WO1996038484A1 - Ethers d'hydrate de carbone polymeres oxydes utilises comme agent sequestrant et leurs procedes de preparation - Google Patents

Ethers d'hydrate de carbone polymeres oxydes utilises comme agent sequestrant et leurs procedes de preparation Download PDF

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Publication number
WO1996038484A1
WO1996038484A1 PCT/NL1996/000218 NL9600218W WO9638484A1 WO 1996038484 A1 WO1996038484 A1 WO 1996038484A1 NL 9600218 W NL9600218 W NL 9600218W WO 9638484 A1 WO9638484 A1 WO 9638484A1
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Prior art keywords
oxidized
mmol
solution
starch
stirring
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PCT/NL1996/000218
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English (en)
Inventor
Andre Heeres
Ido Pieter Bleeker
Kornelis Fester Gotlieb
Hendrick Arend Van Doren
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Coöperatieve Verkoop- En Productievereniging Van Aardappelmeel En Derivaten Avebe B.A.
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Priority to AU59125/96A priority Critical patent/AU5912596A/en
Publication of WO1996038484A1 publication Critical patent/WO1996038484A1/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
    • C08B11/00—Preparation of cellulose ethers
    • C08B11/20—Post-etherification treatments of chemical or physical type, e.g. mixed etherification in two steps, including purification
    • 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
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/223—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin oxidised

Definitions

  • the invention relates to oxidized carbohydrate derivatives, more particularly oxidized carbohydrate ethers, or mixtures thereof.
  • the invention further relates to the use of these carbohydrate ethers as sequestering agent and/or anticrustation agent, as well as to methods for the preparation thereof.
  • the products according to the invention have eminent properties regarding the complexing of metal ions, in particular calcium. These properties can be used advantageously, for instance in detergent formulations.
  • Modern detergents and, more generally, cleaning agents consist, both in solid and liquid form, of complex mixtures of compounds, such as surfactants, bleaching agents, bleach activators, enzymes, fabric softeners, odorants and the like.
  • these products conventionally comprise an ingredient specifically intended to bind the metal ions, and in particular calcium and magnesium ions, present in mains water, by complexing.
  • This complexing should occur in such a manner that the metal ions present do not adversely affect the activity of the other detergent ingredients and that the complex does not precipitate on the materials to be washed and remains behind (anticrustation) .
  • phosphates in particular sodium tripolyphosphate, were used for this metal ion binding activity.
  • phosphates in detergents have since been forbidden by law in many countries.
  • zeolites and/or polycarboxylic acids/carboxylates such as nitrilotriacetic acid (NTA) , ethylenediaminetetraacetic acid (EDTA) , citric acid and polymeric polycarboxylates, for instance polymers with acrylate, maleate or methacrylate groups.
  • NTA nitrilotriacetic acid
  • EDTA ethylenediaminetetraacetic acid
  • citric acid phosphate substitutes
  • polymeric polycarboxylates for instance polymers with acrylate, maleate or methacrylate groups.
  • phosphate substitutes also have several disadvantages, for instance a relatively small extent of biodegradability.
  • they are generally prepared from petrochemical raw materials, the availability of which will diminish in the future. Therefore, in the past decades a great deal of research has been conducted on the preparation, characterization and application possibilities of polycarboxylates based on natural raw materials, in particular carbohydrates and derivatives derived therefrom.
  • Carbohydrate-containing polycarboxylates can be prepared, for instance, by reacting carbohydrates with compounds that contain carboxyl groups.
  • a carboxymethyl derivative can be obtained by allowing the carbohydrates to react with monochloroacetic acid.
  • Activated acrylic acid derivatives are also widely employed.
  • the products obtained have various possibilities for application, inter alia as cation exchanger (see e.g.
  • Chemical Abstracts, 109: 8322w) as an ingredient of granular fertilizer (Chemical Abstracts, ___£: 57049n) , as a dispersing and liquefying agent for ceramic clay (DE-Al-42 43 703) , as support material, stabilizer and solubility increasing agent (WO 91/04988) and as immunologically active compounds (Y. Ohya et al., Carbohydr. Polym., 25. (1994) 123-130) .
  • the invention relates to oxidized polymeric carbohydrate ethers or mixtures thereof with an average degree of polymerization of at least 10.
  • the term 'degree of polymerization' is intended to refer to the number of onosaccharide units of which the polymeric molecules are made up.
  • the sequestering capacity increases as a function of an increasing carboxyl content. This increase does not proceed linearly; upon further oxidation, the sequestering capacity increases to a greater extent than might be expected on the ground of the increase of the carboxyl content.
  • explanations for this behavior have been proposed in the literature (see inter alia M.S. Nieuwenhuizen et al., J. Am. Oil Chem. Soc, fLQ
  • the polymeric carbohydrate ethers are oxidized to such an extent that multidentate conformations can form when these ethers are brought into a solution.
  • the oxidized polymeric carbohydrate ethers according to the present invention possess an improved activity compared with oxidized polymeric carbohydrates such as polyglucuronic acid when they possess a carboxyl content of at least 5 milli- equivalents per gram.
  • the sequestering capacity expressed as the reciprocal of the amount of sample (in grams) necessary to reduce the calcium ion concentration of a 200 ml solution from 10" 1 to 10 ⁇ 5 mol/1 is then at least 2 g "1 .
  • carboxyl content is preferred.
  • the maximum carboxyl content to be achieved, for that matter, is dependent inter alia on the type of substituent and the degree of substitution DS.
  • the products according to the invention have a number of advantages compared with the known oxidized compounds based on carbohydrates, for instance because they have each of the following properties:
  • the oxidized polymeric carbohydrate ethers are obtainable by (selective) oxidation of at least a part, and optionally all, of the primary hydroxyl groups in polymeric carbohydrate derivatives with a degree of polymerization of at least 10.
  • the carbohydrate ethers can be obtained in that first the primary hydroxyl groups in a non-substituted polymer are oxidized and then are etherified. If desired, thereafter again an oxidation reaction can be carried out in order to convert primary hydroxyl groups in the substituents which have been introduced into the polymeric carbohydrate via an ether bond, to carboxyl groups.
  • starting material for the oxidized carbohydrate ethers according to the invention can serve, for instance, substituted or unsubstituted carbohydrate ethers or other polymeric carbohydrate derivatives which contain primary hydroxyl groups.
  • Suitable starting materials are starch derivatives such as carboxymethyl starch, hydroxyethyl starch, hydroxypropyl starch, dihydroxypropyl starch, Ci- ⁇ alkyl starch, cyanoethyl starch and nitro-Ci-g alkyl starch; cellulose derivatives, such as carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, dihydroxypropyl cellulose, Ci-g-alkyl cellulose and cyanoethyl cellulose; and derivatives of other polysaccharides, provided they contain primary hydroxyl groups.
  • Preferably used as starting material for the oxidation reaction are hydroxyethyl starch and, in particular, carboxymethyl starch.
  • starch comprises starch from random sources, such as potatoes, wheat, maize, tapioca, peas, rice and millet; as well as genetically modified variants thereof.
  • the starch can consist of amylose and/or amylopectin; amylose and amylopectin can occur in all kinds of relative ratios. Further, the starch can be partially decomposed chemically or enzymatically or treated otherwise, for instance cross-linked, before starch ethers are prepared therefrom.
  • the term starch also comprises debranched starch. Debranched starch consists for the most part of relatively short ⁇ (1-4) -bound glucose chains having an average degree of polymerization of about 15-25.
  • carbohydrate ethers can be used as starting material for the oxidation reaction and/or the oxidized carbohydrate ethers can be mixed prior to their intended use.
  • the carbohydrate ethers which serve as starting material for the preparation of the products according to the invention can be prepared by conventional methods.
  • the amount of ether substituents expressed as degree of substitution (DS) and represented in moles per mole anhydromonosaccharide units in the polysaccharide, or as molar substitution (MS) , likewise represented in moles per mole anhydromonosaccharide units, can vary from 0 to 2 or higher, preferably from about 0.5 to 1.5, and in particular about l.
  • the invention also relates to a method for the preparation of oxidized carbohydrate ethers, in which at least a part of the primary hydroxyl groups of polymeric carbohydrate ethers with a degree of polymerization of at least 10 is selectively oxidized.
  • this oxidation reaction can be carried out with all reagents that oxidize primary hydroxyl groups with a certain degree of specificity.
  • the reaction is carried out using a catalytic amount of stable nitroxide radicals in the presence of a suitable oxygen donor as oxidizing agent, in particular, TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl) is preferred as catalyst.
  • Sodium hypochlorite optionally in combination with sodium bromide, from which combination hypobromite is formed in situ, is preferably used as oxygen donor.
  • the invention accordingly comprises the selective oxidation of primary hydroxyl groups in carbohydrate derivatives to carboxyl groups, using stable nitroxide radicals and sodium hypochlorite/bromite. This reaction can be carried out in a very simple manner, under mild conditions and on a large scale, in an aqueous solution or suspension, while after the reaction the catalyst can be recovered from the reaction mixture in a simple manner.
  • a carbohydrate derivative preferably a carbohydrate ether
  • a catalytic amount of TEMPO has been added.
  • an oxidizing agent for instance a solution of sodium hypochlorite, preferably in the presence of a catalytic amount of sodium bromide, in water, is added dropwise or batchwise, with stirring.
  • sodium hypochlorite is used as oxidizing agent, the pH will usually be in the range of about 5 to 13, preferably from about 8 to 10.
  • the pH is preferably 9-11.5 if sodium hypochlorite is used in the presence of a catalytic amount of sodium bromide.
  • the pH is maintained constant by dripping to the reaction mixture a base or a solution thereof in water, for instance an aqueous 1 M sodium hydroxide, potassium hydroxide or sodium hydrogen carbonate solution.
  • the oxidation reaction has gone to completion when no consumption of base occurs anymore. If desired, only a part of the primary hydroxyl groups present can be oxidized. This can be effected by adding less oxygen donor, for instance hypochlorite, and/or discontinuing the reaction by adding an (excess of a) quenching substance such as methanol or ethanol. This is within reach of those skilled in the art.
  • the reaction is continued until substantially no consumption of the oxidizing agent occurs anymore.
  • Oxidized carbohydrate ethers with a good sequestering activity can also be obtained, for instance, by oxidizing starch to polyglucuronic acid, followed by a carboxymethylation step. With polyglucuronic acid, there is also the possibility of hydroxyethylation and subsequent oxidation. Thus, oxidized carbohydrate ethers are obtained which have a similar structure to the compounds etherified directly. It is noted there are also methods known in which the oxidation can take place at a lower pH, though with other oxidants than hypohalogenites.
  • the invention relates to the use of an oxidized carbohydrate ether or a mixture of two or more oxidized carbohydrate derivatives according to the invention or manufactured by the methods according to the invention, as sequestering agent or anticrustration agent.
  • the oxidized carbohydrate ethers concerned are used as an ingredient in washing powders or liquid detergent formulations, washing-up liquid formulations, or other cleaning agents.
  • the invention is further elucidated in and by the examples below. These non-limiting examples illustrate a number of aspects of the invention. For instance, the calcium- binding capacity is determined as a measure for the activity of the compounds. Also, some comparative examples have been included.
  • the carboxyl content (in milli-equivalents per gram dry product) was determined in all cases on the basis of the amount of lye in the form of a 0.1 N sodium hydroxide solution required to adjust a solution of 0.50 g of the product under investigation in 60 ml demineralized water, whose pH had priorly been adjusted to 2.00 using a 4.0 N HCl solution, to a pH of 11.50, minus the amount of lye required to adjust a solution of the corresponding starting material (likewise 0.50 g in 60 ml demineralized water, whose pH had priorly been adjusted to 2.00 using a 4.0 N HCl solution) to a pH of 11.50.
  • the value of the corresponding non-- substituted polysaccharide was taken as control.
  • the calcium-binding capacity was measured as follows, according to a conventional method. In 200 ml demineralized water the Ca-hardness was adjusted to 15' DH (German Hardness) by addition of 78.7 mg CaCl 2 .2H 2 0. The solution was buffered with 0.2 g borax. As soon as the potential (measured with a calcium ion selective electrode) remained constant, the solution was titrated in steps (in portions of 5 or 10 ml) with a 1% solution of the sample examined, each addition being followed by a waiting period until the reading was stable. The [Ca 2+ ] corresponding with each potential value was determined separately with a calibration curve. Reference is made to Figs. 1-12. In Figs.
  • Figs. 7-10 the calcium-binding capacities of products according to the invention are represented.
  • the increase of the calcium-binding capacity as a function of the degree of oxidation is shown in Figs. 7-10.
  • Fig. 11 shows that the calcium-binding capacity upon continued oxidation increases faster than would expected solely on the ground of the measured carboxyl content.
  • Fig. 12 shows the calcium-binding capacity of some products that were obtained by etherification of polyglucuronic acid.
  • SC sequestering capacity
  • the sequestering capacity has been calculated for all products and is shown in Table 1, along with the sequestering capacities of some comparative compounds.
  • Tables 2-5 the sequestering capacity is represented as a function of the degree of oxidation.
  • Amylose-V (d.s. 89.12%, 138 mmol; AVEBE) was suspended, with stirring, in 100 ml water, to which 0.13 g TEMPO (0.83 mmoi and 1.02 g NaBr (9,9 mmol) had been added.
  • the pH of the suspension was adjusted to 10.8 using 1 M sodium hydroxide solution.
  • 130 ml of a solution of NaOCl in water (content 145-150 g/1, approx. 267 mmol) was added dropwise, with stirring, over a period of 30 minutes.
  • the pH was maintained at a constant value of 10.8 by addition of 1 M sodium hydroxide solution (pH-stat) .
  • polyglucuronic acid (d.s. 84.02%, 21.3 mmol, CZ 4.5 meq/g) prepared according to the method according to Example 1, was dissolved with stirring in 50 ml water, to which 0.28 g NaBr (2.7 mmol) had been added.
  • the pH of the solution was adjusted to 9.5 using l M sodium hydroxide solution.
  • 30 ml of a solution of NaOCl in water (content 145-150 g/1, approx. 61.5 mmol) was added dropwise, with stirring, over a period of 30 minutes.
  • the pH was maintained at a constant value of 9.5 by addition of 1 M sodium hydroxide solution (pH-stat) .
  • Example 1 Oxidation of carboxymethyl starch a) 5.03 g Carboxymethyl starch (d.s. 94.83%, DS max 0.1, 28.1 mmol; AVEBE) was dissolved with stirring in 100 ml water to which 0.07 g TEMPO (0.45 mmol) and 0.25 g NaBr (2.4 mmol) had been added. The pH of the suspension was adjusted to 10.8 using 1 M sodium hydroxide solution. Then at a temperature of 0 * C, 26 ml of a solution of NaOCl in water (content 145-150 g/1, approx. 53 mmol) was added dropwise, with stirring, over a period of 30 minutes.
  • Carboxymethyl cellulose (d.s. 87.42%; DS 0.5, 21.6 mmol; AKU) was dissolved, with stirring, in 150 ml water, to which had been added 0.05 g TEMPO (0.32 mmol) and
  • Table l lists the sequestering capacities (SC) and the carboxyl contents (CZ, in meq/g) of the polysaccharides/poly- saccharide ethers oxidized in Examples Vl-V5,l-8 and 13-14.
  • Example 11 Sequestering capacity of oxidized hydroxyethyl starch (MS max 1.0) as a function of the degree of oxidation
  • hydroxyethylpolyglucuronic acid (d.s. 95.01%, carboxyl content 3.9 meq/g) is dissolved in 30 ml H 2 O, to which have been added 0.03 TEMPO (0.19 mml) and 0.12 g NaBr (1.2 mml).
  • the pH of the suspension is adjusted to 10.8 using a l M NaOH solution.
  • a temperature of 0°C 10 ml of a solution of NaOCl in water (approx. 21 mmol) is added dropwise, with stirring, over a period of 45 minutes.
  • the pH is maintained at a constant value of 10.8 by addition of l M NaOH solution (pH-stat) .

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Abstract

L'invention concerne des éthers d'hydrate de carbone polymères oxydés ou des mélanges de ceux-ci dont le degré de polymérisation est d'au moins 10. Ces composés ont un excellent pouvoir séquestrant et anti-incrustant, d'où l'avantage que l'on retire à les utiliser dans les agents de nettoiement. L'invention concerne en outre un procédé de préparation d'éthers d'hydrate de carbone polymères oxydés, par lequel au moins une partie des groupes hydroxyle primaires d'éthers d'hydrate de carbone polymères, polymérisés à un degré de polymérisation d'au moins 10, sont oxydés sélectivement.
PCT/NL1996/000218 1995-06-02 1996-06-03 Ethers d'hydrate de carbone polymeres oxydes utilises comme agent sequestrant et leurs procedes de preparation WO1996038484A1 (fr)

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AU59125/96A AU5912596A (en) 1995-06-02 1996-06-03 Oxidized polymeric carbohydrate ethers for use as sequesteri ng agent, and methods for the preparation thereof

Applications Claiming Priority (2)

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NL1000495 1995-06-02
NL1000495A NL1000495C2 (nl) 1995-06-02 1995-06-02 Geoxideerde polymere koolhydraatethers voor toepassing als sequestreer- middel, alsmede werkwijzen ter bereiding daarvan.

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Cited By (23)

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Publication number Priority date Publication date Assignee Title
WO1998055684A1 (fr) * 1997-06-05 1998-12-10 Consortium für elektrochemische Industrie GmbH Systeme a plusieurs composants pour modifier, decomposer ou blanchir la lignine, des materiaux contenant de la lignine ou des substances analogues, et procede d'utilisation de ce systeme
US6228126B1 (en) 1999-08-17 2001-05-08 National Starch And Chemical Investment Holding Corporation Paper prepared from aldehyde modified cellulose pulp and the method of making the pulp
US6319361B1 (en) 1996-03-28 2001-11-20 The Procter & Gamble Company Paper products having wet strength from aldehyde-functionalized cellulosic fibers and polymers
WO2002018448A2 (fr) * 2000-08-31 2002-03-07 Fidia Farmaceutici S.P.A. Polysaccharides percaboxyles, et procede d'elaboration
US6368456B1 (en) 1999-08-17 2002-04-09 National Starch And Chemical Investment Holding Corporation Method of making paper from aldehyde modified cellulose pulp with selected additives
US6379494B1 (en) 1999-03-19 2002-04-30 Weyerhaeuser Company Method of making carboxylated cellulose fibers and products of the method
US6409881B1 (en) 1999-11-08 2002-06-25 Sca Hygiene Products Gmbh Metal-crosslinkable oxidized cellulose-containing fibrous materials and products made therefrom
US6524348B1 (en) 1999-03-19 2003-02-25 Weyerhaeuser Company Method of making carboxylated cellulose fibers and products of the method
US6540876B1 (en) 2000-05-19 2003-04-01 National Starch And Chemical Ivnestment Holding Corporation Use of amide or imide co-catalysts for nitroxide mediated oxidation
US6586588B1 (en) 1999-08-17 2003-07-01 National Starch And Chemical Investment Holding Corporation Polysaccharide aldehydes prepared by oxidation method and used as strength additives in papermaking
US6635755B1 (en) 1999-11-08 2003-10-21 Sca Hygiene Products Gmbh Oxidized polymeric carbohydrates and products made thereof
US6695950B1 (en) 1999-08-17 2004-02-24 National Starch And Chemical Investment Holding Corporation Aldehyde modified cellulose pulp for the preparation of high strength paper products
JP2004512805A (ja) * 1999-02-24 2004-04-30 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 １級アルコールの選択的酸化方法と新規な炭水化物アルデヒド
US6824645B2 (en) 1999-02-24 2004-11-30 Sca Hygiene Products Gmbh Oxidized cellulose-containing fibrous materials and products made therefrom
US6872821B2 (en) 1999-08-17 2005-03-29 National Starch & Chemical Investment Holding Corporation Polysaccharide aldehydes prepared by oxidation method and used as strength additives in papermaking
US6919447B2 (en) 2001-06-06 2005-07-19 Weyerhaeuser Company Hypochlorite free method for preparation of stable carboxylated carbohydrate products
US6936710B2 (en) 2000-12-13 2005-08-30 Sca Hygiene Products Zeist B.V. Process for oxidizing primary alcohols
US7001483B2 (en) 2003-08-05 2006-02-21 Weyerhaeuser Company Apparatus for making carboxylated pulp fibers
EP1743906A2 (fr) * 2005-07-15 2007-01-17 National Starch and Chemical Investment Holding Corporation Polysaccharides modifiés
US7259218B2 (en) 2005-02-17 2007-08-21 The Procter + Gamble Company Processes for making temporary wet strength additives
US7691233B2 (en) 2003-10-16 2010-04-06 The Procter & Gamble Company Temporary wet strength additives
US7879994B2 (en) 2003-11-28 2011-02-01 Eastman Chemical Company Cellulose interpolymers and method of oxidation
US11199371B2 (en) 2017-08-17 2021-12-14 Michael D. Miller Firearm assembly system and method

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Cited By (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6319361B1 (en) 1996-03-28 2001-11-20 The Procter & Gamble Company Paper products having wet strength from aldehyde-functionalized cellulosic fibers and polymers
WO1998055684A1 (fr) * 1997-06-05 1998-12-10 Consortium für elektrochemische Industrie GmbH Systeme a plusieurs composants pour modifier, decomposer ou blanchir la lignine, des materiaux contenant de la lignine ou des substances analogues, et procede d'utilisation de ce systeme
DE19723629B4 (de) * 1997-06-05 2008-12-11 Wacker Chemie Ag Verfahren zum Behandeln von Lignin, ligninhaltigen Materialien oder ähnlichen Stoffen
US6824645B2 (en) 1999-02-24 2004-11-30 Sca Hygiene Products Gmbh Oxidized cellulose-containing fibrous materials and products made therefrom
JP2004512805A (ja) * 1999-02-24 2004-04-30 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 １級アルコールの選択的酸化方法と新規な炭水化物アルデヒド
US6524348B1 (en) 1999-03-19 2003-02-25 Weyerhaeuser Company Method of making carboxylated cellulose fibers and products of the method
US6379494B1 (en) 1999-03-19 2002-04-30 Weyerhaeuser Company Method of making carboxylated cellulose fibers and products of the method
US6368456B1 (en) 1999-08-17 2002-04-09 National Starch And Chemical Investment Holding Corporation Method of making paper from aldehyde modified cellulose pulp with selected additives
US6562195B2 (en) 1999-08-17 2003-05-13 National Starch And Chemical Investment Holding Corporation Paper prepared from aldehyde modified cellulose pulp
US6586588B1 (en) 1999-08-17 2003-07-01 National Starch And Chemical Investment Holding Corporation Polysaccharide aldehydes prepared by oxidation method and used as strength additives in papermaking
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