EP1423435A1 - Materiaux constitues de polysaccharides modifies et procede de fabrication - Google Patents

Materiaux constitues de polysaccharides modifies et procede de fabrication

Info

Publication number
EP1423435A1
EP1423435A1 EP02774311A EP02774311A EP1423435A1 EP 1423435 A1 EP1423435 A1 EP 1423435A1 EP 02774311 A EP02774311 A EP 02774311A EP 02774311 A EP02774311 A EP 02774311A EP 1423435 A1 EP1423435 A1 EP 1423435A1
Authority
EP
European Patent Office
Prior art keywords
polysaccharides
polyaminoglucose
materials according
substance
polysaccharide
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.)
Withdrawn
Application number
EP02774311A
Other languages
German (de)
English (en)
Inventor
Andreas Heppe
Andre Rapthel
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.)
Heppe Biotechnologische Systeme und Materialien GmbH
Original Assignee
Heppe Biotechnologische Systeme und Materialien GmbH
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
Priority claimed from DE10241040A external-priority patent/DE10241040B4/de
Application filed by Heppe Biotechnologische Systeme und Materialien GmbH filed Critical Heppe Biotechnologische Systeme und Materialien GmbH
Publication of EP1423435A1 publication Critical patent/EP1423435A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
    • 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
    • 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
    • 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
    • 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
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/14—Amylose derivatives; Amylopectin derivatives
    • C08L3/18—Ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof

Definitions

  • the invention relates to a new biodegradable material based on renewable raw materials.
  • biodegradable materials consist largely of polysaccharides, natural and synthetic polyesters, polyester amides and combinations of these materials. Some of these products have good material properties, but have so far not been able to displace conventional materials from many areas of application due to partly inadequate mechanical properties or at high costs. The additional effort to compensate for these problems is justified only for special areas of application.
  • Chitin is a material that has been tried and tested for millions of years in nature, for example crayfish or insect wings.
  • the chitin is converted to polyaminoglucose (chitosan) by deacetylation of the aminoacetate group. As a result of this treatment, it becomes water-soluble in the weakly acidic medium and the amino group becomes a functional group via a positive charge.
  • DE 44 38 961 A1 describes thermoplastically processable starch, in which the starch is melted at a temperature between 160.degree. C. and 190.degree. C. by adding polar solvents, preferably glycerol, and by adding thermal and mechanical energy.
  • polar solvents preferably glycerol
  • a frequently used method for improving the properties is the oxidation of the starch, e.g. is described in WO 97/31951.
  • the starch ring is broken up and acid groups are generated. This modifies the structure of the starch and increases the workability.
  • the problem to be solved is to modify polysaccharides in such a way that with small additions of polyamine glucose a new substance is formed with which significant improvements in properties occur.
  • the mechanical properties of the new materials produced on the basis of renewable raw materials should correspond to those of conventional plastics.
  • a new substance based on polysaccharides and polyamine glucose is produced, which is characterized in that polyaminoglucose forms complex chemical bonds with polysaccharides.
  • polyaminoglucose forms complex chemical bonds with polysaccharides.
  • the chemical bonds in the new polyelectrolyte complex can mainly be described by dipole interactions, such as hydrogen bonds. Physical interactions such as van de Waal's forces also occur in the new material.
  • R polysaccharide or polyaminoglucose
  • R ' polyaminoglucose or polysaccharide Y
  • X oxygen, nitrogen and or sulfur
  • H hydrogen
  • Polysaccharides are preferably understood to mean starch and cellulose, their derivatives such as e.g. acetate and propinate or butyrate or also sulfates and phosphates, but also chemically modified variants such as dialdehydes and carboxyls.
  • polyaminoglucose preferably means chitosan (1,4- ⁇ -polyaminoglucose) and its derivatives such as e.g. Carboxylmethylchitosan, chitosan acetate, chitosan lactate, chitin as a derivative with its derivatives as well as special chemical derivatives of polyaminoglucose, e.g. Heparin, hyaluronic acid and kerutan sulfate.
  • chitosan 1,4- ⁇ -polyaminoglucose
  • its derivatives such as e.g. Carboxylmethylchitosan, chitosan acetate, chitosan lactate, chitin as a derivative with its derivatives as well as special chemical derivatives of polyaminoglucose, e.g. Heparin, hyaluronic acid and kerutan sulfate.
  • substance A) is a chemical complex and represents a new substance.
  • Substance A) is essential for the new material.
  • the chemical bonds of substance A are caused by thermal activation and the following interaction Formed hydrogen bonds.
  • substance B) is a chemical complex and represents a new substance.
  • the substance B) is essential for the new material. It is characterized in that high-molecular polysaccharides are partially broken down and partially oxidized by means of an oxidizing agent, aldehyde and carboxy groups being formed. Strong chemical bonds form in the form of hydrogen bonds. Theoretical structure of substance B
  • substance C) is a chemical complex and represents a new substance.
  • Substance C) is essential for the new material.
  • the substance C) is characterized by a modification by means of reactive catalysis with one or more oxidizing agents. This modification, mainly of the polysaccharide, creates aldehyde as well as carboxy groups. At the same time, high-molecular polysaccharides are partially broken down. The chemical bonds created, between polysaccharide and polyaminoglucose, are predominantly hydrogen bonds and compounds that react to form a Schiff base through dehydration.
  • substance D) is a chemical complex and represents a new substance.
  • the substance D) is essential for the new material.
  • the substance D) is characterized by a modification by means of selective catalysis using a selective catalyst, a selectively acting auxiliary and one or more oxidizing agents. This modification mainly degrades highly branched polysaccharides so that linear, long-chain polysaccharides are formed. In addition, aldehyde as well as carboxy groups are generated. The chemical bonds generated, between polysaccharide and polyaminoglucose, are predominantly hydrogen bonds and compounds that can react to form a Schiff base via dehydration.
  • substance E) is a chemical complex and represents a new substance.
  • Substance E) is essential for the new material.
  • Substance E) is characterized by modification of substance A), substance B), substance C) and / or substance D) via esterification.
  • R polysaccharide or polyaminoglucose
  • R ' polyaminoglucose or polysaccharide
  • the new materials are based on the combination of polysaccharides and polyaminoglucose in a ratio of polysaccharides to polyaminoglucose between 999: 1 to 3: 7.
  • Starch is preferably used as the polysaccharide.
  • Chromium sulfuric acid, ozone and hydrogen peroxide are suitable as oxidizing agents for polysaccharides for the production of substances B, C and D.
  • hydrogen peroxide in concentrations between 0.01 and 5 parts based on the polysaccharide produces an acid content between 0.01 and 1 mmol / g in the polysaccharides.
  • the catalyst for the chemical modification of the substances C and D is preferably a heterogeneous catalyst, a cobalt nickel full metal catalyst and as a homogeneous catalyst iron (II) sulfate in a concentration of 0.01-10 parts, based on the Polysaccharide.
  • a selectivating agent preferably potassium iodide, is added in concentrations of between 0.01 and 5 parts based on the polysaccharides.
  • the polyaminoglucose used is preferably chitosan with a degree of deacetylation of 50 to 99.9%, a viscosity of 5cps to 10000cps and an ash content of 0.1 to 7%.
  • Chitosan with a degree of deacetylation of 80 to 92%, a viscosity of 500cps to 2000cps and an ash content of 0.1 to 1% is preferably used.
  • the preferred acetylating agent used is acetic anhydrite in a proportion between 0.1 and 15 parts, based on the sum of polysaccharides and polyaminoglucose.
  • the intimate mixing of the main components to achieve substances A, B, C, D and E can be done by stirring in solution, kneading, rolling and / or extrusion.
  • the solids concentration should be relatively low. It should be between 1 to 20 parts, preferably 4 to 8 parts, based on the solvent, which is preferably water. In the other variants of intensive mixing, the proportion of solvents can be significantly lower.
  • the proportion of solids here can be between 10 to 80 parts, preferably between 40 and 70 parts, based on the solvent, which is preferably glycerol. Heating the mass during the mixing process intensifies the mixing and accelerates the desired reactions.
  • the maximum temperature must not be higher than 220 ° C, preferably it should be between 60 ° C and 120 ° C.
  • property-improving components can also be added to the processing of substances A, B, C, D and E:
  • a nitrogen-containing auxiliary preferably urea, or its derivatives such as N, N-dimethylurea or dimethylacetamide between 0.1 to 50 parts, based on the sum of polysaccharides and polyaminoglucose.
  • a nitrogen-containing auxiliary preferably urea, or its derivatives such as N, N-dimethylurea or dimethylacetamide between 0.1 to 50 parts, based on the sum of polysaccharides and polyaminoglucose.
  • a plasticizer can be added in a proportion between 0.1 and 25 parts to increase flexibility.
  • Polyvinyl alcohol as well as in combination collagen, gelatin and / or rubber from 5 to 100 parts, based on the sum of polysaccharides and
  • organic acids preferably stearic acid, ascorbic acid and / or longer-chain dicarboxylic acids such as adipic acid and / or oxalic acid, and also modified waxes and / or polyphosphates, preferably sodium polyphosphate, can be used as additives in the proportion of 0.1 to 10 parts, based on the sum of polysaccharides and polyaminoglucose.
  • the material hydrophobic In order to make the material hydrophobic, it can be mixed with alkali silanes, waxes, preferably waxes modified with acrylic acid, and / or resins, preferably anionic, in a proportion of 0.1 to 20 parts, based on the sum of polysaccharides and polyaminoglucose, and / or be coated.
  • Casting films of high quality can be produced from the mixtures produced in the manner described above, or the following products can be produced using known extrusion techniques: • Extrusion films Injection molded articles, moldings
  • Capsules e.g. filled capsules for bacteria, yeast, enzymes, active ingredients
  • connection are made in a beaker using a commercially available hot plate.
  • 26 g of wheat starch are homogenized in 368 ml of water and heated to 65 ° C with stirring.
  • 132 ml of a 1% chitosan solution are added and heated to 75 ° C.
  • 2 g of urea and 4 ml of glycerin are added.
  • the mixture is heated to 85 ° C.
  • the resulting complex is gel-like and transparent to slightly milky.
  • the fabric can be directly processed by casting.
  • the partly dehydrated form is particularly characterized by very high strength.
  • connection are made in a beaker using a commercially available hot plate.
  • 26 g of wheat starch are homogenized in 368 ml of water and heated to 65 ° C with stirring.
  • 1 g of hydrogen peroxide-urea adduct, 200 mg of potassium iodide and a full metal catalyst are added in the form of a wire mesh.
  • 132 ml of a 1% chitosan solution are added and heated to 75 ° C.
  • 2 g of urea and 4 ml of glycerol are added.
  • the mixture is heated to 85 ° C.
  • the resulting complex is gel-like and transparent to slightly milky.
  • the fabric can be directly processed via casting.
  • a cast film film produced in this way is particularly notable for its very high strength and elongation.
  • thermoplastically processable blend mixture in the form of substance C from wheat starch, chitosan, urea and glycerin:
  • connection are made in a commercial kneader (Babender kneader).
  • 36 g of wheat starch are homogenized in 92 ml of water and heated to 100 ° C. with kneading.
  • 1 g of hydrogen peroxide / urea adduct and 200 mg of iron (II) sulfate are added.
  • 1.8 g of a 5% chitosan solution are added and heated to 110 ° C.
  • 2 g of urea and 1.6 g of glycerol are added.
  • the mixture is heated to 120 ° C.
  • the resulting complex is gel-like and transparent to slightly yellow.
  • the fabric can be processed directly.
  • a commercial press is used to produce the film. This is preheated to 120 ° C. 3 g of the mass produced in the kneader are positioned between two polytetrafluoroethylene plates and fixed between the press with a 100 mm thick metal ring. The sample is heated for 10 minutes at 120 ° C and a pressure of 30 bar. The sample is then relieved of pressure and removed from the press for cooling.
  • the film that is formed is flexible and transparent to slightly yellow. The fabric is characterized by high elongation and high tensile strength.
  • the solution is directly processed further by adding 5 ml of acetic anhydrite at short intervals and holding at 80 ° C. for a further 5 minutes. 10 ml of 99% ethanol are then added rapidly and the mixture is stirred vigorously for a further 10 minutes while cooling. The solution can then be further processed into film using cast film technology.
  • a cast film sheet produced in this way is characterized in particular by very high strength and elongation and by the fact that it is hydrophobic.
  • the properties of the materials can be influenced in a targeted way by changing the composition
  • the strength of the materials is higher than that of polyethylene and achieves comparable values with polypropylene.

Landscapes

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

Abstract

L'invention concerne de nouveaux matériaux à base de polysaccharides et de polyaminoglucose, ainsi qu'un procédé de fabrication de ces matériaux par interactions chimiques. Le matériau A est caractérisé par une réaction chimique entre polysaccharides et polyaminoglucose. Le matériau B est caractérisé par une modification au moyen d'un ou plusieurs agents d'oxydation. Le matériau C est caractérisé par une modification par catalyse réactive au moyen d'un ou plusieurs agents d'oxydation. Le matériau D est caractérisé par une modification par catalyse réactive au moyen d'un ou plusieurs agents d'oxydation. Le matériau E est caractérisé par une modification des matériaux A, B, C et D par estérification au moyen d'anhydrites acides. La combinaison de différents agents auxiliaires et additifs connus permet de varier les propriétés des matériaux dans une large mesure.
EP02774311A 2001-09-04 2002-09-03 Materiaux constitues de polysaccharides modifies et procede de fabrication Withdrawn EP1423435A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE10143535 2001-09-04
DE10143535 2001-09-04
DE10241040A DE10241040B4 (de) 2001-09-04 2002-09-02 Werkstoffe aus modifizierten Polysacchariden und Verfahren zu ihrer Herstellung
DE10241040 2002-09-02
PCT/DE2002/003276 WO2003022887A1 (fr) 2001-09-04 2002-09-03 Materiaux constitues de polysaccharides modifies et procede de fabrication

Publications (1)

Publication Number Publication Date
EP1423435A1 true EP1423435A1 (fr) 2004-06-02

Family

ID=26010069

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02774311A Withdrawn EP1423435A1 (fr) 2001-09-04 2002-09-03 Materiaux constitues de polysaccharides modifies et procede de fabrication

Country Status (2)

Country Link
EP (1) EP1423435A1 (fr)
WO (1) WO2003022887A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BRPI0512259B1 (pt) * 2004-06-21 2017-09-12 Evonik Degussa Gmbh Process for the production of water-absorbing polysaccharide, water-absorbing polysaccharide
DE102004029713B4 (de) * 2004-06-21 2014-10-30 Evonik Degussa Gmbh Verfahren zur Herstellung eines wasserabsorbierenden Polysaccharids und dessen Verwendung
DE102008027261A1 (de) * 2008-06-06 2009-12-10 Martin-Luther-Universität Halle-Wittenberg Verfahren zur Verbesserung der physikalisch-chemischen Eigenschaften bioabbaubarer Werkstoffe
US8361926B2 (en) 2008-11-25 2013-01-29 Evonik Stockhausen, Llc Water-absorbing polysaccharide and method for producing the same
CN103624989B (zh) * 2013-11-08 2016-05-04 苏州万图明电子软件有限公司 一种改性复合膜材料制备方法
DE102019100123B4 (de) 2019-01-04 2021-02-04 Excor Korrosionsforschung Gmbh Zusammensetzungen und Verfahren zur Vorbehandlung von Substraten für die nachfolgende Fixierung von Dampfphasen-Korrosionsinhibitoren

Family Cites Families (7)

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Publication number Priority date Publication date Assignee Title
JP2572233B2 (ja) * 1987-07-03 1997-01-16 日本ピー・エム・シー株式会社 紙の表面塗工用組成物
JPS6481837A (en) * 1987-09-24 1989-03-28 Lion Corp Highly water-resistant composition
JPH01156341A (ja) * 1987-12-12 1989-06-19 Kanebo Ltd ポリイオンコンプレックスゲルの製造法
JPH06102735B2 (ja) * 1990-03-12 1994-12-14 工業技術院長 新規な分解性複合素材及びその製造方法
JPH0686549B2 (ja) * 1990-05-11 1994-11-02 工業技術院長 デンプン・キトサン系の微生物分解性素材及びその製造方法
JPH04126734A (ja) * 1990-09-17 1992-04-27 Agency Of Ind Science & Technol デンプン・キトサン系の微生物分解性発泡体及びその製造方法
EP1098663A1 (fr) * 1998-07-21 2001-05-16 Alpenstock Holdings Limited Formulation a liberation lente comprenant un polysaccharide anionique

Non-Patent Citations (1)

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Also Published As

Publication number Publication date
WO2003022887A1 (fr) 2003-03-20

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