripolyphosphate builder in water of 150 ppm hardness.
  • REDEfOSlTlON TEST The basic functions of a detergent solution may be conveniently divided into two distinct operations. First, removal of soil from the substrate and suspension thereof in the detergent solution, and second, prevention of redeposition of the suspended soil. Redeposited soil is more tenaciously held on the fabric surface and is difficult to remove by subsequent washings. As a result a built detergent formulation which causes considerable redeposition may still wash fabrics brighter in the first few washings but gradually impart a permanent yellow or grey cast on the fabric.
  • the redeposition test is intended to show the ability of the detergent formula tion to prevent redeposition of soil during the wash as well as the rinse cycle. The redeposition data are decreases in reflectance (AR) of unsoiled swatches when washed with standard soiled swatches.
  • B'ICA 1-butene-2,3A-trlcnrboxylle acid
  • AA acry1ic acid
  • IA lta conic acid
  • MAA mcthacry1ic acid
  • MVE mcthyl vinyl ether
  • SIP P sodium tripolyphosphatc.
  • Each of the builders tested was prepared according 2.
  • An aliphatic polycarboxylic acid according to to the procedures set forth in Examples 1 to 9, herein claim 1 having the name, l-butene-2,3,4-tricarboxylic above.
  • the preparative procedures and sequestering acid-itaconic acid-acrylic acid (l:1:1)copolymer. capacity of some of these builders are presented in the 3.
  • An aliphatic polycarboxylic acid according to following table: claim 1 having the name, copoly(1-butene-2,3,4-tricar- Homoand copolymers of 1-butene 2,3,4-tricarboxylie acid and their calcium sequestering capacities Sequestoring capacity Prepared from Co, Example Name (mononn-rs) lropnrntivn procedure (solvent, catalyst, temperature and time) gJlOU g. loly BTCA 'IMBTC llnlk Wilyllltlllltllill A0202, 50.
  • Copoly BTCA-MA (1:1) BTCA and MAn solllutionI polymerization (xylene, BZZOQ, reflux, 3 hr.) and 8.8 ydro ysis.
  • Copoly BICA-MVE (5:2) TMBIO and MVE Bulk polymerization B2102, 100, 24 hr.) and hydrolysis... 8.0 Copoly B'ICA-VA... 'IMBTC and VAe.
  • 1-23 33 Copoly BTCA-AA-MA (1 'IMBTC AA and MA Solution pclymerization (benzene, B2102, reflux, 12 hr.) 13

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3859224A (en) * 1971-09-24 1975-01-07 Hoechst Ag Detergent composition containing, as a builder, the sodium salt of glycerol tricitrate
US5362413A (en) * 1984-03-23 1994-11-08 The Clorox Company Low-temperature-effective detergent compositions and delivery systems therefor
US20090217723A1 (en) * 2008-03-03 2009-09-03 Specialty Fertilizer Products Dual salt fertilizer giving enhanced crop yields

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5431846A (en) * 1993-05-20 1995-07-11 Lever Brothers Company, Division Of Conopco, Inc. Copolymers and detergent compositions containing them

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2782227A (en) * 1950-08-28 1957-02-19 Monsanto Chemicals Polycarboxylates
FR1539973A (fr) * 1967-08-16 1968-09-20 Toyo Rayon Co Ltd Nouveaux esters de l'acide butène-polycarboxylique et procédé pour leur préparation
US3463734A (en) * 1966-06-16 1969-08-26 Monsanto Co Builders for synthetic detergents

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2782227A (en) * 1950-08-28 1957-02-19 Monsanto Chemicals Polycarboxylates
US3463734A (en) * 1966-06-16 1969-08-26 Monsanto Co Builders for synthetic detergents
FR1539973A (fr) * 1967-08-16 1968-09-20 Toyo Rayon Co Ltd Nouveaux esters de l'acide butène-polycarboxylique et procédé pour leur préparation

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3859224A (en) * 1971-09-24 1975-01-07 Hoechst Ag Detergent composition containing, as a builder, the sodium salt of glycerol tricitrate
US5362413A (en) * 1984-03-23 1994-11-08 The Clorox Company Low-temperature-effective detergent compositions and delivery systems therefor
US20090217723A1 (en) * 2008-03-03 2009-09-03 Specialty Fertilizer Products Dual salt fertilizer giving enhanced crop yields

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NL7111028A (forum.php) 1972-02-15
CA985702A (en) 1976-03-16
BE771102A (fr) 1972-02-09
GB1374591A (en) 1974-11-20
SE7500525L (forum.php) 1975-01-17
CH556908A (de) 1974-12-13
FR2103974A5 (forum.php) 1972-04-14
CH570353A5 (forum.php) 1975-12-15
DE2139048A1 (de) 1972-02-17
GB1374592A (en) 1974-11-20

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