MXPA99011877A - Copolymers of poly hidroxicarboxylate - Google Patents

Abstract

The invention provides novel polyether hydroxycarboxylate copolymers, which are effective sequestering agents. The polyether hydroxycarboxylate copolymer when used in a cleaning composition improves or "creates" the cleaning efficiency of the surfactant by inactivation of hardening ions. In addition, the depolyether hydroxycarboxylate copolymers aid in the cleaning by dispersion and suspension of spots to prevent redeposition of spots. The polyether hydroxycarboxylate copolymer has the structure wherein M + is a cation wherein M is independently selected from hydrogen, ammonia, alkali metals, alkaline earth metals, zinc, copper, organic amines, amino acids and aminosaccharides; R2 and R3 are independently hydrogen or a substituted or unsubstituted alkyl group having from 1 to 4 carbon atoms, n is from about 2 to about 100, X1 and X2 are independently 0 to 1, a is from 0 to 99 mole percent, and b is from 100. to 1 mole percent, with the proviso that (a + b) is 100 percent mol

Description

COPOLYMERS OF POLYETER HYDROXYCARBONYLATE DESCRIPTION OF THE INVENTION The invention relates to novel polyether hydroxycarboxylate copolymers, which are effective sequestering agents. The polyether hydroxycarboxylate copolymer when used in a cleaning composition, improves or "creates" the cleaning efficiency of a surfactant through the inactivation of hardened ions. The copolymers also aid in the cleaning by dispersion and suspension of stains in cleaning articles. The role of the sequestering agents in softening water through the complexion of "hardened" cations in supplied water is well known. Sequestering agents are recognized as auxiliaries in detergent processes because they form a soluble complex with calcium and magnesium ions which can react with soaps and other anionic surfactants and likewise adversely affect detergency. Polyphosphates such as tripolyphosphates and pyrophosphates are widely used as ingredients in detergent compositions in part due to their property of hardened sequestering ions. Such compounds contain phosphorus as well as nitrogen containing compounds, for example nitrileacetates, are highly effective. However, the effect of the phosphorus content and the nitrogen content of these sequestering agents until the eutrophication of lakes and streams has been questioned and the use of phosphates in detergent compositions has been subjected to governmental scrutiny, regulation or prohibition. These circumstances have developed a need for effectively and efficiently high sequestering agents, free of phosphorus and nitrogen and builders. U.S. Patent No. 3,692,685, discloses detergent compositions containing an ether polycarboxylate having the structure: In the above structure of U.S. Patent No. 3,692,685, R is H or -CH2C00Na. U.S. Patent No. 4,228,300 describes ether polycarboxylate sequestering agents and builders having the structure In the above structure, U.S. Patent No. 4,228,300, M is an alkali metal or ammonium, Ri and R2 are hydrogen, methyl or ethyl and R; is hydrogen, methyl, ethyl or COOM. U.S. Patent No. 3,769,223 discloses l-oxacyclopropan-2,3-dicarboxylic acid (ie, epsxysuccinic acid) and its soluble salts as detergent builders. U.S. Patent No. 3,776,850 describes polymers to be used as detergent builders which have the structure: In the above structure of US Pat. No. 3,776,850, R is hydrogen or other specific radicals and n is from 2 to about 40, preferably from 2 to about 6. The polymers are prepared by polymerization of the diethyl ester of 1-oxacyclopropan-2, 3-dicarboxylic (i.e., epoxysuccinic acid) in the presence of boron trifluoride catalyst followed by saponification. The detergent compositions are exemplified in which n is either to have an average value of (about 3 or 4. In fact, the synthesis method described produces mixtures of materials which contain very low levels of n = 3 components and n = 4. U.S. Patent No. 4,654,159 discloses the use of polyepoxy succinic acid as a sequestering agent in detergent compositions The invention provides a novel polyether hydroxycarboxylate copolymer comprising: wherein M + is a cation wherein M is independently selected from the group consisting of hydrogen, ammonia, alkali metals, alkaline earth metals, zinc, copper, organic amines, amino acids, and aminosarcharides; Ri is the residue of an ethylenically unsaturated comonomer having at least one functional group which is selected from the group consisting of carboxylic acid, sulfonic acid and phosphonic acid, R2 and R3 are independently selected from the group consisting of hydrogen, and substituted or unsubstituted alkyl group having 1 to 4 carbon atoms; n is from about 2 to about 100; Xj and; •: - are independently 0 or 1; a is from 0 to 99 mole percent; and b is 100 to 1 mole percent, with the proviso that (a + b) is 100 mole percent. According to another aspect of the invention, it also provides a cleaning composition comprising from about 0.5 to about 98 weight percent, based on the weight of the cleaning composition, of the polyether hydroxycarboxylate copolymer. In the cleaning composition, the polyether hydroxycarboxylate copolymer improves or "creates" the cleaning efficiency of a surfactant by inactive hardening ions such as calcium and magnesium, and other metal ions such as iron. The polyether hydroxycarboxylate copolymers soften water through sequestration. In addition, the polyether hydroxycarboxylate copolymers aid in the cleaning by dispersion and suspension of stains to prevent redeposition of stains in cleaning articles. The polyether hydroxycarboxylate copolymers have the structure: wherein M + is a cation wherein M is independently selected from the group consisting of hydrogen, ammonia, alkali metals, alkaline earth metals, zinc, copper, organic amines, amino acids, and aminosaccharides. Preferably, the cation is independently hydrogen or sodium. In the above structure of the polyether hydroxycarboxylate copolymer, R and R3 are independently selected from the group consisting of hydrogen, and an alkyl group having from 1 to 4 carbon atoms, a substituted alkyl group having from 1 to 4 carbon atoms, and combinations thereof. When R2 and R3 are hydrogen, the monomer used to prepare the repeating unit (a) is maleic acid. However, methylmaleic acid (citraconic acid) and other substituted cisbutadioic acids can be substituted by maleic acid. In the above structure for the polyether hydroxycarboxylate copolymer, Ri is the residue of an ethylenically unsaturated comonomer having at least one functional group which is selected from the group consisting of carboxylic acid, sulfonic acid and phosphonic acid. Suitable ethylenically unsaturated comonomers having a carboxylic acid functional group are acrylic acid, methacrylic acid, itaconic acid, ethacrylic acid, alpha-chloroacrylic acid, alpha cyano acrylic acid, crotonic acid, alpha phenylacrylic acid, beta acryloxy propionic acid, sorbic acid , angelic acid, cinnamic acid, glutaconic acid, 2-acrylamido glycolic acid, .tricarboxyethylene. A preferred ethylenically unsaturated number having carboxylic acid functional groups is an itaconic acid. Suitable ethylenically unsaturated comonomers having a functional group of sulfonic acid or phosphonic acid are vinylsulfonic acid, metalylsodium sulfonate, 2-acrylamido-2-methylpropanesulfonic acid, allyloxybenzenesulfonic acid, and vinylphosphonic acid. Preferred ethylenically unsaturated comonomers having a functional group of sulfonic acid or phosphonic acid are vinylsulfonic acid and vinylphosphonic acid. Thus, the polyether hydroxycarboxylate copolymer is prepared from (a) and (b) repeat units. The repeating units (a) are derived from either maleic acid, methylmaleic acid or other substituted cisbutanedioic acids. The repeating units (b) are derived from an ethylenically unsaturated comonomer having at least one functional group which is selected from the group consisting of carboxylic acid, sulfonic acid and phosphonic acid.

In the above structure for the polyether hydroxycarboxylate copolymer, n is from about 2 to about 100. Preferably n is from about 2 to about 20, more preferably from 2 to 10. The letters xx and x ^ are independently 0 or 1. The letter a is from 0 to 99 mole percent, preferably 20 to 100 mole percent. The letter b is from 0 to 99 percent in mol, preferably 0 to 80 mole percent, with the proviso that (a + b) is 100 mole percent. A preferred process for preparing the polyether hydroxycarboxylate copolymers involves mixing the responsible monomer (s) to repeat units (a) and the responsible comonomer (s) to repeat the (b) together with water to form a mixture. The monomers and comonomers in the mixture are neutralized or partially neutralized using a base. A preferred base is sodium hydroxide. Preferably, at least 609; of the total acid groups are neutralized. The next step involves epoxidation of the ethylenically unsaturated double bonds in the monomers and comonomers to form a mixture of epoxides. Methods for epoxidation are well known in the art, such as described by G. B. Payne and P. H. Williams in the Journal of Organic Chemistry, vol. 24, p. 54 (1959) which is incorporated herein for reference. For example, a combination of an oxidizer such as hydrogen peroxide and a catalyst such as sodium tungstate can be used. It is within the scope of the invention that not all of the ethylenically unsaturated double bonds present in the monomers and comonomers are epoxidized. Optionally, the step of neutralization or partial neutralization can be carried out after forming the epoxides. The epoxides are polymerized by means of an anionic polymerization process to form the polyether hydroxycarboxylate copolymer product. Any monomer and / or comonomer which has not been epoxidized can be polymerized such that either xi, x2 or both are equal to 0 in the polyether hydroxycarboxylate copolymer product. Preferably, xx and y.- are equal to 1 in the polyether hydroxycarboxylate copolymer. The polymerization is carried out in the presence of calcium hydroxide or other alkaline calcium salts. A description of a method for the polymerization of an epoxide derived from maleic acid is included in U.S. Patent No. 4,654,159, which is incorporated herein by reference. The polyether hydroxycarboxylate copolymer product containing sodium and calcium salts can be used in the form of an aqueous solution. Alternatively, the sodium or calcium salts can be replaced by means of an ion exchange by an alkali metal, such as sodium or ammonium, substituted ammonium or hydrogen. The optional removal of low molecular weight components (n = 1) can be carried out using a suitable process such as vacuum distillation. In one embodiment of the invention, the process can be represented as follows: Catalyst Water Base H, 0, epoKidiza or wherein CH2CH4 is an ethylenically unsaturated comonomer containing the carboxylic acid, carbonic acid, sulfonic acid group or a combination thereof The concentration of the polyether hydroxycarboxylate copolymer in a cleaning composition is from about 0.5 to about 98 percent by weight, based on the weight of the cleaning composition. Preferably, the polyether copolymers are present in an amount of about 1 to about 20 weight percent, more preferably 1 to 10 weight percent, based on the weight of the cleaning composition. The polyether hydroxycarboxylate copolymer can be used in any cleaning composition. Examples of cleaning compositions contain the polyether hydroxycarboxylate copolymers are laundry detergents, stain removers, dishwashing detergents, and hard surface cleaners. Examples of articles which can be cleaned using the cleaning compositions are fabrics, such as clothes, linen, folders, or upholstery; hard surfaces such as counter tops, windows, floors, plates, glass or tiles; or cars. The cleaning composition may be a solid or liquid composition. If the cleaning composition is solid, the cleaning composition can be in any usual physical form, such as, for example, powders, beads, flakes, bars, tablets, noodles, pascas, and suspension. If the cleaning composition is liquid, the cleaning composition preferably disperses or solubilizes the polyether hydroxycarboxylate copolymer. The cleaning composition can be aqueous or non-aqueous. For example, the polyether hydroxycarboxylate copolymer can be dissolved or dispersed in water, in one or more inert solvents or diluents. Preferably, the cleaning composition is aqueous. The cleaning compositions may contain any additional components which are used in cleaning compositions. Such additional components are well known to those skilled in the art and include one or more surfactants, builders, ion exchangers, alkalis, anti-corrosion materials, antiredeposition materials, optical brighteners, fragrances, dyes, chelating agents, enzymes, decolorizers, brighteners, agents antistatics, foam control agents, solvents, hydrotropes, bleaching agents, perfumes, fading precursors, water, damping agents, stain removal agents, stain release agents, softening agents, opacifiers, inert diluents, damping agents, corrosion inhibitors, gray matter inhibitors, anti-redeposition agents, stabilizers, opacifiers, fillers, builders, phosphate co-builders, and phosphate replacement builders. Combinations of such additional components can be used. Preferable cleaning compositions are prepared using the polyether hydroxycarboxylate copolymers containing at least one surfactant. Suitable surfactants include nonionic, anionic, cationic and amphoteric surfactants. The surfactants usable in the cleaning composition can also be jones. Anionic surfactants include, for example, alkylbenzene sulphonates from Ce to C? , C 2 to C 6 alkanesulphonates, C 2 to C 2 alkyl sulfates, C 2 to C 6 alkylsulphosuccinate, sulfated ethoxylated alkanols from C 2 to C 1? Nonionic surfactants include, for example, alkylphenol ethoxylates from Cg to Cj.2, C ?2 to C2 alkanol alkoxylates, and block copolymers of ethylene oxide and propylene oxide. Optionally, the end groups of polyalkylene oxides can be blocked, whereby the free OH groups of the polyalkylene oxides can be etherified, esterified, acetalized and / or aminated. Another modification consists in reacting the free OH groups of the polyalkene oxide with isocyanates. Nonionic surfactants also include alkyl glycosides from C4 to C, as well as the alkoxylate products obtainable therefrom by alkoxylation, particularly those obtainable by the reaction of alkyl glycosides with ethylene oxide. Cationic surfactants contain hydrophilic functional groups in which the range of the functional groups are positive when dissolved or dispersed in an aqueous solution. Normal cationic surfactants include, for example, amine compounds, oxygen containing amines, and quaternary amine salts. Amphoteric surfactants contain both acidic and basic hydrophilic groups. Amphoteric surfactants are preferably derived from secondary and tertiary amines, derived from quaternary ammonium compounds, quaternary phosphonium or tertiary sulfonium. The cationic atom in the quaternary compound can be part of a heterocyclic ring. The amphoteric surfactant preferably contains at least one aliphatic group, which contains about 3 to about 18 carbon atoms. At least one aliphatic group preferably contains a water-soluble anionic group such as carboxy, sulfonate or phosphonium. Generally, anionic surfactants, such as linear alkyl sulfonates (LAS) are preferred for use in solid cleaning compositions containing polyether hydroxycarboxylate copolymers. Mixtures of nonionic and anionic surfactants such as alcohol ethoxylates and LAS are preferred in liquid cleaning compositions containing the hydroxycarboxylic or polyether copolymer. The surfactants are optionally present in an amount of from about 0 to about 50 weight percent, preferably from about 2 to about 45 weight percent, and more preferably from about 5 to about 40 weight percent of the cleaning composition . Examples of builders which may be present in the cleaning composition include, for example, phosphates, such as pyrophosphates, polyphosphates, or sodium tripolyphosphate. Further examples are zeolites, sodium carbonate, polycarboxylic acids, nitriloacetic acid, citric acid, tartaric acid, salts of the above acids and monomeric, oligomeric or polymeric phosphonates. Constructor combinations can also be used. The builders are optionally present in an amount of from about 0 to about 85 weight percent, preferably from about 5 to about 50 weight percent based on the total weight of the cleaning composition. Liquid cleaning compositions containing the polyether hydroxycarboxylate copolymer may contain up to 80 weight percent water or solvents or combinations thereof. Typical solvents which may be used include oxygen containing solvents such as alcohols, esters, glycos, and glycol ethers. Alcohols that can be used in cleaning compositions include, for example, methanol, ethanol, isopropanol, and tertiary butanol. Esters which may be used include, for example, amyl acetate, butyl acetate, ethyl acetate, and glycol esters. The glycols and glycol ethers which are used as solvents include, for example, ethylene glycol, propylene glycol, and ethylene or propylene glycol oligomers. Solid cleaning compositions containing the polyether hydroxycarboxylate copolymer preferably contain up to 60 weight percent of one or more solid inert diluents such as sodium sulfate, sodium chloride, sodium borate or selected polymers such as polyethylene glycol or propylene glycol. The cleaning composition may contain from 0 to about 50 weight percent of one or more buffering agents. Buffering agents include, for example, one or more alkali metal salts, such as silicates, carbonates or sulfates. Buffering agents also include, for example, organic alkalis such as triethanolamine, monoethanolamine and triisopropanolamine.

Other additives, which optionally may be included in the cleaning compositions especially for detergent compositions are bleaching agents, used in an amount of up to about 30 weight percent, corrosion inhibitors such as silicates used in an amount of up to 25 per cent. percent by weight, agents that inhibit the deposition of dyes, used in an amount of up to about 20 weight percent, and gray matter inhibitors used in an amount of up to about 5 weight percent. Bleaching agents are, for example, perborates, percarbonates, or chloride-generating substances such as chloroisocyanurates. Suitable silicates used as corrosion inhibitors are, for example, sodium silicate, sodium disilicate, and sodium metasilicate. Suitable dye inhibiting agents are, for example, polyvinylpyrrolidone. Examples of gray matter inhibitors are for example, carboxymethylcellulose, methylcellulose, hydroxypropylmethylcellulose, and graft copolymers of vinyl acetate and polyalkene oxides having a molecular weight of 1,000 to 15,000. In a cleaning composition, the polyether hydroxboxylate copolymer improves or "builds" the cleaning efficiency of a surfactant by hardening inactivating ions such as calcium and magnesium, and other metal ions such as iron. The polyether hydroxboxylate copolymers soften water by sequestration. In addition, the polyether hydrocarboxylate copolymers assist in the cleaning by dispersion and suspension of spots to prevent redeposition of stains on cleaning substrates. The following non-limiting examples illustrate additional aspects of the invention. EXAMPLE 1 (COMPARATIVE) Preparation of a polyepoxy succinic acid. Maleic anhydride, 22.3 g (0.227 mol) is mixed with 32 g of deionized water. The maleic acid is neutralized by the addition of 29.3 drops (0.366 moles) of a 50% NaOH solution. The neutralization is carried out under cooling using an ice bath. The mixture is heated to 55 ° C and 0.792 g (0.0024 mole) of sodium tungstate dihydrate are added and dissolved in 3 g of deionized water. The hydrogen peroxide, 23.1 g (0.238 mol) of a 35% solution, is added to the mixture over a period of 15 to 30 minutes while maintaining a temperature of 55 ° C to 65 ° C. Sodium hydroxide, 7 g of a 50% solution is added. The reaction temperature is maintained at 60 ° C for two hours. Calcium hydroxide, 0.84 g (0.014 mol) is added, and the reaction temperature is increased from 95 ° C to 100 ° C for three hours to form a polyepoxy succinic acid product which was slightly cloudy. EXAMPLE 2 Preparation of polyether hydroxboxylate copolymer containing 10 mole percent of iraconic acid as a comonomer. Maleic anhydride, 20 g (0.204 mol) and 3 g (0.023 mol) of itaconic acid are mixed with 32 g of deionized water. Maleic acid and itaconic acid are neutralized by dropwise addition of 29.3 (0.366 moles) of 50% NaOH solution. The neutralization was carried out under cooling using an ice bath. The mixture was heated to 55 ° C and 0.792 g (0.0024 mol) of sodium tungstate dihydrate dissolved in 3 g of deionized water were added. Sodium peroxide, 23.1 g (0.238 mol) of 35% solution was added, added to the mixture for a period of 30 to 60 minutes while maintaining a temperature of 55 ° C to 65 ° C. The reaction mixture was heated at 60 ° C for two hours. Sodium hydroxide, 7 g of 50% solution was added. The reaction temperature was maintained at 60 ° C for two hours. Calcium hydroxide, 0.84 g (0.014 mole) was added, and the reaction temperature was increased from 95 ° C to 100 ° C for four hours to form a copolymerized product. The product of the polyether hydroxboxylate copolymer was a clean amber colored solution. EXAMPLE 3 Preparation of a hydroxboxylate or polyether copolymer containing 10 mole percent vinylphosphonic acid as a comonomer. Maleic anhydride was mixed, 20 g (0.204 moles) and 3.12 g of 80% solution (0.023 moles) of vinylphosphonic acid (commercially available as ITC 467 from Albright and Wilson) with 32 g of deionized water. Maleic acid and vinylphosphonic acid were neutralized by the addition of 28.8 (0.36 mol) drops of 50% NaOH solution. The neutralization was carried out under cooling using an ice bath. The mixture was heated to 55 ° C and 0.792 g (0.0024 mole) of sodium tungstate dihydrate dissolved in 3 g of deionized water were added. Hydrogen peroxide, 23.1 g (0.348 mole) of a 35% solution was added to the mixture over a period of 30 to 60 minutes while maintaining a temperature of 55 ° C to 65 ° C. The reaction mixture was heated at 60 ° C for two hours. Sodium hydroxide, 7 g of 50 solution, was added with cooling. The reaction temperature was maintained at 60 ° C for two hours. Calcium hydroxide, 0.84 g (0.014 mole) was added and the reaction temperature increased from 95 ° C to 100 ° C for five to six hours to form a copolymerized product. The polyether hydroxycarboxylate copolymer product was a slightly opaque white solution. EXAMPLE 4 Preparation of polyether hydroxycarboxylate copolymer containing 7.5 mole percent itaconic acid as a comonomer. Maleic anhydride, 20.6 g (0.2099 moles) and 2.2 g (0.017 moles) of itaconic acid were mixed with 33.5 g of deionized water. The mixture was heated to 60 ° C to form a clear homogeneous solution. The sodium tungstate dihydrate 1089 g (0.0033 mol) was then added and dissolved in 4.0 g of deionized water. The reaction mixture changed to a yellow color. Hydrogen peroxide, 27.6 g (0.284 moles) of a 35% solution, was added to the mixture over a period of 30 to 60 minutes while maintaining a temperature of 55 ° C to 65 ° C. The reaction mixture changed to a clear water white color and was heated at 60 ° C for three to four hours for 30 to 60 minutes while maintaining a temperature of 55 to 65 ° C. The reaction temperature was maintained at 60 ° C for three to four hours. Sodium hydroxide 32.7 g (0.408 mole) is added to the reaction for 30 to 60 minutes while maintaining a temperature of 60 to 70C. The reaction is then maintained at 60C for 4 to 5 hours. The reaction mixture is cooled to below room temperature. Sodium hydroxide 2.3 g (0.045 mol) of a 50"solution was added to complete the neutralization. Calcium hydroxide 1.3 (0.022 mol) was added, and the reaction temperature was increased from 95 ° C to 100 ° C for seven to eight hours to form a copolymer product. The polyether hydroxycarboxylate copolymer product was a light yellow slightly clear solution. EXAMPLE 5 Calcium Binding Properties The calcium binding properties of the polyepoxy succinic acid polymer prepared in Example 1 and the polyether hydroxycarboxylate copolymers prepared in Examples 2-4 were evaluated in a Hampshire Binding test. The Hampshire Binding test procedure was as follows: (1) Prepare a 0.25 M calcium acetate solution (2) Prepare a 2 percent by weight polymer solution based on solids from each of the polyepoxy succinic acid polymers in Example 1 and polyether hydroxycarboxylate copolymers prepared in Example 2-4 (3) Prepare a 2 weight percent solution of sodium carbonate. (4) Mix 50 grams of polymer and copolymer solutions with 10 ml of sodium carbonate solution. Dilute with deionized water to 100 ml. (5) Grind the mixture prepared in step 4 with the 0.25 M calcium acetate solution until the mixture remains cloudy. TABLE 1 Polymer / Copolymer Calcium binding polymer in mg of CaCO3 / g Succinic acid polyepoxy of 65 Example 1 Polyether carboxylate with 208 10.0 mol% itaconic acid of Example 2 Polyether carboxylate with 206 10 mol% vinyl phosphonic acid of Example 3 Polyether carboxylate with 219 7.5 mol% itaconic acid of Example 4 The data in the Table 1 indicate that the polyether hydroxycarboxylate copolymers of the invention have superior calcium binding properties when compared to polyepoxy succinic acid.

EXAMPLE 6 Evaluation of anti-redeposition properties The polyepoxy succinic acid polymer prepared in Example 1 and the polyether hydroxycarboxylate copolymers prepared in Examples 2-4 were evaluated for anti-redeposition properties. The anti-redeposition test was conducted on a terg-o-tometro using three cotton samples of 4 x 4.5"and three EMPA 213 4 x 4.5" (polycotton samples available from Test Fabrics). Five 4 x 4"polycotton samples were used as ballast, the wash cycle was 10 minutes using 0.9 g / l of UNBUILT liquid detergent (composition listed below) and 150 ppm of hardened water with a Ca ratio of Mg of 2: 1. The solid used was 0.3 g / 1 of pink clay, 0.16 g / 1 of clay close to black and 0.9 g / 1 of a mixture of oil (70% vegetable oil and 30% mineral oil). The polymers and copolymers were dosed at 4 weight percent of the weight of the detergent The rinsing cycle was 3 minutes using 150 ppm of hardened water with a Ca to Mg ratio of 2: 1. were carried out and the samples were dried in a drum dryer in fixing medium.The values of L ab before the first cycle and after the third cycle were measured as Li, ai, bi, and L- :, a2, b2 respectively.

? E = [(L - L2) 2 + (ai - a2) 2 + (^ - b2) 2] 0'5 The UNBUILT liquid detergent contained 22. J percent by weight of NEODOL 25-7, 18.8 percent in weight of BIOSOFT D40, 3 weight percent triethanolamine, 5 weight percent ethanol, 2 weight percent potassium chloride, and 48.8 weight percent water, NEODOL 25-7 is an alcohol ethoxylate containing Cu-Cis alcohol with 7 moles of ethoxylation, available from Shell Chemical Co. BIOSOFT D40 is a sodium dodecylbenzenesulfonate, available from Stepan Chemical Co. The test results are summarized in Table II. Table II Anti-redeposition Test The results of the test in Table II clearly showed that the polyether hydroxycarboxylate copolymers of the invention have superior anti-redeposition properties when compared to polyepoxy succinic acid. EXAMPLE 7 Evaluation of polymers as Iron Chelation in alkaline conditions. The polyepoxy succinic acid polymer prepared in Example 1 and the polyether hydroxycarboxylate copolymer containing 10 mole percent of itaconic acid prepared in Example 2 were evaluated for their ability to chelate calcium under alkaline conditions. The yield of the polymer and copolymer was again compared with the disodium tetraacetate of ethylenediamine (Versene 100) which is usually a chelating agent. Three individual solutions containing 5 g of the test polymer or copolymer in 500 g of deionized water were prepared. The solutions were stirred by means of a magnetic stir plate and the pH of the solutions was adjusted to 12.0 + -1.0 by the addition of a 50% sodium hydroxide solution. 5 ml of 0.1M ferric chloride solution was added at room temperature (25 ° C) to each solution. Stirring was maintained for 5 minutes. The solutions were removed from a magnetic stir plate and then observed for two minutes in the presence of a brown precipitate of ferric hydroxide which did not dissolve. If a precipitate is present, the test is stopped. If a precipitate is not present, the solutions are placed back on the stir plate and 5 ml of 0.1M ferric chloride solution is added and the pH is adjusted to 12.0 +/- 0.1 by the addition of a sodium hydroxide solution to the solution. fifty%. The temperature and stirring were maintained for 5 minutes. The solutions were removed from the stir plate and then observed for two minutes in the presence of a brown precipitate. This procedure was repeated until the precipitate appeared. The number of thousands of FeCl3 0.1M required to form a precipitate is recorded. 5 ml was subtracted from the last crushing to make my. For example, if the precipitate is first announced after 40 ml of FeCl3, the iron chelation capacity (FeCV) is recorded as 35 ml of FeCl3). If the precipitate is present after the first 5 ml, the chelate has no chelation value for its test. The results of the test are summarized in Table III. TABLE III Ferrous Chelation Test Polymer / Copolymer Iron Chelation Capacity (0.1M FeCl3 in Polymer Trituration of Example 1 Copolymer of Example 2 >50 EDTA (Versene 100) 5 The test results in Table III clearly showed that the polyether hydroxycarboxylate copolymer of Example 2 effectively ironed high alkalinity system while EDTA was not effective as a low auxiliary processing unit. such alkaline conditions. However, the results of the Table III test show that the polyether hydroxycarboxylate copolymers of the invention are superior chelating agents when compared to the polyepoxy succinic acid polymers. While not wishing to be bound by any particular theory, the present inventors believe that the copolymers of the invention are effective chelating agents because they form a stable chelate with ferric ions and without delaying the formation of a brown precipitate of ferric hydroxide. EXAMPLE 8 Preparation of a polyether hydroxycarboxylate copolymer containing 100 mole percent of acrylic acid as a comonomer Acrylic acid, 36.0 g (0.5 mole) was mixed with 25.0 g of deionized water. Sodium tungstate dihydrate 2.36 g (0.0071 ml) was dissolved in 6.0 water clesionizacla which was then added. The reaction mixture was returned in an opaque white solution. Hydrogen peroxide, 60.7 g (0.625 moles) of a 35% solution was added to the mixture over a period of 1 to 2 hours while maintaining the reaction at a temperature of 20 ° C to 30 ° C.% The reaction mixture was returned to a light yellow color and heated to 60 ° C for five hours. The reaction mixture was cooled to room temperature. Sodium hydroxide, 30.0 g (0.375) of a 50% solution, was added for 30 to 60 minutes to partially neutralize the acrylic acid to 75 mole percent. The reaction mixture was then heated to 60 ° C for 8 to 10 hours. The reaction was then cooled to room temperature and 6.5 g of a 50% solution of sodium hydroxide (0.08125 moles) was added. Calcium hydroxide, 3.08 (0.0416 moles) was added, and the reaction temperature increased from 95 ° C to 100 ° C for seven to eight hours to form a copolymerization product. The polyether hydroxycarboxylate copolymer product was an opaque white solution which was neutralized with 3.0 g of citric acid (0.0156 moles) to reduce the pH to 10. While the invention has been described with particular reference to certain embodiments thereof, it should be understood that changes and modifications can be made by those with ordinary experience in the art within the scope and spirit of the following claims.

Claims (7)

1. RBIVIDICACIQNES 1. A polyether hydroxycarboxylate copolymer having the structure characterized in that M + is a cation wherein M is independently selected from the group consisting of hydrogen, ammonia, alkali metals, alkaline earth metals, zinc, copper, organic amines, amino acids, and amine saccharides; R is the residue of an ethylenically unsaturated comonomer having at least one functional group which is selected from the group consisting of carboxylic acid, sulfonic acid and phosphonic acid; R2 and R3 are independently selected from the group consisting of hydrogen, and a substituted or unsubstituted alkyl group, having 1 to 4 carbon atoms; n is from about 2 to about 100; x and v._ are independently 0 or 1; a is from 0 to 99 mole percent; and b is from 100 to 0 mole percent, with the proviso that (a + b) is 100 mole percent.
2. 2. The polyether hydroxycarboxylate copolymer according to claim 1, characterized in that the copolymer is prepared from maleic acid and itaconic acid.
3. 3. The polyether hydroxycarboxylate copolymer according to claim 1, characterized in that the copolymer is prepared from maleic acid and vinylphosphonic acid.
4. 4. The polyether hydroxycarboxylate copolymer according to claim 1, characterized in that the copolymer is prepared from maleic acid and malonic acid.
5. 5. The polyether hydroxycarboxylate copolymer according to claim 1, characterized in that n is from about 2 to about 20.
6. 6. The polyether hydroxycarboxylate copolymer according to claim 1, characterized in that the letter a is 20 to 99 mole percent, and letter b is 1 to 80 mole percent, with the proviso that (a + b) is 100 mole percent. A cleaning composition, comprising at least one surfactant and from about 0.5 to about 98 weight percent, based on the weight of the cleaning composition, of a polyether hydroxycarboxylate copolymer having the structure: wherein the polyether hydroxycarboxylate copolymer improves the cleaning efficiency of the surfactant by inactivation of hardening ions, and wherein M1 'is a cation wherein M is independently selected from the group consisting of hydrogen, ammonia, alkali metals, alkaline earth metals , zinc, copper, organic amines, amino acids, and amino saccharides; Ri is the residue of an ethylenically unsaturated comonomer having at least one functional group which is selected from the group consisting of carboxylic acid, sulfonic acid and phosphonic acid; R2 and R3 are independently selected from the group consisting of hydrogen, and a substituted or unsubstituted alkyl group, having 1 to 4 carbon atoms; n is from about 2 to about 100; xx and x_ are independently 0 or 1; a is from 0 to 99 mole percent; and b is from 100 to 0 mole percent, with the proviso that (a + b) is 100 mole percent. SUMMARY The invention provides novel polyether hydroxycarboxylate copolymers, which are effective sequestering agents. The polyether hydroxycarboxylate copolymer when used in a cleaning composition improves or "creates" the cleaning efficiency of the surfactant by inactivation of hardening ions. In addition, the polyether hydroxycarboxylate copolymers aid in the cleaning by dispersion and suspension of spots to prevent redeposition of spots. The polyether hydroxycarboxylate copolymer has the structure wherein M + is a cation wherein M is independently selected from hydrogen, ammonia, alkali metals, alkaline earth metals, zinc, copper, organic amines, amino acids and aminosaccharides; R2 and R are independently hydrogen or a substituted or unsubstituted alkyl group, having 1 to 4 carbon atoms; n is from about 2 to about 100; xi and x2 are independently 0 to 1; a is from O to 99 mole percent; and b is from 100 to 1 mole percent, with the proviso that (a + b) is l O mole percent.