EP0707601A1 - Method of preparing carboxymethylated polygalactomannans - Google Patents

Method of preparing carboxymethylated polygalactomannans

Info

Publication number
EP0707601A1
EP0707601A1 EP94919614A EP94919614A EP0707601A1 EP 0707601 A1 EP0707601 A1 EP 0707601A1 EP 94919614 A EP94919614 A EP 94919614A EP 94919614 A EP94919614 A EP 94919614A EP 0707601 A1 EP0707601 A1 EP 0707601A1
Authority
EP
European Patent Office
Prior art keywords
alkali metal
chloroacetic acid
polygalactomannans
metal hydroxide
metered
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
EP94919614A
Other languages
German (de)
French (fr)
Inventor
Peter Horlacher
Andreas Sander
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.)
Gruenau Illertissen GmbH
Original Assignee
Chemische Fabrik Gruenau AG
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 Chemische Fabrik Gruenau AG filed Critical Chemische Fabrik Gruenau AG
Publication of EP0707601A1 publication Critical patent/EP0707601A1/en
Ceased legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G9/00—Frozen sweets, e.g. ice confectionery, ice-cream; Mixtures therefor
    • A23G9/52—Liquid products; Solid products in the form of powders, flakes or granules for making liquid products ; Finished or semi-finished solid products, frozen granules
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
    • A23L29/206—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
    • A23L29/238—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin from seeds, e.g. locust bean gum or guar gum
    • 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
    • C08B37/0096—Guar, guar gum, guar flour, guaran, i.e. (beta-1,4) linked D-mannose units in the main chain branched with D-galactose units in (alpha-1,6), e.g. from Cyamopsis Tetragonolobus; Derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M7/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made of other substances with subsequent freeing of the treated goods from the treating medium, e.g. swelling, e.g. polyolefins
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G2200/00—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF containing organic compounds, e.g. synthetic flavouring agents
    • A23G2200/06—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF containing organic compounds, e.g. synthetic flavouring agents containing beet sugar or cane sugar if specifically mentioned or containing other carbohydrates, e.g. starches, gums, alcohol sugar, polysaccharides, dextrin or containing high or low amount of carbohydrate
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions

Definitions

  • the invention relates to a continuous process for the carboxymethylation of galacto annanes. This is done in an extruder.
  • the invention thus relates to a process for the preparation of carboxymethylated polygalactomannans by reacting polygalactomannans with alkali salts of chloroacetic acid in the presence of at least molar amounts of alkali metal hydroxide, characterized in that polygalactomannans, alkali metal hydroxide and chloroacetic acid are added in a continuous manner and / or introduces their alkali metal salts in the presence of water into an extrusion machine, subject them to intensive mixing and removing the product after it has passed through the extrusion machine for drying or further processing.
  • carboxymethylate polygalactomannans in extruders.
  • Devices with one or more screws that can run in the same direction or in opposite directions are suitable as extruders. Double-screw extruders running in the same direction are particularly suitable.
  • the polygalactomannans, the Alkali hydroxide and chloroacetic acid or its alkali metal salts are metered in simultaneously or in succession.
  • the polygalactomannan is added to the head of the machine.
  • Alkali metal hydroxide is then added simultaneously or downstream. It is preferred to use sodium hydroxide as the alkali metal hydroxide and this as an aqueous preparation, i.e. Use sodium hydroxide solution with 20 to 70 wt .-% NaOH content.
  • Chloroacetic acid or an alkali metal salt of chloroacetic acid, preferably sodium chloroacetate, is then added simultaneously or downstream.
  • polygalactomannan and alkali metal hydroxide are added simultaneously and metered in downstream, for example 2 to 5 D downstream, of chloroacetic acid or the chloroacetic acid alkali metal salt, in particular chloroacetic acid sodium salt.
  • chloroacetic acid by this method, the amount of alkali hydroxide is 2 to 2.5 moles per mole of chloroacetic acid.
  • the amount of alkali metal hydroxide is 1 to 1.5 moles of alkali metal hydroxide per mole of salt.
  • the sodium monochloroacetate or monochloroacetic acid can be added in solid form together with the alkali metal hydroxide and the polygalactomannan.
  • the first three substances mentioned are preferably added downstream as an aqueous solution or suspension. It is preferred to provide the addition of the aqueous sodium monochloroacetate or monochloroacetic acid solution after the addition of alkali metal hydroxide.
  • the process according to the invention is carried out at temperatures between 60 and 150 ° C., preferably at temperatures between 70 and 120 ° C.
  • a suitable neutralizing agent is, for example, acetic acid, but inorganic acids can also be used or other solid or liquid mono- or polybasic carboxylic acids are used.
  • degrees of substitution of 0.03 to 3.0 carboxymethyl groups per anhydro sugar unit can be set.
  • Products with a degree of substitution of 0.1 to 0.5 carboxymethyl groups per anhydro sugar unit are preferred.
  • the person skilled in the art only has to calculate the amount of chloroacetic acid or its alkali salt per anhydroglucose unit and take the conversion (based on chloroacetic acid) into account.
  • guar e.g. B. guar flour or guar splits
  • guar gum 1.2-polygalactomannan
  • locust bean gum 1.4-polygalacto annan
  • the products according to the invention have the advantage of a higher molecular weight compared to products produced batchwise from powders in boilers weight, they are obtained with greater purity and are more uniform in their composition.
  • the method according to the invention offers economic advantages.
  • the products according to the invention are used in numerous very different branches of industry. They can be used, for example, in the textile industry as a thickening agent or, after molecular weight reduction, as a sizing agent, in the paper industry as a mass additive in paper manufacture and in the food industry for stabilizing ice cream, soups, sauces and the like.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Textile Engineering (AREA)
  • Food Science & Technology (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Organic Chemistry (AREA)
  • Molecular Biology (AREA)
  • Dispersion Chemistry (AREA)
  • Nutrition Science (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

The invention concerns a method for the continuous preparation of carboxymethylated polygalactomannans, the aim of the invention being to increase the yield of high-viscosity products. This is achieved by continuously feeding polygalactomannans, an alkali-metal hydroxide and chloroacetic acid and/or alkali-metal salts of chloroacetic acid in the presence of water to an extruder, mixing these components thorougly and removing the product produced by the extruder for drying or other treatment.

Description

"Verfahren zur Herstellung von carboxymethylierten Polyqalaktomannanen""Process for the preparation of carboxymethylated polyqalactomannans"
Die Erfindung betrifft ein kontinuierliches Verfahren zur Carboxymethyl- ierung von Galakto annanen. Dabei wird in einem Extruder gearbeitet.The invention relates to a continuous process for the carboxymethylation of galacto annanes. This is done in an extruder.
Es ist bereits bekannt, Stärke in einem Extruder zu Carboxymethylstärke umzusetzen. In einem Artikel von F. Meuser et al. in Starch/Stärke 42, (1990), Nr. 9, s. 330 bis 336 findet sich dazu die systematische Betrach¬ tung der Derivatisierung von Stärke mit einem Kochextruder als Reaktor. Die Autoren stellen heraus, daß das Arbeiten im Extruder es ermöglicht, die Stärke in weniger feuchtem Zustand zu derivatisieren und dabei gleich¬ zeitig zu verkleistern und partiell zu trocknen. Bedeutung wird der Tat¬ sache zugemessen, daß sich durch den Eintrag mechanischer Energie der strukturelle Aufbau der Makromoleküle ändert. Kritisch wird der Umset¬ zungsgrad der Reagentien gesehen. Zwar kann der Fachmann aus diesem Artikel viele wertvolle Rückschlüsse auf die Behandlung der Stärke beziehen. Da jedoch die Stärke beim Erwärmen in Gegenwart von Wasser ihre Struktur ändert (Verkleisterung) sind keine Rückschlüsse auf solche Polysaccharide möglich, die eine derartige Verkleisterungsreaktion nicht zeigen.It is already known to convert starch to carboxymethyl starch in an extruder. In an article by F. Meuser et al. in Starch / strength 42, (1990), No. 9, s. 330 to 336 there is the systematic consideration of the derivatization of starch with a cooking extruder as a reactor. The authors point out that working in an extruder makes it possible to derivatize the starch in a less moist state and, at the same time, gelatinize and partially dry it. Significance is given to the fact that the structural structure of the macromolecules changes due to the introduction of mechanical energy. The degree of implementation of the reagents is viewed critically. The expert can draw many valuable conclusions from this article about the treatment of starch. However, since the starch changes its structure when heated in the presence of water (gelatinization), no conclusions can be drawn about those polysaccharides that do not show such a gelatinization reaction.
Aus dem US-Patent 4,269,975 ist es bekannt, Guar aus Guarsplits unter Mit¬ verwendung eines Extruders herzustellen. Dabei werden die Guarsplits zu¬ nächst in einem horizontalen Mischer während einer Zeitdauer von einer Viertelstunde hydratisiert und die hydratisierte Zubereitung anschließend durch den Extruder gegeben. Aus diesem US-Patent kann der Fachmann nicht entnehmen, daß Guar in einem Extruder chemisch umgesetzt werden kann. Zu¬ mindest kann nicht entnommen werden, daß eine derartige Reaktion ohne Vor¬ behandlung möglich ist. Es ist weiter bekannt, Polysaccharide ganz allgemein dispergiert in Nicht¬ Lösungsmitteln mit Alkalilauge und Chloressigsäure bzw. deren Alkalime- tallsalzen zu Carboxymethylderivaten umzusetzen. Nachteilig bei derartigen Verfahren ist die Mitverwendung von Lösungsmitteln und die damit verbun¬ denen Probleme.From US Pat. No. 4,269,975 it is known to produce guar from guar splits using an extruder. The guar splits are first hydrated in a horizontal mixer for a period of a quarter of an hour and the hydrated preparation is then passed through the extruder. From this US patent, the person skilled in the art cannot conclude that guar can be reacted chemically in an extruder. At least it cannot be deduced that such a reaction is possible without pretreatment. It is also known to convert polysaccharides very generally dispersed in non-solvents with alkali metal hydroxide solution and chloroacetic acid or their alkali metal salts to give carboxymethyl derivatives. A disadvantage of such methods is the use of solvents and the problems associated therewith.
Weiterhin ist es bekannt, Polygalaktomannane in Pulverform zu carboxyme¬ thylieren. Da sich jedoch aus Polygalaktomannanen mit hohen Galaktosege- halten wie z. B. Guaran bereits in kaltem Wasser hochviskose Lösungen bil¬ den, ist der Wassergehalt bei Umsetzung in Pulverform begrenzt. Bei zu hohen Wassergehalten entstehen hochviskose Lösungen die nicht mehr zu handhaben sind. Bei Arbeiten mit sehr wenig Wasser müssen hohe Reaktions¬ zeiten in Kauf genommen werden.Furthermore, it is known to carboxylate polygalactomannans in powder form. However, since polygalactomannans with high galactose contents such. B. guaran already form highly viscous solutions in cold water, the water content is limited when implemented in powder form. If the water content is too high, highly viscous solutions are created that are no longer manageable. When working with very little water, high reaction times have to be accepted.
Vor dem Hintergrund dieses Standes der Technik war es Aufgabe der Erfin¬ dung, ein kontinuierliches Verfahren zu schaffen, daß es ermöglicht Poly¬ galaktomannane, wie insbesondere Guar, zu ihren Carboxymethylderivaten umzusetzen. Insbesondere sollte das Verfahren es ermöglichen, Derivate zu erhalten, deren wäßrige Lösungen sich durch hohe Viskosität auszeichnen. Weiterhin sollte das Verfahren eine kurze Reaktionszeit ermöglichen.Against the background of this prior art, it was the object of the invention to create a continuous process which enables polygalactomannans, such as guar in particular, to be converted into their carboxymethyl derivatives. In particular, the process should make it possible to obtain derivatives whose aqueous solutions are distinguished by high viscosity. Furthermore, the process should allow a short reaction time.
Gegenstand der Erfindung ist somit ein Verfahren zur Herstellung von car¬ boxymethylierten Polygalaktomannanen durch Umsetzung von Polygalakto¬ mannanen mit Alkalisalzen der Chloressigsäure in Gegenwart von zumindest molaren Mengen an Alkalihydroxid, dadurch gekennzeichnet, daß man in kon¬ tinuierlicher Arbeitsweise Polygalaktomannanen, Alkalihydroxid und Chlor¬ essigsäure und/oder deren Alkalimetallsalze in Gegenwart von Wasser in eine Extrusionsmaschine einführt, der intensiven Zwangsdurchmischung un¬ terwirft und das Produkt nach Durchlaufen der Extrusionsmaschine zur Trocknung oder Weiterverarbeitung entnimmt.The invention thus relates to a process for the preparation of carboxymethylated polygalactomannans by reacting polygalactomannans with alkali salts of chloroacetic acid in the presence of at least molar amounts of alkali metal hydroxide, characterized in that polygalactomannans, alkali metal hydroxide and chloroacetic acid are added in a continuous manner and / or introduces their alkali metal salts in the presence of water into an extrusion machine, subject them to intensive mixing and removing the product after it has passed through the extrusion machine for drying or further processing.
Nach dem erfindungsgemäßen Verfahren wird vorgeschlagen, Polygalakto¬ mannane in Extrudern zu carboxymethylieren. Als Extruder sind Geräte mit einer oder mehreren Schnecken geeignet, die gleichsinnig oder gegensinnig laufen können. Besonders geeignet sind gleichsinnig laufende Doppel¬ schnecken-Extruder. In diese Extruder können die Polygalaktomannane, das Alkalihydroxid und die Chloressigsäure bzw. deren Alkalimetallsalze gleichzeitig oder nacheinander eindosiert werden.According to the process of the invention, it is proposed to carboxymethylate polygalactomannans in extruders. Devices with one or more screws that can run in the same direction or in opposite directions are suitable as extruders. Double-screw extruders running in the same direction are particularly suitable. The polygalactomannans, the Alkali hydroxide and chloroacetic acid or its alkali metal salts are metered in simultaneously or in succession.
Nach einer bevorzugten Ausführungsform der Erfindung gibt man am Kopf der Maschine das Polygalaktomannan ein. Gleichzeitig oder stromabwärts wird dann Alkalimetallhydroxid zugegeben. Dabei ist es bevorzugt, als Alkali¬ metallhydroxid Natriumhydroxid einzusetzen und dies als wäßrige Zuberei¬ tung, d.h. Natronlauge mit 20 bis 70 Gew.-% NaOH-Anteil einzusetzen. Gleichzeitig oder stromabwärts wird dann weiterhin Chloressigsäure oder ein Alkalimetallsalz der Chloressigsäure, vorzugsweise Natriumchloracetat zugesetzt.According to a preferred embodiment of the invention, the polygalactomannan is added to the head of the machine. Alkali metal hydroxide is then added simultaneously or downstream. It is preferred to use sodium hydroxide as the alkali metal hydroxide and this as an aqueous preparation, i.e. Use sodium hydroxide solution with 20 to 70 wt .-% NaOH content. Chloroacetic acid or an alkali metal salt of chloroacetic acid, preferably sodium chloroacetate, is then added simultaneously or downstream.
Nach einer besonders bevorzugten Ausführungsform der Erfindung gibt man Polygalaktomannan und Alkalimetallhydroxid, vorzugsweise Natriumhydroxid gleichzeitig zu und dosiert stromabwärts, also zum Beispiel 2 bis 5 D stromabwärts Chloressigsäure oder das Chloressigsäurealkalimatellsalz, insbesondere Chloressigsäurenatriumsalz. Beim Einsatz von Chloressigsäure nach diesem Verfahren beträgt die Menge an Alkalihydroxid 2 bis 2,5 Mol pro Mol Chloressigsäure. Beim Einsatz eines Alkalimetallsalzes der Chlor¬ essigsäure beträgt die Menge an Alkalihydroxid 1 bis 1,5 Mol Alkalihy¬ droxid pro Mol Salz.According to a particularly preferred embodiment of the invention, polygalactomannan and alkali metal hydroxide, preferably sodium hydroxide, are added simultaneously and metered in downstream, for example 2 to 5 D downstream, of chloroacetic acid or the chloroacetic acid alkali metal salt, in particular chloroacetic acid sodium salt. When using chloroacetic acid by this method, the amount of alkali hydroxide is 2 to 2.5 moles per mole of chloroacetic acid. When using an alkali metal salt of chloroacetic acid, the amount of alkali metal hydroxide is 1 to 1.5 moles of alkali metal hydroxide per mole of salt.
Die Zugabe des Natriummonochloracetats bzw. der Monochloressigsäure kann in fester Form zusammen mit dem Alkalihydroxid und dem Polygalaktomannan erfolgen. Bevorzugt werden die drei erstgenannten Stoffe jedoch getrennt als wäßrige Lösung oder Supension stromabwärts zugegeben. Dabei ist es bevorzugt, die Zugabe der wäßrigen Natriummonochloracetat bzw. Monochlor- essigsäurelösung nach der Alkalihydroxidzugabe vorzusehen.The sodium monochloroacetate or monochloroacetic acid can be added in solid form together with the alkali metal hydroxide and the polygalactomannan. However, the first three substances mentioned are preferably added downstream as an aqueous solution or suspension. It is preferred to provide the addition of the aqueous sodium monochloroacetate or monochloroacetic acid solution after the addition of alkali metal hydroxide.
Nach dem erfindungsgemäßen Verfahren wird bei Temperaturen zwischen 60 und 150 °C gearbeitet, vorzugsweise bei Temperaturen zwischen 70 und 120 °C.The process according to the invention is carried out at temperatures between 60 and 150 ° C., preferably at temperatures between 70 and 120 ° C.
Nach einer weiteren Ausführungsform des Verfahrens ist es möglich 4 bis 6 D stromaufwärts vom Ende der Extrusionsstrecke Säure zur Neutralisierung des Reaktionsgemisches zuzudosieren. Ein geeignetes Neutralisationsmittel ist beispielsweise Essigsäure, aber es können auch anorganische Säuren oder andere feste oder flüssige ein- oder mehrbasige Carbonsäuren einge¬ setzt werden.According to a further embodiment of the process, it is possible to meter in acid 4 to 6 D upstream from the end of the extrusion section in order to neutralize the reaction mixture. A suitable neutralizing agent is, for example, acetic acid, but inorganic acids can also be used or other solid or liquid mono- or polybasic carboxylic acids are used.
Um unnötige thermische oder mechanische Belastung der eingesetzten Stoffe oder Produkte zu vermeiden, hat es sich als günstig erwiesen, die Verweil- zeit im Extruder auf 30 bis 300 sec. einzustellen. Unter diesen Ver¬ fahrensbedingungen findet sowohl eine recht weitgehende Umsetzung statt als auch der Erhalt des Molekulargewichts. Derartig hergestellte Sub¬ stanzen zeigen bezogen auf Trockensubstanz als 3 %ige Lösung eine Visko¬ sität von 5 bis 200 Pas (Brookfield, AVT, 20 UPM, 23 °C).In order to avoid unnecessary thermal or mechanical stress on the materials or products used, it has proven to be advantageous to set the residence time in the extruder to 30 to 300 seconds. Under these process conditions, there is both a fairly extensive implementation and also the maintenance of the molecular weight. Substances produced in this way, based on dry matter as a 3% solution, have a viscosity of 5 to 200 Pas (Brookfield, AVT, 20 rpm, 23 ° C.).
Nach dem erfindungsgemäßen Verfahren wird die eingesetzte Chloressigsäure bzw. ihre Alkalimetallsalze zu nahezu 100 % umgesetzt. Über 75 % der ein¬ gesetzten Chloressigsäure ist an das Polygalaktomannan gebunden. Wobei der Rest größtenteils als Glykolsäure bzw. als deren Alkalimetallsalz vor¬ liegt.Almost 100% of the chloroacetic acid used or its alkali metal salts are converted in the process according to the invention. Over 75% of the chloroacetic acid used is bound to the polygalactomannan. The remainder is mostly in the form of glycolic acid or its alkali metal salt.
Erfindungsgemäß lassen sich Substitutionsgrade von 0,03 bis 3,0 Carboxy- methylgruppen pro Anhydrozuckereinheit einstellen. Bevorzugt sind Produkte mit einem Substitutionsgrad von 0,1 bis 0,5 Carboxymethylgruppen pro Anhy¬ drozuckereinheit. Zur Einstellung eines bestimmten Substitutionsgrad braucht der Fachmann lediglich die Menge an Chloressigsäure bzw. ihrem Alkalisalz bezogen pro Anhydroglucoseeinheit auszurechnen und den Umsatz (bezogen auf Chloressigsäure) zu berücksichtigen. Mit anderen Worten: Soll ein Produkt mit einen Substitutionsgrad 0,75 hergestellt werden, so wird man ungefähr ein Mol Chloressigsäure pro 243 g Guaran (Anhydro annoseein- heit) bzw. 202,5 g 1.4-Polygalaktomannan einsetzen und 2 bis 2,5 Mol Al¬ kalihydroxid zufügen.According to the invention, degrees of substitution of 0.03 to 3.0 carboxymethyl groups per anhydro sugar unit can be set. Products with a degree of substitution of 0.1 to 0.5 carboxymethyl groups per anhydro sugar unit are preferred. To set a certain degree of substitution, the person skilled in the art only has to calculate the amount of chloroacetic acid or its alkali salt per anhydroglucose unit and take the conversion (based on chloroacetic acid) into account. In other words: If a product with a degree of substitution of 0.75 is to be produced, approximately one mole of chloroacetic acid per 243 g of guarane (anhydro annose unit) or 202.5 g of 1,4-polygalactomannan and 2 to 2.5 moles are used Add alkali hydroxide.
Nach dem erfindungsgemäßen Verfahren können unterschiedliche Polygalakto¬ mannane eingesetzt werden. Bevorzugt sind Guar, z. B. Guarmehl oder Guar¬ splits, Guaran (1.2-Polygalaktomannan), Johannisbrotkernmehl (1.4-Poly- galakto annan) oder vergleichbare Produkte aus der Pflanze Tara bzw. der Pflanze Cassia occidentalis.Different polygalactomannans can be used in the process according to the invention. Preferred are guar, e.g. B. guar flour or guar splits, guar gum (1.2-polygalactomannan), locust bean gum (1.4-polygalacto annan) or comparable products from the Tara plant or the Cassia occidentalis plant.
Die erfindungsgemäßen Produkte zeigen gegenüber chargenweisen aus Pulvern in Kesseln hergestellten Produkten den Vorteil eines höheren Molekularge- wichts, sie werden mit größerer Reinheit erhalten und sind gleichmäßiger in ihrer Zusammensetzung. Darüber hinaus bietet das erfindungsgemäße Ver¬ fahren wirtschaftliche Vorteile.The products according to the invention have the advantage of a higher molecular weight compared to products produced batchwise from powders in boilers weight, they are obtained with greater purity and are more uniform in their composition. In addition, the method according to the invention offers economic advantages.
Die erfindungsgemäßen Produkte finden aufgrund ihres hohen Wasseraufnahme¬ vermögens in zahlreichen sehr unterschiedlichen Industriezweigen Verwen¬ dung. Sie können beispielsweise in der Textilindustrie als Verdickungs- mittel oder nach Molekulargewichtsabbau als Schlichtemittel, in der Papierindustrie als Massezusatz bei der Papierherstellung und in der Lebensmittelindustrie zur Stabilisierung von Speiseeis, Suppen, Saucen und dergleichen eingesetzt werden. Because of their high water absorption capacity, the products according to the invention are used in numerous very different branches of industry. They can be used, for example, in the textile industry as a thickening agent or, after molecular weight reduction, as a sizing agent, in the paper industry as a mass additive in paper manufacture and in the food industry for stabilizing ice cream, soups, sauces and the like.
Beispiele:Examples:
Als Extruder wurde ein gleichsinnig laufender DoppelSchneckenextruder mit einem Schneckendurchmesser von 40 mm (ZSK 40, Werner & Pfleiderer GmbH, Stuttgart) und einer effektiven Verfahrenslänge von 28 D unter den in Ta¬ belle 1 aufgeführten Bedingungen in den Versuchsreihen eingesetzt. Die Viskositäten des entsprechend carboxymethylierten Polygalaktomannans sind ebenfalls dieser Tabelle zu entnehmen.A co-rotating twin-screw extruder with a screw diameter of 40 mm (ZSK 40, Werner & Pfleiderer GmbH, Stuttgart) and an effective process length of 28 D was used as the extruder in the test series under the conditions listed in Table 1. The viscosities of the corresponding carboxymethylated polygalactomannans can also be found in this table.
Tabelle 1:Table 1:
Beispiele 1 2 VergleichsbeispielExamples 1 2 Comparative Example
Dosierunα Tkα/hlDosage α Tkα / hl
Guar 20 20 12)Guar 20 20 12)
NaOH (50 %) 3,5 3,5 0,182)NaOH (50%) 3.5 3.5 0.18 2 )
Natriummonoch1or- acetatlösung (39 %) 11,2 11,2 0,312)3)Sodium monochloroacetate solution (39%) 11.2 11.2 0.312) 3)
Temperatur4) [°C] 80 110 80Temperature 4 ) [° C] 80 110 80
Drehzahl [Upm] 200 200Speed [rpm] 200 200
Verfahrenslänge [D] 28 28Process length [D] 28 28
Viskosität [ Pas]5) 33000 28600 170Viscosity [Pas] 5 ) 33000 28600 170
VWZ6) [sek.] 35 40 -VWZ 6 ) [sec.] 35 40 -
1) Vergleich, "Pulver"-Herstellung1) Comparison, "powder" manufacture
2) Einheiten in [kg]2) units in [kg]
3) Natriumacetatlösung 48 %ig ) Gehäusetemperatur3) Sodium acetate solution 48%) housing temperature
5) 23 °C; 3 %ig, bezogen auf Trockensubstanz 6) Verweilzeitmaximum5) 23 ° C; 3%, based on dry matter 6) Maximum dwell time
Zur Durchführung des Vergleichsbeispiels wurde in einem Lödigemischer ge¬ arbeitet. Die Reaktionszeit betrug 3 Stunden. Aufgrund des alkalischen Ab¬ baus des Produkts betrug die erhaltene Viskosität nur 170 Pas gemessen im Brookfield-Viskosi eter bei 23 °C. To carry out the comparative example, a Lödige mixer was used. The reaction time was 3 hours. Due to the alkaline degradation of the product, the viscosity obtained was only 170 Pas measured in a Brookfield viscometer at 23 ° C.

Claims

P a t e n t a n s p r ü c h e: Patent claims:
1. Verfahren zur Herstellung von carboxymethylierten Polygalaktomannanen durch Umsetzung von Polygalaktomannanen mit Alkalisalzen der Chlor¬ essigsäure in Gegenwart von zumindest molaren Mengen an Alkalihy¬ droxid, dadurch gekennzeichnet, daß man in kontinuierlicher Arbeits¬ weise Polygalaktomannane, Alkalihydroxid und Chloressigsäure und/oder deren Alkalimetallsalze in Gegenwart von Wasser in eine Extrusions¬ maschine einführt, der intensiven Zwangsdurchmischung unterwirft und das Produkt nach Durchlaufen der Extrusionsmaschine zur Trocknung oder Weiterverarbeitung entnimmt.1. Process for the preparation of carboxymethylated polygalactomannans by reacting polygalactomannans with alkali metal salts of chloroacetic acid in the presence of at least molar amounts of alkali metal hydroxide, characterized in that polygalactomannans, alkali metal hydroxide and chloroacetic acid and / or their alkali metal salts are added in a continuous manner Introducing the presence of water into an extrusion machine, subjecting it to intensive mixing and removing the product for drying or further processing after it has passed through the extrusion machine.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man Tempera¬ turen zwischen 60 und 150 °C, vorzugsweise zwischen 70 und 120 °C ein¬ stellt.2. The method according to claim 1, characterized in that one sets temperatures between 60 and 150 ° C, preferably between 70 and 120 ° C.
3. Verfahren nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß man zuerst Alkalihydroxid und anschließend das Alkalisalz der Chloressigsäure zudosiert, wobei 1 bis 1,5 Mol Alkalihydroxid pro Mol Salz eingesetzt werden.3. The method according to any one of claims 1 or 2, characterized in that first alkali metal hydroxide and then the alkali metal salt of chloroacetic acid are metered in, 1 to 1.5 moles of alkali metal hydroxide being used per mole of salt.
4. Verfahren nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß man zuerst Alkalihydroxid und anschließend Chloressigsäure zu¬ dosiert, wobei das Mol-Verhältnis 2 bis 2,5 Mol Alkalihydroxid pro Mol Chloressigsäure beträgt.4. The method according to any one of claims 1 or 2, characterized in that first alkali metal hydroxide and then chloroacetic acid zu¬ metered, the molar ratio being 2 to 2.5 moles of alkali metal hydroxide per mole of chloroacetic acid.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man die Chloressigsäure und/oder ihr Alkalisalz 2 bis 5 D stromab¬ wärts zudosiert.5. The method according to any one of claims 1 to 4, characterized in that the chloroacetic acid and / or its alkali metal salt is added 2 to 5 D downstream.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man 4 bis 6 D stromaufwärts vom Ende der Extrusionsstrecke Säure zur Neutralisierung des Reaktionsgemisches eindosiert.6. The method according to any one of claims 1 to 5, characterized in that 4 to 6 D upstream of the end of the extrusion section acid metered in to neutralize the reaction mixture.
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man die Verweilzeit auf 30 bis 300 sec. einstellt. 7. The method according to any one of claims 1 to 6, characterized in that the residence time is set to 30 to 300 sec.
8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß man einen Substitutionsgrad von 0,03 bis 3,0 Carboxymethylgruppen pro Anhydroglukoseeinheit einstellt, insbesondere einen Substitutions¬ grad von 0,1 bis 0,5.8. The method according to any one of claims 1 to 7, characterized in that a degree of substitution of 0.03 to 3.0 carboxymethyl groups per anhydroglucose unit is set, in particular a degree of substitution of 0.1 to 0.5.
9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß man als Polygalaktomannane Guar, Johannisbrotkernmehl oder ver¬ gleichbare Produkte aus der Pflanze Tara bzw. Cassia occidentalis ein¬ setzt.9. The method according to any one of claims 1 to 8, characterized in that guar, locust bean gum or comparable products from the plant Tara or Cassia occidentalis are used as polygalactomannans.
10. Verwendung der Verfahrensprodukte als Schlichtemittel bei der Behand¬ lung von Textilfasern, oder als Verdickungsmittel für wäßrige Zube¬ reitungen. 10. Use of the process products as sizing agents in the treatment of textile fibers or as thickeners for aqueous preparations.
EP94919614A 1993-06-16 1994-06-07 Method of preparing carboxymethylated polygalactomannans Ceased EP0707601A1 (en)

Applications Claiming Priority (3)

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DE4319915A DE4319915A1 (en) 1993-06-16 1993-06-16 Process for the preparation of carboxymethylated polygalactomannans
PCT/EP1994/001845 WO1994029353A1 (en) 1993-06-16 1994-06-07 Method of preparing carboxymethylated polygalactomannans

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US20070261998A1 (en) * 2006-05-04 2007-11-15 Philip Crane Modified polysaccharides for depressing floatable gangue minerals

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US2520161A (en) * 1946-04-25 1950-08-29 Gen Mills Inc Carboxyalkyl ethers of carbohydrate gums
US3855149A (en) * 1972-11-13 1974-12-17 Patterson Co C Method of increasing cold water solubility of locust bean gum
DE4137237A1 (en) * 1991-11-13 1993-05-19 Gruenau Gmbh Chem Fab CONTINUOUS METHOD FOR DEGRADING HETEROPOLYSACCHARIDES

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