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WO1996003439A1 - Procede de production de polycarboxylates par oxydation de polysaccharides - Google Patents

Procede de production de polycarboxylates par oxydation de polysaccharides Download PDF

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Publication number
WO1996003439A1
WO1996003439A1 PCT/EP1995/002775 EP9502775W WO9603439A1 WO 1996003439 A1 WO1996003439 A1 WO 1996003439A1 EP 9502775 W EP9502775 W EP 9502775W WO 9603439 A1 WO9603439 A1 WO 9603439A1
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WO
WIPO (PCT)
Prior art keywords
nitrogen dioxide
oxidation
temperature
polysaccharides
starch
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP1995/002775
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German (de)
English (en)
Inventor
Thomas Möller
Herbert Fischer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of WO1996003439A1 publication Critical patent/WO1996003439A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
    • C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • C08B15/04—Carboxycellulose, e.g. prepared by oxidation with nitrogen dioxide
    • 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 a simplified process for the production of polycarboxylates by selective oxidation of polysaccharides with gaseous nitrogen dioxide.
  • oxidizing agents are used for the oxidation of polysaccharides, in particular polyglucosans composed exclusively of glucose.
  • examples include (air) oxygen, hydrogen peroxide, sodium hypochlorite or bromite, periodic acid or periodates, lead (IV) acetate, nitrogen dioxide and cerium (IV) salts.
  • These oxidizing agents react very differently with the anhydroglucose units, cf. For example, the formula pictures in Houben-Weyl loc. cit., page 2124.
  • both process variants have their disadvantages: the non-aqueous work-up with the aid of the vacuum treatment may take a period of several hours to days, and the aqueous work-up, in addition to the occurrence of contaminated wastewater, makes a drying step of the purified product unavoidable, if this is not in aqueous liquid to pasty agents should be used.
  • the invention accordingly relates to a process for the preparation of polycarboxylic acids or their salts from polysaccharides by oxidation with gaseous nitrogen dioxide / dinitrogen tetroxide at a temperature in the range from 30 ° C. to 150 ° C. with conversion of at least part of the primary alcohol groups of the polysaccharides into carboxyl groups and counter ⁇ if necessary at least partial neutralization of the carboxylic acid groups formed, which is characterized in that the supply of nitrogen dioxide / dinitrogen tetroxide is terminated when the desired degree of conversion of the primary alcohol groups into carboxyl groups has been reached at most 90%, and the temperature by at least 10 ° C increased.
  • This degree of conversion can be determined in a simple manner by determining the acid number of the oxidation product, as described, for example, in the international patent application WO 93/16110.
  • the oxidation can be carried out as described in international patent application WO 93/16110, as long as care is taken to ensure that the reaction carried out there until the end is carried out only so long that the desired degree of oxidation, that is to say the degree of conversion of the primary alcohol groups into carboxyl groups, is achieved only to a maximum of 90%, preferably 60% to 85% and in particular 65% to 80% becomes.
  • the desired degree of oxidation is only completely achieved in the post-oxidation phase, that is to say when the nitrogen dioxide / dinitrogen tetroxide feed has ended and in comparison to the oxidation phase by at least 10 ° C., preferably 15 ° C. to 80 ° C. and in particular 20 ° C to 50 ° C elevated temperature. Care should be taken to ensure that an increase in the temperature does not exceed an upper limit of 160 ° C., since decomposition has been increasingly observed at higher temperatures.
  • a polycarboxylate produced by the process according to the invention has a significantly lower exothermic energy potential than products in which the process step characterizing the invention was not carried out. This has a favorable effect on its shelf life.
  • the present invention breakable before reaching the complete conversion oxidation reaction is preferably carried out at temperatures from 30 ° C to 70 ° C, in particular from 40 ° C to 60 C C.
  • Oxygen alone or in a mixture with gas which is inert under the reaction conditions, can be present, the addition of which can be carried out once during the reaction or several times, if desired continuously, during the reaction. If the latter is carried out, the oxidation reaction can, as is known, be controlled via oxygen metering as a function of temperature or pressure become. The addition of oxygen is preferably controlled so that the reaction temperature remains in the range from 30 ° C. to 70 ° C.
  • Noble gases such as helium or argon and carbon dioxide, but in particular nitrogen, nitrogen monoxide and dinitrogen monoxide, but also any mixtures of such gases can be used as inert gases, ie gases which do not react under the desired process conditions.
  • the oxygen content in the gas mixture is preferably in the range from 1% by volume to 30% by volume, in particular from 3% by volume to 10% by volume.
  • a preferred embodiment of the method according to the invention includes the supply of oxygen by injecting air.
  • a further preferred embodiment of the process is characterized in that a pressure of less than 10 bar, in particular from 2 bar to 6 bar, is set at the desired reaction temperature in the reaction system before the start of the oxidation reaction by pressing in an inert gas and then Oxygen or a mixture of oxygen is injected with said inert gas several times, if desired continuously.
  • the addition of nitrogen dioxide / nitrous oxide can take place before or after the addition of oxygen or the start of the addition of oxygen. It may be necessary to heat the reaction vessel to the desired reaction temperature after the initial injection of the inert gas.
  • the reaction temperature can generally be maintained without the need for external heating solely by adding the amount of oxygen.
  • the oxidizing agent from the gas phase acts directly on the solid, thoroughly mixed substrates.
  • Oxidation in a fluidized bed made of polysaccharide, the fluidizing agent of which is a gas containing nitrogen dioxide, is preferred.
  • Fluid bed is to be understood - without being limited to this type of generation - the phenomenon that can be observed when on horizontal right-hand, perforated bottoms, fine-grained bulk goods are flowed through from below by gases, referred to as eddies.
  • eddies the work of D. Kunii and 0.
  • a useful reactor for the process according to the invention is also the device disclosed in European patent EP 051 147 B1 (there FIG. 1), in which a fluidized bed through which gas flows is located in a cylinder in which a shaft equipped with stirring arms rotates. It is also possible to use a reactor with a multi-stage fluidized bed, as described in Beränek / Rose / Winterstein, "Fundamentals of Fluidized Bed Technology", Krauskopf-Verlag, 1975, page 72. With such a device, the continuous reaction is easily possible.
  • the fluidizing agent can leave the reaction system after flowing through the polysaccharide and, according to the invention, is replaced by a fluidizing agent which does not contain nitrogen dioxide / nitrous oxide tetroxide before the desired degree of oscillation has been reached.
  • This fluidizing agent is preferably an inert gas described above.
  • the fluidizing agent containing nitrogen dioxide after flowing through the polysaccharide with reoxidation of the spent nitrogen dioxide, for example by passing the fluidizing agent through a particulate solid, oxygen-transferring oxidizing agent adsorbed onto a solid carrier material or dissolved in liquids care must be taken to ensure that this reoxidation is terminated before the desired degree of oxidation of the polysaccharide has been reached.
  • the reaction time required until the addition of nitrogen dioxide / dinitrogen tetroxide has ended essentially depends on the desired degree of oxidation and the temperature.
  • the following information can serve as a guideline: At a temperature of 50 ° C and normal pressure using 12 molar equivalents of nitrogen dioxide per hour, based on hydroxyl groups to be oxidized, 18% to 22% after 30 minutes. after 60 minutes 60% to 70% and after 1.5 hours, 85% to 95% of the primary alcohol groups are converted into carboxyl groups.
  • polysaccharide used is largely uncritical for the process according to the invention. The only prerequisites are that it contains carbohydrate units containing primary alcohol groups and is present in a form which permits intensive mixing with the gaseous oxidizing agent and preferably the formation of a fluidized bed, in particular in powder form.
  • Native polyglucans in particular starch and / or cellulose, but also other polysaccharides, for example polygalactomannans such as guar and carubin, are suitable.
  • the polysaccharides can also be used in chemically or physically modified form, provided that they still contain oxidizable primary alcohol groups.
  • starches of different provenance in particular potato starch, wheat starch, corn starch and / or tapioca starch, as are commercially available as conventional powders, are preferred. Since cellulose often causes problems in the formation of a fluidized bed due to its fibrous nature, it is preferably used in the form of micropowder.
  • the process according to the invention is preferably carried out over a period of time such that the oxidation product on average is at least 15 mol% of oxidized anhydroglucose units of the formula I
  • polyglucan-based polycarboxylates are obtained which preferably contain at least 25 mol%, in particular, of the oxidized anhydroglucose units, in particular of the formula I contain at least 35 mol% in the molecule, with a further advantage being no significant amounts of other oxidation secondary products.
  • the upper limit of the content of units according to formula I is 100 mol%, in particular approximately 95 mol%.
  • the process according to the invention preferably produces polycarboxylates which have units of the formula I in the range from 70 mol% to 100 mol%, corresponding to a carboxyl group content of up to about 25% by weight.
  • the polysaccharide to be oxidized tends to agglomerate and to form channels, which is feared in fluidized bed technology
  • its flow behavior can be achieved by adding small amounts of, in particular, solid additives, to which, for example, magnesium oxide, calcium fluoride, calcium phosphate, finely divided zeolites or silica gel, in particular the Silicon dioxide sold under the name Aerosil (R) can be significantly improved.
  • R Aerosil
  • high effects become apparent when using low amounts of additives of preferably 0.1% by weight to 5% by weight, in particular 0.25% by weight to 1% by weight, in each case based on polysaccha to be oxidized ⁇ rid, reached.
  • the polysaccharide used preferably contains not more than 15% by weight, in particular not more than 10% by weight, of water.
  • FIG. 1 shows a tubular reactor (1) with a temperature sensor (2) which can be kept at the desired temperature with the aid of a thermostat (3) and in which the polysaccharide to be oxidized is flowed through by nitrogen dioxide from a storage container (4) and inert gas N2 , the gas flows being regulated by valves (7, 8 and 9).
  • the gas is preferably passed through a dust separator (5) and, after passing through a condenser (6) in which condensable components, in particular water and nitrogen oxides, are separated, leaves the apparatus.
  • a basic reagent that is to say to convert them from the acid to the salt form.
  • An aqueous solution, the alkali metal hydroxide, ammonium hydroxide, is preferably used as the neutralizing agent and / or contains organic base used. Neutralization is also possible directly after the oxidation reaction, for example by gassing the reaction vessel with ammonia. Salt formation is also possible under reducing conditions, for example using sodium borohydride.
  • the neutralizing agent is preferably used in amounts such that all carboxyl groups of the oxidation product are converted into the salt form.
  • Salt formation can also take place under the conditions of use or further processing of the polycarboxylates in their acid form, for example in the production or use of detergents or cleaning agents by customary alkaline components of such agents.
  • the polycarboxylates produced by the process according to the invention contain extremely low nitrate and nitrite contents of generally less than 3% by weight and are preferably used as builders or co-builders in washing or cleaning agents. In such agents, they are preferably used as co-builders in amounts of 0.5% by weight to 10% by weight, in particular 2% by weight to 7% by weight, based in each case on the total weight of the Agents that contain inorganic builders are used as the main builder.
  • the detergents and / or cleaning agents are particularly preferably used in the latter agents, the main being zeolite NaA, as described, for example, in connection with textile detergents in German patent specification DE 24 12837, and / or layered silicates, as described in European patent application EP 164 514 -Builder and polycarboxylic acids or their salts produced by the process according to the invention in proportions of 2: 1 to 5: 1.
  • the composition of the detergents and / or cleaning agents can otherwise be chosen practically as desired in the context of known formulations. Examples
  • Starch was oxidized in the apparatus shown in FIG.
  • Nitrogen at a rate sufficient to fluidize the starch was passed through the reactor (1) and heated to 50 ° C. by means of a thermostat (3).
  • Nitrogen dioxide was passed through the fluidized bed from a temperature-controlled storage bottle (4). The amounts of gas were adjusted to 150 standard liters per hour using flow meters calibrated for air. After 3 hours, the supply of nitrogen dioxide was stopped and a sample (VI) of the product was taken. The reactor temperature was raised to 80 ° C within 30 minutes and held at this temperature for 30 minutes.
  • a polycarboxylic acid P2 (sample V2) was obtained analogously to Example 1, but the reaction time was 4 hours until the reheating phase.
  • the data of the products are also given in Table 1. The clearly lower nitrite and nitrate content of the product P2 produced by the process according to the invention compared to V2 can also be seen here.
  • Example 2 was repeated in such a way that the temperature was not increased after the addition of nitrogen dioxide had ended, but left at approx. 50 ° C.
  • a polycarboxylate V3 was obtained with the data likewise given in Table 1.
  • Example 1 As stated in Example 1, 1042.8 g of potato starch were mixed with 0.5% by weight of Aerosil (R) 200 and oxidized in the reactor according to Figure 1, a pressure of 2 bar being set in contrast to Example 1. After 2 hours, the supply of nitrogen dioxide was stopped, the reactor temperature was raised to 80 ° C. in the course of 30 minutes and kept at this temperature for 30 minutes. The mixture was then cooled to room temperature. A polycarboxylic acid P3 was obtained as a white, free-flowing powder with an acid number of 363, the nitrate and nitrite contents of which corresponded to those of Pl.
  • R Aerosil
  • Reactor temperature sensor thermostat nitrogen dioxide storage container dust separator condenser, 8.9 adjustable valves

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • General Health & Medical Sciences (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production d'acides polycarboxylique ou de leurs sels à partir de polysaccharides, par oxydation avec du dioxyde d'azote/tétroxyde d'azote gazeux, ledit procédé consistant à faire réagir au moins une partie des groupes alcool primaires des polysaccharides pour obtenir des groupes carboxyle ainsi que le cas échéant à neutraliser au moins une partie des groupes acide carboxylique obtenus. Ce procédé permet de simplifier la préparation requise, principalement en interrompant l'apport de dioxyde d'azote/tétroxyde d'azote lorsque le taux de conversion souhaité des groupes alcool en groupes carboxyle est atteint à 90 % au maximum, et que la température augmente d'au moins 10 °C. Les polycarboxylates obtenus sont utilisés par exemple sous forme d'adjuvant ou de co-adjuvant dans des agents de lavage et de nettoyage.
PCT/EP1995/002775 1994-07-26 1995-07-14 Procede de production de polycarboxylates par oxydation de polysaccharides Ceased WO1996003439A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19944426443 DE4426443A1 (de) 1994-07-26 1994-07-26 Verbessertes Verfahren zur Herstellung von Polycarboxylaten durch Oxidation von Polysacchariden
DEP4426443.7 1994-07-26

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WO1996003439A1 true WO1996003439A1 (fr) 1996-02-08

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6440940B1 (en) 1997-12-18 2002-08-27 Peter J. Doyle Bioresorbable alginate derivatives
US9376648B2 (en) 2008-04-07 2016-06-28 The Procter & Gamble Company Foam manipulation compositions containing fine particles

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19507717A1 (de) * 1995-03-07 1996-09-12 Henkel Kgaa Verfahren zur Herstellung von neutralisierten Polycarboxylaten auf Polysaccharid-Basis
DE19510313A1 (de) * 1995-03-22 1996-09-26 Henkel Kgaa Verbessertes Oxidationsverfahren zur Herstellung von Polycarboxylaten aus Polysacchariden
DE19936613B4 (de) 1999-08-04 2010-09-02 Henkel Ag & Co. Kgaa Verfahren zur Herstellung eines Waschmittels mit löslichem Buildersystem
FR2940293B1 (fr) 2008-12-18 2013-12-20 Kalys Nouveau procede d'hydrolyse controlee des polysaccharides.
DE102010034782A1 (de) 2010-08-18 2012-02-23 Carl Freudenberg Kg Verfahren zur Herstellung von oxidierten Cellulose-Fasern, oxidierten Cellulose-Faserflächengebilden oder oxidierten Cellulose-Vliesstoffen sowie deren Verwendung

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993016110A1 (fr) * 1992-02-11 1993-08-19 Henkel Kommanditgesellschaft Auf Aktien Procede de fabrication de polycarboxylates a base de polysaccharides

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993016110A1 (fr) * 1992-02-11 1993-08-19 Henkel Kommanditgesellschaft Auf Aktien Procede de fabrication de polycarboxylates a base de polysaccharides

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6440940B1 (en) 1997-12-18 2002-08-27 Peter J. Doyle Bioresorbable alginate derivatives
US9376648B2 (en) 2008-04-07 2016-06-28 The Procter & Gamble Company Foam manipulation compositions containing fine particles

Also Published As

Publication number Publication date
DE4426443A1 (de) 1996-02-01

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