WO2006010470A1 - Procede de production de polysaccharides et de derives de polysaccharides contenant des groupes aminoalkyle - Google Patents

Procede de production de polysaccharides et de derives de polysaccharides contenant des groupes aminoalkyle Download PDF

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Publication number
WO2006010470A1
WO2006010470A1 PCT/EP2005/007540 EP2005007540W WO2006010470A1 WO 2006010470 A1 WO2006010470 A1 WO 2006010470A1 EP 2005007540 W EP2005007540 W EP 2005007540W WO 2006010470 A1 WO2006010470 A1 WO 2006010470A1
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WO
WIPO (PCT)
Prior art keywords
polysaccharide
water
substituents
cellulose
optionally
Prior art date
Application number
PCT/EP2005/007540
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German (de)
English (en)
Inventor
Meinolf Brackhagen
Jürgen Engelhardt
Klaus Nachtkamp
Wolfgang Koch
Thomas Schulze
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Wolff Cellulosics Gmbh & Co. Kg
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
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Application filed by Wolff Cellulosics Gmbh & Co. Kg filed Critical Wolff Cellulosics Gmbh & Co. Kg
Publication of WO2006010470A1 publication Critical patent/WO2006010470A1/fr

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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
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/08—Ethers
    • C08B31/12—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch
    • C08B31/125—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch having a substituent containing at least one nitrogen atom, e.g. cationic starch
    • 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
    • C08B11/02—Alkyl or cycloalkyl ethers
    • C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
    • C08B11/14—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals with nitrogen-containing groups
    • C08B11/145—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals with nitrogen-containing groups with basic nitrogen, e.g. aminoalkyl ethers
    • 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

Definitions

  • the invention relates to a process for the preparation of aminoalkyl-containing polysaccharides and polysaccharide derivatives by etherification of free hydroxyl groups of polysaccharides or polysaccharide derivatives and the aminoethyl polysaccharides or Polysaccharid ⁇ derivatives themselves.
  • Chitosan 2-amino-2-deoxy-cellulose
  • Chitosan is the only cationic polysaccharide that can be used in large quantities. It is used, inter alia, as an acid-stable thickener in cosmetic preparations, as a paper auxiliaries and as a chelating agent and flocculant.
  • the extraction of this natural polysaccharide is a complex process, which is reflected in high prices of the products. The high price has hitherto hindered the widespread use of chitosan.
  • cellulose or cellulose derivatives with small amounts of organic solvents in a kneader, e.g. react with diethylaminoethyl chloride.
  • Kneaders consist of e.g. from a doppelmuldenf ⁇ rmigen kneading chamber in which two mutually stripping kneading blades rotate and cover almost the entire kneading space.
  • Kneaders are characterized by high investment costs, based on the small reactor volume. In contrast, stirred tanks or reaction mixers with a capacity of a few 10 m 3 are relatively inexpensive to produce.
  • the invention therefore provides a process for the preparation of aminoalkyl phenomenon termed by polysaccharides and polysaccharide derivatives, characterized in that
  • reaction product is filtered off, washed, optionally dried and ground.
  • % N measured nitrogen value in% by weight, based on dry product
  • Mve molecular weight of the etherifying reagent in g / mol
  • a water-miscible aprotic solvent in admixture with water in the ratio used according to the invention during the reaction shows no phase separation at room temperature.
  • the water-miscible used according to the invention Aprotic solvents have no hydroxyl or amino groups which can react with the etherification reagent.
  • Preferred water-miscible aprotic solvents are open-chain or cyclic ethers of the general formula
  • Cyclic ethers e.g. Dioxane, can also be used.
  • ethers are cyclic or open chain ethers having 2-10 carbon atoms and 1-3 oxygen atoms, most preferably the ether is non-cyclic, especially dimethoxyethane is used.
  • Non-water-miscible ethers e.g. Diethyl ether or methyl tert-butyl ether are not suitable.
  • open-chain or cyclic compounds of the type R 3 SO 2 R c for example tetrahydrothiophene-1, 1-dioxide (sulfolane) are used.
  • Polysaccharides are preferably natural polysaccharides obtained from plants or microorganisms or their constituents, such as e.g. Dextran, pullulan, starch, and cellulose. Preferably, cellulose is used. Polysaccharides containing carboxylic acid or sulfonic acid groups, e.g. Xylans, xanthan gum and carrageenan can also be used.
  • Polysaccharide derivatives are derivatives of polysaccharides, in particular hydroxyethyl, hydroxypropyl, methyl and ethyl polysaccharides and polysaccharides mixed with these substituents. Particularly preferred are methyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose, methyl hydroxypropyl cellulose and ethyl hydroxypropyl cellulose.
  • the total degree of substitution of these derivatives, if it is a cellulose ether, is preferably between 0.1 and 4, more preferably between 0.5 and 3.
  • the average degree of substitution of alkyl substituents (DS A i k yi) is between 0 and 2, 5 particularly preferably between 0 and 1.7.
  • the molar degree of substitution of hydroxyalkyl substituents (MS H yd r o x y a i k yi) is between 0 and 3.5, more preferably between 0 and 2.5.
  • the polysaccharide derivative used is preferably a water-insoluble cellulose ether or a cellulose ether having a thermal flocculation point in water.
  • Suitable etherifying agents are compounds of the general formula
  • X is a leaving group, preferably chlorine, bromine, iodine or a sulfonic acid residue R'SO 3 , where R 'is an aromatic or aliphatic radical having 1 to 24 C atoms, for example para-toluyl or methyl,
  • X is preferably chlorine and
  • n must be at least 2
  • radicals Ri and R 2 independently of one another are aliphatic or branched or cyclic, where appropriate heteroatom-substituted alkyl or aryl substituents or H. Two radicals R 1 and R 2 can form a ring together with the nitrogen.
  • Ri and R 2 independently contain 1 to 24 C atoms.
  • etherifying reagents to be used according to the invention are N-2-chloroethyldiisopropylamine, N-2-chloroethyldiethylamine, N-3-chloropropyldiethylamine, N-2-chloroethyldimethylamine and N-2-chloropropyldimethylamine ,
  • the radicals R 1 and R 2 can form a cyclic radical together with the nitrogen.
  • etherifying reagents used according to the invention in which two radicals R 1 and R 2 form a ring together with the nitrogen, are N-2-chloroethylpyrrolidine, N-2-chloroethylpiperidine and N-2-chloroethylmorpholine.
  • the etherification reagents can be used in the form of the ammonium salts, for example preferably of a hydrochloride. Both the solid and a solution of, for example, 65% or 50% by weight in water or other solvent may be used.
  • etherification reagent About 0.1-3 mol, preferably about 0.3-2 mol, more preferably about 1-2 mol of etherification reagent are used per mol of anhydroglucose, if cellulose is used as starting material.
  • 0.01 to 1.5 mol, preferably 0.1 to 1 mol, particularly preferably 0.1 to 0.8 mol of etherifying reagent per mol of anhydroglucose are sufficient.
  • the polysaccharide or polysaccharide derivative is preferably stirred with an inorganic base, preferably an alkali metal or alkaline earth metal hydroxide, particularly preferably sodium hydroxide, before the addition of the etherification reagent so that alkali metal cellulose can form.
  • an inorganic base preferably an alkali metal or alkaline earth metal hydroxide, particularly preferably sodium hydroxide
  • the order of addition can also be reversed. In this case, the formation of alkali cellulose takes place in situ.
  • the base can be added in solid form or in the form of a solution. If exclusively solid bases are used, it may be necessary to add some water, since a certain amount of water must be present in the system during the alkalization.
  • At least 1 mol of water should be present per mol of anhydroglucose, preferably at least 5 mol of water per mol of anhydroglucose, more preferably at least 10 mol of water per mol of anhydroglucose.
  • acid formed during etherification can be linked by the amino group.
  • the amount of base must be increased accordingly if the etherifying reagent in the form of an ammonium salt e.g. is used as the hydrochloride. Then, in addition, at least an equimolar amount, based on the ammonium salt, of base must be added to remove the amine, e.g. from the hydrochloride, release.
  • the reaction is carried out in the presence of a water-miscible aprotic solvent in a stirred vessel or reaction mixer.
  • a reaction mixer can be used become. These are, for example, under the name AU In One Reactor ® by the company. Draiswerke, Mannheim or under the name Druvatherm ® reactor. By the company Gebr.
  • the reaction is preferably carried out at temperatures from 40 0 C to about 9O 0 C, particularly preferably 60 ° C to about 75 0 C.
  • the reaction time depends on the reactor, the type of polysaccharide or derivative and the amount of aminoalkyl derivative used, and is preferably from 30 minutes to about 4 hours.
  • the product is e.g. freed by filtration of salts and by-products. This is optionally neutralized before or after the filtration. Preference is given to neutralizing before filtration.
  • the filter cake is washed with a suitable washing medium.
  • a suitable washing medium in addition to the water-miscible aprotic solvents, e.g. acetone and their mixtures with water proven. In many cases, it is also possible to purify first with water and then with an organic solvent. However, depending on the nature of the product and the by-products, a suitable washing medium must be selected by appropriate experimentation. But it is also possible not to remove the by-products and use the product in uncleaned form for technical applications.
  • the product isolated from the reaction medium and optionally purified is dried and mashed. Commercially available devices can be used for this purpose.
  • amino-containing polysaccharides and derivatives can be prepared in simple, widespread systems and in high yield.
  • Another object of the invention are therefore amino group-containing polysaccharide derivatives a) substituents of the type - (CH 2 ) H -NR 1 R 2 bound to the cellulose or a side chain, eg hydroxyalkyl chain, wherein n is at least 2 and the radicals R 1 and R 2 are independently aliphatic or branched or cyclic, optionally substituted by hetero atoms substituted alkyl or aryl substituents or H or two radicals R 1 and R 2 may form a ring together with the nitrogen, wherein R 1 and R 2 independently contain 1 to 24 carbon atoms and
  • the indicated DS refers to pure aminoethylcellulose, ie the total amount was corrected for the water content, the chloride and acetate ion content as well as the sodium ion content.
  • the sodium ion content was determined from the sulfate ash, assuming that it consists of 100% Na 2 SO 4 .
  • the chemicals were obtained from the trade.
  • the nitrogen content was determined by the Kjeldahl method and is based on a double determination of the sample.
  • the viscosities were determined in a solution of 2% by weight of the polymer at a shear rate of 2.55 s -1 with a rheometer of the type Rotovisko VT 550, from Haake.
  • Cellulose (17.2 g, dry content 94.24%) is dissolved in a mixture of the indicated dispersing agent (330.8 g) and water (41.1 g) in a 500 ml glass four-necked flat-bottomed round bottomed stirring apparatus with an impeller. Stirrer suspended.
  • Cellulose (63.7 g, dry content approx. 95%) is suspended in a mixture of the specified dispersant and water in a 2 liter double-walled glass reactor with MIG stirrer.
  • Sodium hydroxide prills (59.2 g) is added and after 1 h at room temperature the propylaminoethylchlorid diisopropyl hydrochloride added (148.1 g) and the reaction mixture heated under a nitrogen atmosphere at 70 0 C. After a reaction time of 4 h, the mixture is allowed to cool and enters the reaction mixture in acetone acetoacetate. The product is washed several times with ethanol / acetone / water 40/40/10 (wt .-%) and acetone, dried and ground.
  • PA isopropyl alcohol
  • TBA tert-butyl alcohol
  • ground cellulose is suspended in a mixture of dimethoxyethane and water in a 500 ml glass four-necked round bottomed round bottomed stirring apparatus with an impeller stirrer.
  • Example 9 the ratio of cellulose to slurry 1: 10.3 and is thus outside the preferred range. In this experiment it was observed that the approach was difficult to stir and therefore the reagents could not be sufficiently distributed.
  • ground cellulose (17.0 g, dry content 95.12%) is suspended in a mixture of dioxane (331 g) and water (57.5 g).
  • Sodium hydroxide prills (12 g) are added and, after 1 h at room temperature, 30 g of diisopropylaminoethyl hydrochloride are added and the reaction mixture is heated to the stated temperature under a nitrogen atmosphere. After a reaction time of 4 h, the batch is allowed to cool and enters the reaction mixture in acetone. The product is neutralized with acetic acid and gewa ⁇ several times with 80% aqueous acetone and finally acetone, dried and ground.
  • ground cellulose (17.3 g, dry content 93.6%) is suspended in a mixture of dimethoxyethane (331 g) and water (41 g).
  • Sodium hydroxide solution (50% by weight in water, 32.3 g) is added and, after 1 h at room temperature, 40 g of diisopropylaminoethyl hydrochloride are added and the reaction mixture is heated to the indicated temperature under a nitrogen atmosphere. After a reaction time of 4 h, the batch is allowed to cool and enters the reaction mixture in acetone. The product is neutralized with acetic acid and washed several times with 80% aqueous acetone and finally acetone, dried and ground.
  • Example 18 the reaction temperature was out of the preferred range, resulting in a low yield.
  • Examples 19-24 the procedure is as in Examples 14-18, with the difference that the reaction temperature is 7O 0 C and the composition of the liquid phase is varied.
  • DEC diethylaminoethyl chloride hydrochloride
  • the amount of NaOH is also adjusted to 3 moles per mole of anhydroglucose (two moles per mole of etherifying reagent).

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

Abstract

Procédé de production de polysaccharides et de dérivés de polysaccharides contenant des groupes aminoalkyle, qui consiste (a) à disperser un polysaccharide ou un dérivé de polysaccharide dans un mélange de solvant aprotique miscible dans l'eau et d'eau, (b) à alcaliniser le polysaccharide ou le dérivé de polysaccharide avec une base inorganique, (c) à ajuster, pendant l'alcalinisation, la quantité d'eau utilisée dans la plage située entre 1 et 55 mol d'eau par unité d'anhydroglucose, (d) à effectuer ensuite une amination avec un réactif d'éthérification à une température éventuellement accrue, (e) à neutraliser éventuellement le produit obtenu et (f) à filtrer le produit de réaction, puis à le laver et éventuellement ensuite à le sécher et à le broyer. La présente invention concerne également des dérivés de polysaccharides contenant des groupes amino, ayant un degré total de substitution déterminé.
PCT/EP2005/007540 2004-07-23 2005-07-12 Procede de production de polysaccharides et de derives de polysaccharides contenant des groupes aminoalkyle WO2006010470A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200410035870 DE102004035870A1 (de) 2004-07-23 2004-07-23 Verfahren zur Herstellung aminoalkylgruppenhaltiger Polysaccharide und Polysaccharidderivate
DE102004035870.2 2004-07-23

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006133845A1 (fr) * 2005-06-15 2006-12-21 Dow Wolff Cellulosics Gmbh Derives de guar contenant des groupes aminoalkyle
EP2072530A1 (fr) 2007-12-21 2009-06-24 Dow Wolff Cellulosics GmbH Procédé de fabrication de dérivés de cellulose contenant des groupements amino dans un liquide ionique
CN101235094B (zh) * 2008-02-29 2010-12-22 华中农业大学 一种絮凝剂的生产方法,用该方法生产的絮凝剂及应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BRPI1010282B1 (pt) * 2009-03-27 2017-05-02 Hercules Inc polímeros aminados e seu uso em composições de origem aquosa

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2623042A (en) * 1949-12-23 1952-12-23 Hercules Powder Co Ltd Preparation of acid-soluble cellulose derivative
FR1395090A (fr) * 1963-03-28 1965-04-09 Hercules Powder Co Ltd Perfectionnement aux éthers d'amidon dans le papier
DE1946722A1 (de) * 1969-09-16 1971-05-13 Henkel & Cie Gmbh Verfahren zur Herstellung von Diaminoalkylgruppen enthaltenden Cellulosederivaten
GB1474551A (en) * 1973-04-05 1977-05-25 Modokemi Ab Use of tertiary nitrogen-containing cellulose ethers as aggre gating agents
US4129722A (en) * 1977-12-15 1978-12-12 National Starch And Chemical Corporation Process for the preparation of high D. S. polysaccharides
US4460766A (en) * 1981-11-30 1984-07-17 Hoechst Aktiengesellschaft Dispersing auxiliary for preparing cellulose ethers

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2623042A (en) * 1949-12-23 1952-12-23 Hercules Powder Co Ltd Preparation of acid-soluble cellulose derivative
FR1395090A (fr) * 1963-03-28 1965-04-09 Hercules Powder Co Ltd Perfectionnement aux éthers d'amidon dans le papier
DE1946722A1 (de) * 1969-09-16 1971-05-13 Henkel & Cie Gmbh Verfahren zur Herstellung von Diaminoalkylgruppen enthaltenden Cellulosederivaten
GB1474551A (en) * 1973-04-05 1977-05-25 Modokemi Ab Use of tertiary nitrogen-containing cellulose ethers as aggre gating agents
US4129722A (en) * 1977-12-15 1978-12-12 National Starch And Chemical Corporation Process for the preparation of high D. S. polysaccharides
US4460766A (en) * 1981-11-30 1984-07-17 Hoechst Aktiengesellschaft Dispersing auxiliary for preparing cellulose ethers

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006133845A1 (fr) * 2005-06-15 2006-12-21 Dow Wolff Cellulosics Gmbh Derives de guar contenant des groupes aminoalkyle
US7777026B2 (en) 2005-06-15 2010-08-17 Dow Global Technologies Inc. Aminoalkyl-containing guar derivatives
EP2072530A1 (fr) 2007-12-21 2009-06-24 Dow Wolff Cellulosics GmbH Procédé de fabrication de dérivés de cellulose contenant des groupements amino dans un liquide ionique
CN101235094B (zh) * 2008-02-29 2010-12-22 华中农业大学 一种絮凝剂的生产方法,用该方法生产的絮凝剂及应用

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