Copolymers of allyliminodiacetic acid with unsaturated carboxyli

Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...

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526240, 510361, C08F 2600

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active

055480497

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BRIEF SUMMARY
In recent years, polymeric carboxylic acids, such as polyacrylic acid, polymethacrylic acid, polyhydroxyacrylic acid, and polymaleic acid, as well as their copolymers have gained great importance in phosphate-reduced and phosphate-free detergents. The advantages of polymer carboxylic acids are based on their good dispersing action of precipitates in the washing liquor, in particular of calcium carbonate and soil particles, and on a good transport capacity of calcium ions from the aqueous washing liquor into the zeolites of the detergents.
However, the complexing properties of polycarboxylic acids to heavy metal ions are absolutely insufficient. Since, however, heavy metal ions of Cu, Fe, and Mn, which are always present in washing liquors, decompose the peroxidic bleaching agents of a detergent, thus not only impairing the washing result, but also causing damage to the textile fabric, detergents must contain effective heavy metal complexing agents to exclude the negative effects of heavy metal ions. Typical heavy metal complexing agents used in phosphate-free detergents are nitrilotriacetate, ethylene diamine tetraacetate, or aminomethylene phosphonic acids.
D'Alelio, Journal of Macromolecular Science-Chemistry, Vol. A6, pp. 513-567 (1972), describes polymers and their metal complexes which are produced by reacting polyglycidyl methacrylate with aminoacetic acid or iminodiacetic acid, respectively.
A great disadvantage of these polymers is the susceptibility to hydrolysis of the methacrylic acid ester group. In particular in alkaline washing liquors and at elevated temperatures the ester group is unstable and saponified rapidly. As a consequence, hydrolysis of these polymers results in a homopolymethacrylic acid which no longer has complexing properties to heavy metal ions.
U.S. Pat. No. 4,868,263 describes copolymers of an .alpha.,.beta.-unsaturated monomer for the water treatment, preferably with an acid group and amine-containing allyl ethers as the second monomer which is produced of allyl glycide ether and an amino-functional compound. Monoalkylamines or dialkylamines and aminocarboxylic acids, e.g., N-methylglycine and iminodiacetic acid are used as amino-functional compounds. The monomers based on allyl ethers are monomers which react very slowly in radical polymerization and strongly tend to terminate the chain transfer (cf. Houben-Weyl, Methoden der Organischen Chemie, Vol. 14/1, p. 1145). Owing to these properties, allyl ethers only give polymers having low molecular weights, and the conversion of the allyl ether monomer frequently remains incomplete.
EP 0 437 843 describes copolymers of unsaturated acids and alkenylaminomethylene phosphonic acids as well as their use as complexing agents and as co-builders in detergents.
It was the object of the present-invention to provide polycarboxylic acids which are free of phosphorus, have hydrolytic stability and complexing properties and whose molecular weights can be varied over a wide range.
Thus, the subject matter of the present invention are polymers of having the formula (I) ##STR2## wherein R.sup.1 =hydrogen, C.sub.1 -C.sub.4 alkyl or --COOM, R.sup.2 =hydrogen or C.sub.1 -C.sub.4 alkyl, R.sup.3 =hydrogen, C.sub.1 -C.sub.4 alkyl or CH.sub.2 COOM, and M=hydrogen, ammonium, an alkali metal or an alkaline-earth metal, and
The polymers according to the present invention combine the known properties of two product classes in one polymer. The polymers exhibit the good dispersing properties of the polycarboxylic acids and, at the same time, they complex heavy metal ions to a great extent which is comparable to the classical complexing agents nitrilotriacetate or ethylene diamine tetraacetate. By varying the monomer ratios and the molecular weight polymers having optimized properties can be produced for different applications. The polymers are used in the scale inhibition of saline waters, e.g., in water coolers, or for the dispersion of Ca-carbonate in washing liquors and dyeing baths, or as builder and co-builder in detergents, or as stabilizer for perox

REFERENCES:
patent: 2901495 (1959-08-01), Teeter et al.
patent: 3887653 (1975-06-01), Konishi et al.
patent: 4058656 (1977-11-01), Markiewitz et al.
patent: 4868263 (1989-09-01), Chen et al.
patent: 5256315 (1993-10-01), Lockhart et al.

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