WO2000061639A1 - Amidon oxyde et son utilisation, en particulier en tant que superabsorbant - Google Patents

Amidon oxyde et son utilisation, en particulier en tant que superabsorbant Download PDF

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Publication number
WO2000061639A1
WO2000061639A1 PCT/EP2000/002456 EP0002456W WO0061639A1 WO 2000061639 A1 WO2000061639 A1 WO 2000061639A1 EP 0002456 W EP0002456 W EP 0002456W WO 0061639 A1 WO0061639 A1 WO 0061639A1
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Prior art keywords
starch
carbon atoms
oxidized starch
oxidation
oxidized
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PCT/EP2000/002456
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German (de)
English (en)
Inventor
Richard Fisher
Wolfgang A. Herrmann
P. Jochen Zoller
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Celanese Chemicals Europe Gmbh
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Publication of WO2000061639A1 publication Critical patent/WO2000061639A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/18—Oxidised starch

Definitions

  • the present invention relates to oxidized starch and its use, in particular as a superabsorbent.
  • Starch is a biopolymer (approx. 30% amylose and approx. 70% amylopectin), which is to be understood as the condensation product of ⁇ -D-glucose units.
  • the condensation of the ⁇ -D-glucose units with one another mainly occurs as a 1,4 linkage, as a result of which a linear chain molecule is formed.
  • a 1, 6 linkage of the ⁇ -D-glucose units causes branches along the chain.
  • strength can be expressed in a simplified manner using the following formula,
  • n describes the number of anhydroglucose units linked together glucosidically.
  • starch This simplified structural formula for starch is intended to be the basis for further derivatives listed below, but there are also branches. conditions, ie ⁇ -1, 6-links, even if these are not explicitly shown in the above and in the following formulas.
  • native starch ie chemically non-derivatized, natural starch, which is described according to the present invention with the structural formula mentioned above, is actually a polycondensate of ⁇ -D-glucose, which is mainly 1, 4 linkage and also 1, 6 - Has link.
  • Native starch is made from corn, cereals, potatoes, peas, cassava, rice, millet, etc. won.
  • the number n of anhydroglucose units linked together glucosidically with native starch is generally between 20 and 15,000.
  • starch In the industrial field, starch is used primarily in a modified form.
  • starch graft polymers based on acrylate are used on a large scale as absorption materials, which in particular bind and store water.
  • Water-binding and storing absorption materials are known under the term "superabsorbents" and are used particularly in the manufacture of incontinence articles.
  • carboxyiat groups are present, for example, as sodium or potassium salts in addition to free carboxylic acid groups, the degree of neutralization being between 60 and 90 mol%.
  • n describes the number of anhydroglucose units in the original strength.
  • a modified starch in which at least 90 mol% of the primary alcohol groups present in the original starch are oxidized to carboxyl groups, ie a substance with the following structure
  • n and m are integers and the quotient n / m is greater than 0.9.
  • WO 91/04988 describes the selective oxidation of starch to ⁇ -polyglucuronic acid or ⁇ -polyglucuronate using chlorine bleach and Additives are known with which the starch interacts with or interacts with the addition (eg carboxylic acids). According to this method, at least 67% of the primary alcohol groups present in the original starch are oxidized to carboxyl groups.
  • the object of the present invention is to provide an oxidized starch which is particularly suitable for the production of absorption materials.
  • the oxidizing agent is introduced into the acidic starch solution in an amount of 0.1-1.9 equivalents, based on the anhydroglucose units present in the native starch;
  • MTO methyltrioxorhenium
  • alkylrhenium oxide which is an alkyl group of the general formula -C n H 2 n + ⁇ , in which n is an integer and is 2 to 20, or one Cycloalkyl group of the general formula -C n H 2n - ⁇ , in which n is an integer and is 3 to 10, contains, or Re0 3 or Re 2 0 7 , in a molar ratio of the anhydroglucose units present in the native starch to the rhenium compound used between 1: 1 and 1000: 1; and
  • the oxidation is carried out in water or in a carboxylic acid or in an organic solvent or in a mixture which contains at least two of these constituents, and
  • the oxidation is carried out at a temperature between 0 and 50 ° C.
  • Another object of the invention relates to a method for producing oxidized starch by oxidation of native starch in an acid solvent, which is characterized in that
  • the oxidizing agent is introduced into the acidic starch solution in an amount of 0.1-1.9 equivalents, based on the anhydroglucose units present in the native starch; b) the oxidation is carried out in the presence of a catalyst comprising:
  • MTO methyltrioxorhenium
  • alkylrhenium oxide which is an alkyl group of the general formula -CnH 2n + ⁇ , in which n is an integer and is 2 to 20, or a cycloalkyl group of the general formula -CnH 2 n- ⁇ , in which n is an integer and is 3 to 10, contains, or ReO 3 or Re 2 0 7 , in a molar ratio of the anhydroglucose units present in the native starch to the used
  • Rhenium compound between 1: 1 and 1000: 1;
  • the oxidation is carried out in water or in a carboxylic acid or in an organic solvent or in a mixture which contains at least two of these constituents, and
  • the oxidation is carried out at a temperature between 0 and 50 ° C.
  • Hydrogen peroxide alkali or alkaline earth metal percarbonates, alkali or alkaline earth metal perborates and others are used as the oxidizing agent Peroxo compounds, aliphatic and aromatic peroxo acids, such as peracetic acid or perbenzoic acid.
  • the preferred oxidizing agent is hydrogen peroxide.
  • the carboxylic acid used in step a), in step c) and that used in b) (iii) can be both different and identical.
  • the same carboxylic acid is preferably used to prepare the starch solution (step a), to carry out the reaction after step c) and to dissolve the hydrogen halide according to b) (iii).
  • Suitable carboxylic acids are aliphatic or aromatic mono- and dicarboxylic acids with 1-12 carbon atoms in the molecule. Aliphatic monocarboxylic acids having 2-6 carbon atoms in the molecule, in particular acetic acid, propionic acid, n- and i-butyric acid and the isomeric valeric acids, are preferably used. The use of acetic acid is particularly preferred. Mixtures of carboxylic acids can also be used, but a carboxylic acid is preferably used.
  • HBr and HCl, in particular HBr, are particularly suitable as hydrogen halide.
  • organic solvent use is made of polar organic solvents, such as, for example, aliphatic or cycloaliphatic mono- or polyalcohols having 1 to 6 carbon atoms, such as, for example, methanol, ethanol, glycerol or neopentyl glycol, and also mono-, di-, triethyiene glycol or polyethylene glycol with an average molecular weight of 320 to 650, aliphatic or cycloaliphatic ethers with 2 to 10 carbon atoms, such as diethyl ether or 1,4-dioxane, aliphatic or cycloaliphatic ketones with 3 to 8 carbon atoms, such as acetone, methyl isobutyl ketone, polyhalogenated hydrocarbons with 1 to 8 carbon atoms, such as methylene chloride or chloroform and alkylbenzenes with 7 to 10 carbon atoms, such as toluene or ethylbenzene.
  • R 1 and R 2 are the same or different and represent an alkyl group with 4-12 carbon atoms
  • at least the carbon atoms bonded directly to the nitrogen atom each carrying two identical or different alkyl groups with 1-4 carbon atoms, or R 1 and R 2 together form an alkyl-substituted five- or six-membered heterocycle with the nitrogen atom.
  • the carbon atoms bonded directly to the nitrogen atom each carry two identical or different alkyl groups with 1-4 carbon atoms.
  • two methyl groups are bonded to the carbon atoms adjacent to the nitrogen atom. If there is a six-membered heterocycle, the carbon atom in the 4-position to the nitrogen atom can carry further substituents.
  • substituents are the tertiary-butyl group, the amino group NR 3 R 4 in which R 3 and R 4 are identical or different and hydrogen or represent a straight-chain or branched alkyl group with 1-4 carbon atoms, or the hydroxy or an alkoxy group with 1-4 carbon atoms, in particular the methoxy group.
  • 2,2,6,6-Tetramethylpiperidin-1-yloxyl, 2,2,6,6-tetramethylpiperidin-4-methoxy-1-yloxyl, 2,2,6,6-tetramethylpiperidine-4-hydroxy-1 are particularly preferred -yloxyl or 2,2,6,6-tetra-methylpiperidine-4-amino-1 -yloxyl.
  • Methyltrioxorhenium has proven particularly effective among the rhenium compounds.
  • the starch oxidized according to the invention shows three essential differences in its application properties compared to known oxidized starches:
  • the starch oxidized according to the invention forms a gel in the acidic solution, while the known oxidized starches dissolve without gel formation. Furthermore, the method according to the invention for producing the starch oxidized according to the invention is distinguished by the use of environmentally friendly and inexpensive oxidizing agents, such as Hydrogen peroxide.
  • the starch oxidized according to the invention can be produced much more simply and cost-effectively.
  • the amount of oxidizing agent can be reduced in order to provide an absorption material with comparable properties.
  • significantly fewer salts have to be removed after the reaction than in the known processes.
  • the macromolecules produced according to the invention also show little or no degradation of the 1,4 linkages of the ⁇ -D-glucose units.
  • the oxidized starch of the prior art shows a comparatively greater breakdown of the macromolecule compared to the starting product, which is due to the ⁇ -elimination in the more alkaline environment.
  • Studies of the starch oxidized according to the invention have shown that, in addition to primary alcohol and carboxyl groups, it also has aldehyde groups, some of which are present as free groups and some are hydrates.
  • n + m + o means the number of anhydroglucose units of the native starch used.
  • the hydrogen peroxide is introduced into the starch solution in an amount of 0.3 to 1.7 equivalents, based on the anhydroglucose units present in the native starch.
  • HBr is used in solution in acetic acid and as the di-tertiary alkyl nitroxyl 2,2,6,6-tetramethyipiperid-1-yloxyl or 2,2,6,6-tetramethylpiperidine-4-methoxy-1-yloxyl .
  • ditertiaralkylnitroxyl can also be dispensed with.
  • the oxidation reaction is selective to the Polyglucuronic acids expire.
  • the procedure is then as usual, with the only exception that a rhenium-containing catalyst is used without the addition of di-tertiary alkyl nitroxyl.
  • An oxidation system consisting of MTO, hydrogen peroxide and bromide is then preferably used to produce oxidized starch.
  • the starch oxidized according to the invention can be crosslinked with crosslinking agents such as borax, diepoxides, dialdehydes, titanates.
  • starch oxidized according to the invention is particularly suitable for the production of seed and / or fertilizer carriers, as a material in galenics, as a thickener, soil improver, adhesive or binder.
  • native starch (7.0 g, water content approx. 10%, approx. 39 mmol) is suspended in 150 ml glacial acetic acid (100%). 97.3 mg of MTO (0.39 mmol of methyltrioxorhenium), 60.1 mg of TEMPO (0.39 mmol of 2,2,6,6-tetramethylpiperidin-1-yloxyl) and 1 ml of HBr (30% by weight dissolved in glacial acetic acid) are added. While stirring (300 rpm), 20 ml of a 30% H 2 0 2 solution in water are slowly injected. After the reaction (about 2 h), about 200 ml of methanol are added to the solution while stirring, the oxidized starch precipitating in the form of a gel.
  • the TA value (total absorption) and the CRET value (absorption capacity after spinning) are determined.
  • approx. 340 mg (mass m1) of the ground and sieved product (0.5 - 0.315 mm grain size) are weighed into a tea bag.
  • the bag is closed with three clips and weighed again (mass m2).
  • the bag is then allowed to swell in 50 ml of a NaCl solution (0.9 g / l NaCl) for 20 minutes.
  • the bag is allowed to drain for three minutes and the mass of the moist tea bag (mass m3) is determined.
  • the TA value is determined according to the following equation:
  • the CRET value is determined according to the following equation:

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

Amidon oxydé, obtenu par oxydation d'amidon naturel dans un solvant acide. Selon la présente invention, a) l'oxydant est introduit dans le solvant acide à raison de 0,1 à 1,9 équivalent, par rapport à la quantité d'unité d'anhydroglucose contenues dans l'amidon naturel; b) l'oxydation est effectuée en présence d'un catalyseur contenant i) méthyltrioxorhénium (MTO) ou un oxyde d'alkylrhénium ou ReO3 ou Re2O7, ii) un alkylnytroxyle ditertiaire et iii) un hydracide halogéné dissous dans un acide carboxylique; c) l'oxydation est effectuée dans de l'eau, ou dans un acide carboxylique ou dans un solvant organique ou dans un mélange qui contient au moins deux desdites substances, en tant que solvant; et d) l'oxydation est effectuée à une température située entre 0 et 50 °C. La présente invention concerne encore la préparation d'amidon oxydé, ainsi que son utilisation en tant que superabsorbant, support de semences ou d'engrais, agent d'amendement du sol, matière pour produits pharmaceutiques ou adhésif et liant.
PCT/EP2000/002456 1999-03-27 2000-03-21 Amidon oxyde et son utilisation, en particulier en tant que superabsorbant WO2000061639A1 (fr)

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DE19914067.7 1999-03-27
DE1999114067 DE19914067C1 (de) 1999-03-27 1999-03-27 Oxidierte Stärke, Verfahren zu deren Herstellung sowie deren Verwendung, insbesondere als Superabsorber

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010007139A1 (fr) 2008-07-18 2010-01-21 Solvay Sa Procédé d'oxydation de groupes alcool et/ou aldéhyde
US9376648B2 (en) 2008-04-07 2016-06-28 The Procter & Gamble Company Foam manipulation compositions containing fine particles
CN111217774A (zh) * 2018-11-25 2020-06-02 中国科学院大连化学物理研究所 催化氧化5-羟甲基糠醛到2,5-呋喃二甲酸的方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010004478A1 (de) 2010-01-12 2011-07-14 Riesinger, Birgit, 48346 Neue Technologien zur Verwendung in Wundauflagen mit superabsorbierenden Polymeren

Citations (1)

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WO1995007303A1 (fr) * 1993-09-07 1995-03-16 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Procede d'oxydation des glucides

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JP4380799B2 (ja) * 1996-12-18 2009-12-09 ネーデルランドセ・オルガニザテイエ・フール・テゲパスト−ナトウールベテンシヤツペリーク・オンデルツエク・テイエヌオー 超吸収性材料並びに該材料の製造法
JPH10204102A (ja) * 1997-01-27 1998-08-04 Mitsubishi Gas Chem Co Inc 水溶性トリカルボキシ多糖類の製造方法

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HERRMANN W A ET AL: "Multiple bonds between main group elements and transition metals, 155. (Hexamethylphosphoramide)methyl(oxo)bis(eta-peroxo)rhenium(VII), the first example of an anhydrous rhenium peroxo complex: crystal structure and catalytic properties", JOURNAL OF ORGANOMETALLIC CHEMISTRY,CH,ELSEVIER-SEQUOIA S.A. LAUSANNE, vol. 520, no. 1, 9 August 1996 (1996-08-09), pages 139 - 142, XP004036468, ISSN: 0022-328X *
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NOOY DE A E J ET AL: "TEMPO-MEDIATED OXIDATION OF PULLULAN AND INFLUENCE OF IONIC STRENGTH AND LINEAR CHARGE DENSITY ON THE DIMENSIONS OF THE OBTAINED POLYELECTROLYTE CHAINS", MACROMOLECULES,US,AMERICAN CHEMICAL SOCIETY. EASTON, vol. 29, no. 20, 23 September 1996 (1996-09-23), pages 6541 - 6547, XP000625600, ISSN: 0024-9297 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9376648B2 (en) 2008-04-07 2016-06-28 The Procter & Gamble Company Foam manipulation compositions containing fine particles
WO2010007139A1 (fr) 2008-07-18 2010-01-21 Solvay Sa Procédé d'oxydation de groupes alcool et/ou aldéhyde
US8609895B2 (en) 2008-07-18 2013-12-17 Solvay Sa Process for the oxidation of alcohol and/or aldehyde groups
CN111217774A (zh) * 2018-11-25 2020-06-02 中国科学院大连化学物理研究所 催化氧化5-羟甲基糠醛到2,5-呋喃二甲酸的方法
CN111217774B (zh) * 2018-11-25 2022-08-02 中国科学院大连化学物理研究所 催化氧化5-羟甲基糠醛到2,5-呋喃二甲酸的方法

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