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Carboxylate Ester of Polysaccharide Carboxylatester Von Polysaccharid Ester De Carboxylate De Polysaccharide

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Carboxylate Ester of Polysaccharide Carboxylatester Von Polysaccharid Ester De Carboxylate De Polysaccharide (19) TZZ¥_ _T (11) EP 3 122 786 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C08B 37/00 (2006.01) C11D 3/22 (2006.01) 03.01.2018 Bulletin 2018/01 C11D 17/06 (2006.01) (21) Application number: 15708839.4 (86) International application number: PCT/EP2015/055056 (22) Date of filing: 11.03.2015 (87) International publication number: WO 2015/144438 (01.10.2015 Gazette 2015/39) (54) CARBOXYLATE ESTER OF POLYSACCHARIDE CARBOXYLATESTER VON POLYSACCHARID ESTER DE CARBOXYLATE DE POLYSACCHARIDE (84) Designated Contracting States: • DETERING, Jürgen AL AT BE BG CH CY CZ DE DK EE ES FI FR GB 67117 Limburgerhof (DE) GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO • SCHNEIDER, Ulrich PL PT RO RS SE SI SK SM TR 67063 Ludwigshafen (DE) • NEUMANN, Jessica (30) Priority: 25.03.2014 EP 14161502 67590 Monsheim (DE) (43) Date of publication of application: (74) Representative: BASF IP Association 01.02.2017 Bulletin 2017/05 BASF SE G-FLP-C006 (73) Proprietor: BASF SE 67056 Ludwigshafen (DE) 67056 Ludwigshafen am Rhein (DE) (56) References cited: (72) Inventors: EP-A1- 0 703 243 EP-A1- 0 792 888 • SHABELINA, Natalia WO-A1-00/18860 WO-A1-01/00771 68163 Mannheim (DE) WO-A1-2006/117071 US-A- 3 022 287 • WITTELER, Helmut US-A- 4 659 849 67157 Wachenheim (DE) Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 3 122 786 B1 Printed by Jouve, 75001 PARIS (FR) EP 3 122 786 B1 Description [0001] The invention relates to carboxylate ester of polysaccharide characterised in that it possesses ester bonds with trimellitic anhydride and are soluble in water. The invention further relates to methods for the manufacture of these 5 polysaccharides esters and to their use in fabric and home care formulations. [0002] Due to the increasing demand for environmentally friendly and sustainable polymers the development of bio- degradable polymers in the area of fabric care, home care but also in the area of water treatment has become more and more important. Typical state-of-the-art polymers for laundry or automatic dish washing applications are non-bio- degradable. Polymers obtainable by free-radical polymerization and composed of monomers containing carboxy groups 10 and/or sulfonic acid groups have been an important constituent of phosphate-containing and phosphate-free fabric and home care formulations for many years. By virtue of their soil-dispersing and deposit-inhibiting effect, they make a considerable contribution to the cleaning and rinsing performance of fabric and home care formulations. For instance, they ensure that no salt deposits of the hardness-forming calcium and magnesium ions remain on the ware or on the textile. These polymers are also used in water-conveying systems as agents for preventing mineral deposits such as 15 e.g. calcium and magnesium sulfate, magnesium hydroxide, calcium and barium sulfate and calcium phosphate on heat transfer surfaces or in pipelines. Water-conveying systems to be mentioned here are inter alia cooling and boiler feed water systems and industrial process waters. However, these polymers are also used as scale inhibitors in the desalination of seawater or brackish water by distillation and by membrane processes such as reverse osmosis or electrodialysis. One disadvantage of these polymers obtainable by free-radical polymerization and composed of monomers containing 20 carboxy groups and/or sulfonic acid groups is that they are not biodegradable. [0003] Many attempts have been made to find biodegradable alternatives to acrylic acid based dispersants and an- tiscalants: WO 01/00771 A1 reports the esterification of fructans with acetic anhydride in water and its use as a bleach activator. 25 The degree of substitution of the obtained acetylated fructan lies in the range of from 0.4 to 2.5. US 5,877,144 describes aliphatic carboxylate esters of inulin having at least six monosaccharide units linked together wherein the inulin is esterified with anhydrides of carboxylic acids such as acetic anhydride, lauric anhydride, palmitic anhydride. The inulin esters have a degree of substitution of less than 0.5 and are proposed as surfactants. Makromol. Chem. 187, 125-131 (1986) reads on the derivatives of inulin by esterification with succinic anhydride 30 and the use of 4-dimethylaminopyridine and 1-methyl-imidazole as acylation catalysts. Carbohydrate Polymers 64 (2006) 484-487 describes the esterification of starch with succinic anhydride in water and in organic solvents such as dimethylsulfoxide and the formation of biodegradable hydrogels. US2011/0257124 A1 reads on apolysaccharide osmoticcomprising monosaccharide monomerswhich are esterified with a dicarboxylic and/or tricarboxylic acid. The tricarboxylic acid is citric acid. The osmotic is used in a dialysis 35 solution for peritoneal dialysis treatment. EP 1 939 219 A1 discloses non-crosslinked, highly citrated, water-soluble polysaccharides, their preparation process in an organic solvent and their use in cosmetic and pharmaceutical formulations. EP 0 703 243 A1 describes a process for preparing polysaccharides with one or more hydrophobic side chains in a mixture comprising at most 25% by weight of water. The hydrophobic side chains are C6-C24 alk(en)yl compounds, 40 resulting from the esterification of starch with e.g. C6-C24 alk(en)yl succinic anhydride. US 6,063,914 reads on a process for producing starch maleates by reacting starch with maleic acid anhydride in water. The pH is maintained constant between 7 and 11, preferably between 8 and 9, during the reaction of the anhydride with the starch. 45 [0004] Though many of the described esterified polysaccharides are biodegradable, many fail to exhibit an acceptable performance as to their calcium carbonate inhibition capacity. The inhibition of inorganic scale such as calcium carbonate is a very important parameter when it comes to applications in the field of fabric and home care. The inhibition of inorganic scale enables a control of water hardness, thus increasing the effectiveness of washing agents such as surfactants. The inhibition of organic scale prevents as well the redeposition of soil and has an impact on rinsing, thus enabling a reduction 50 of water spots and an improvement of shine on surfaces such as glasses. Besides, biodegradable polysaccharide esters are usually easily hydrolyzed at a basic pH: this is an issue for their application in laundry and automatic dish washing where the pH of the wash liquor generally lies in the range of 8 to 11. Additionally the long-term stability of such polysaccharide esters in liquid fabric and home care formulations is affected by their insufficient hydrolysis stability. In particular, for those of the biodegradable polysaccharide esters who exhibit an acceptable performance as to their 55 calcium carbonate inhibition capacity, their lack of stability leads to a decrease and even an absence of effective inorganic scale inhibition. [0005] It was therefore an object of the invention to provide substances which at the same time are biodegradable and can be advantageously used for cleaning purposes or for the purpose of scale inhibition in water-conveying systems 2 EP 3 122 786 B1 and are stable against hydrolysis at basic pH. It was a further object of the invention to provide substances which can be readily incorporated into formulations for cleaning purposes in their various presentation forms. It has surprisingly been found that these objects are achieved, as is evident from the disclosure of the present invention, by a carboxylate ester of polysaccharide, wherein the polysaccharide is esterified with trimellitic anhydride and wherein 5 the degree of substitution of the polysaccharide lies in the range of from 1 to 2.5. The polysaccharide is preferably a water-soluble polysaccharide such as inulin, maltodextrin, xyloglucan, alginate, starch or a mixture thereof. Preferably, the polysaccharide is inulin or maltodextrin. It is to be noted that low molecular weight water-soluble polysaccharides such as inulin and maltodextrin are also soluble in certain organic solvents such as dimethylformamide, dimethylsulfoxide and pyridine. 10 Starch is a mixture of amylose and amylopectin, wherein the amount of amylose is present in the mixture in an amount of 20 to 30wt% and the amylopectin is present in the mixture in an amount of 70 to 80wt%. Amylose is a linear polysac- charide consisting of α-1,4-linked D-glucose. Amylopectin is a high molecular weight polysaccharide with the same backbone as amylose but with α-1,6-linked branching points every 24 to 30 glucose units. Maltodextrin is a polysaccharide produced by partial hydrolysis of starch and consists of α-1,4-linked D-glucose. 15 Xyloglucan has a backbone of β-1,4-linked glucose residues, most of which is substituted with 1-6 linked xylose side chains. The xylose residues are often capped with a galactose residue. Alginate is a linear copolymer comprising homopolymeric blocks of β-1,4-linked D-mannuronate and α-L-guluronate residues, covalently linked together in different sequences or blocks. Inulin is a linear polydisperse polysaccharide and consists of a chain βof-2,1-linked furanoid fructose units which is terminated at the reducing end by an α-D glucose molecule. The most important sources of inulin 20 are chicories (Cichorium intybus), dahlias (Dahlia Pinuata Cav.) and Jerusalem artichokes (Helianthus tuberosis). The molecular weight distribution and average chain length depends on the type of plant from which it is isolated, on the weather conditions during the growth of the plant and on the age of the plant.
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