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WO2000039212A1 - Materiaux polymeres biodegradables ou melanges de polymeres ternaires a base de polysaccharide ou d'un derive de polysaccharide - Google Patents

Materiaux polymeres biodegradables ou melanges de polymeres ternaires a base de polysaccharide ou d'un derive de polysaccharide Download PDF

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Publication number
WO2000039212A1
WO2000039212A1 PCT/IB1999/001866 IB9901866W WO0039212A1 WO 2000039212 A1 WO2000039212 A1 WO 2000039212A1 IB 9901866 W IB9901866 W IB 9901866W WO 0039212 A1 WO0039212 A1 WO 0039212A1
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WO
WIPO (PCT)
Prior art keywords
acid
acids
polysaccharide
starch
bifunctional
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/IB1999/001866
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German (de)
English (en)
Inventor
Jürgen LOERCKS
Harald Schmidt
Ralf Timmermann
Wolfgang Schulz-Schlitte
Michael Voigt
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.)
Bayer AG
BioTec Biologische Naturverpackungen GmbH and Co KG
Original Assignee
Bayer AG
BioTec Biologische Naturverpackungen GmbH and 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
Publication date
Application filed by Bayer AG, BioTec Biologische Naturverpackungen GmbH and Co KG filed Critical Bayer AG
Priority to AU10709/00A priority Critical patent/AU1070900A/en
Publication of WO2000039212A1 publication Critical patent/WO2000039212A1/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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/12—Polyester-amides

Definitions

  • the present invention relates to a biodegradable, polymeric material or a ternary polymer mixture consisting of at least one polysaccharide or derivative thereof, such as starch or thermoplastic starch, and at least two other polymers with different crystallinity, as well as a method for producing a biodegradable polymeric material or a ternary polymer mixture and uses of the biodegradable material and the ternary polymer mixtures containing a polysaccharide or a derivative thereof, such as starch, a starch derivative, such as thermoplastic starch or a cellulose derivative.
  • thermoplastic starch such as in particular thermoplastic starch, starch derivatives, cellulose derivatives or more generally on polysaccharides, as well as polymer mixtures from the polysaccharides mentioned and other degradable polymer components such as polylactic acid, polyvinyl alcohol , Polycaprolactone, tailor-made copolyesters from aliphatic diols and aliphatic and aromatic dicarboxylic acids as well as degradable polyester amides, which are used, for example, with thermoplastic starch in the anhydrous melt
  • Ester reactions and / or as polymer combinations form new degradable polymer materials with a high proportion of renewable raw materials.
  • Other natural additives are additives and plasticizers, such as glycerin and its derivatives, hexavalent sugar alcohols such as sorbitol and its derivatives and other materials suitable as plasticizers or plasticizers.
  • Polysaccharides or starch, starch derivatives and cellulose derivatives are known from a number of publications which have been modified in such a way or are present in suitable polymer mixtures that they are suitable for processing in the plastics processing industry.
  • EP-A 118 240 and EP 0 304 401 describe the production of destructurized starch and use, inter alia, in EP 032 802, EP 408 503, EP 409 789, WO91 / 02024 and WO92 / 19680 Destructured starch in polymer blends.
  • the list of publications in which the use of destructurized starch in suitable polymer mixtures is described can be continued as desired.
  • US Pat. Nos. 3,922,239, 5,011,637, DE 501 889 and EP-A 0 244 206 describe, among other things, cellulose esters and / or reaction or mixed products of cellulose derivatives with lactones, triacetin, etc. , which in turn are suitable for thermoplastic processing in the plastics processing industry.
  • EP 397 819 defines for the first time a process for the production of thermoplastic starch or TPS for short, as well as what is known under the new starch material, thermoplastic
  • thermoplastic starch is to be understood, and what are the serious differences, especially in plastic processing technology, from the destructured starch that has been known for a long time.
  • the thermoplastic starch is produced with the aid of a swelling or plasticizing agent, not only without adding water, but rather using dry or dried starch and / or starch, which is dried by degassing during processing in the extrusion process during the melting phase. Starches contain 14% water, potato starch and even 18% natural moisture as balancing moisture.
  • thermoplastic starch is an exothermic process.
  • the essentially water-free ( ⁇ 5%) native starch is homogenized in an extrusion process with an additive or plasticizer (eg glycerin, glycerol acetate, sorbitol), which lowers the melting temperature of the starch and by adding mechanical energy and Heat melted in a temperature range of 120 - 220 ° C.
  • the thermoplastic starch is free of crystalline components, at least the crystalline components in TPS are less than 5%, while the crystalline components remain very low.
  • the process parameters produce a permanent rearrangement of the molecular structure to thermoplastic starch, which practically no longer comprises any crystalline components and, unlike destructured starch, no longer recrystallizes.
  • Starch such as destructured or thermoplastic Starch and starch derivatives are used as phase mediators for the homogenization of the hydrophilic and polar starch polymer phase and the hydrophobic and non-polar, further polymer phase, which are either added or are preferably produced in situ (for example by transesterification) during the preparation of the polymer mixture.
  • phase mediators i.a. Block copolymers used, among others are described in detail in WO 91/16375, EP 0 539 544, US 5 280 055 and EP 0 596 437. These publications also disclose polymer mixtures of the TPS with, for example, cellulose derivatives, aliphatic polyesters, such as PCL, PHB, PHVB, PLA and PVOH.
  • thermoplastic blends are technologically produced by coupling the phase interfaces between the less compatible polymers so that the distribution structure of the disperse phase is achieved during processing through the optimal processing window (temperature and shear conditions).
  • twin-screw extruders used, for example, for compounding are preferably co-rotating twin-screw extruders with tightly intermeshing screw profiles and have individually temperature-controlled kneading zones.
  • twin-screw extruders are used, preferably with eight chambers or zones, which can optionally be expanded to ten zones and have, for example, the following structure: Extruder design: For example, co-rotating twin-screw extruder
  • Zone 2 same as Zone 1 mixing and plasticizing temp. 140 ° C pressure> 1 bar water content 4 - 15%
  • Zone 3 same as 1 plastification temp. 180 ° C pressure> 1 bar water content 4 - 15% Zone 4 same as 1 plastification temp. 185 ° C pressure> 1 bar water content 4 - 15%
  • Zone 6 sidefeeder, dosing dosing of additional polymers of the additional PolyTemp. 200 ° C mere such as pressure> 1 bar PCL
  • Zone 8 discharge zone, if necessary, homogenization and, if necessary, evaporation of transesterification water of reaction temp. 205 - 210 ° C
  • thermoplastic starch including zone 5
  • PCL polycaprolactone
  • low molecular weight additives including DMSO, butanediol, glycerol, ethylene glycol, propylene glycol, diglyceride, diglycol ether, formamide, DMF, dimethyl urea, dirnethylacetamide, N-methylacetamide, polyalkene oxide, glycerol mono- or - Diacetate, sorbitol, sorbitol ester and citric acid are proposed and used.
  • PVOH, EVOH and their derivatives as well as urea and urea derivatives are occasionally used.
  • starch derivatives When using starch derivatives, cellulose derivatives or generally polysaccharides and / or polysaccharide derivatives for the production of polymer mixtures with further polymer components, the procedure is similar, however, temperature controls adapted to the biopolymers or derivatives used and the other polymers are to be selected.
  • temperature controls adapted to the biopolymers or derivatives used and the other polymers are to be selected.
  • the above example of a starch / polymer mixture is only for better understanding and is in no way intended to limit the present invention.
  • Environmental influences can be produced if polysaccharides or derivatives thereof, such as in particular starch, starch derivatives or cellulose derivatives, are mixed and processed with a mixture of at least two biodegradable high molecular weight polymers. It is advantageous if one of the polymer components has a high crystallinity, such as, for example, aliphatic, biodegradable polyesters, such as polycaprolactone, polylactide or succinic acid.
  • the effect of the significantly increased stability against environmental influences arises from the fact that at least two biodegradable polymers are mixed in the melt with the polysaccharide or the derivative thereof, for example with the starch, such as preferably thermoplastic starch, which, for example, is not completely miscible, but instead only partially compatible with each other.
  • the starch such as preferably thermoplastic starch, which, for example, is not completely miscible, but instead only partially compatible with each other.
  • This layer structure ensures that the property advantages of the individual components of this mixture can be advantageously combined with one another.
  • the starch or thermoplastic starch is preferably present in one of the at least two added polymers.
  • the water absorption of mixtures of biodegradable polyester amides and the polysaccharides, such as starch or thermoplastic starch can be significantly reduced if one or more aliphatic polyesters, such as polylactide, polycaprolactone or succinic acid ester, are used as the third mixture component.
  • Polycaprolactone is preferably used. This makes it possible, for example, to produce moldings with a longer service life against the action of moist ingredients.
  • mixtures according to the invention of at least one polysaccharide or derivatives thereof, such as, for example, starch or thermoplastic starch and at least two other biodegradable polymers also have advantages in the following properties: for example gas barrier against oxygen and water vapor, gas barrier against flavoring agents or higher temperature stability.
  • Films produced according to the invention have the diverse requirements that are placed on food packaging.
  • the mixtures according to the invention allow the production of multilayered shaped bodies by simple processing from an aggregate.
  • the mixture can be obtained either by simply mixing the various polymer granules with subsequent processing or by prior compounding of the individual components. This eliminates the need for multi-layer extrusion, such as coextrusion.
  • Polysaccharides or derivatives thereof are generally suitable for producing the mixtures proposed according to the invention, for example the materials mentioned below:
  • Arabicum Acacia gum, tragacanth, carragenan, furcelaran, ghatti, guar, locust bean, psyllium, quince, tamarind-karaya gum;
  • Fermentation products dextran, xanthan, curdlan, scleroglucan;
  • Bacterial extracts yeast glucan, pullulan, Zanflo-10, Zanflo-21: Reg.Mark Kelco Division, Merck & Co., Inc., PS-7: Azotobacter indicus, Bacterium alginate: Azotobacter vinelandii,
  • starches such as grain, tapioca, potato, wheat, rice, etc.;
  • Celluloses and cellulose derivatives such as carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and also methyl ether of pectin, hydroxypropyl alginates;
  • Shellfish extracts, chitin and chitosan Shellfish extracts, chitin and chitosan.
  • Corn starch potato starch, corn sugar, agar, Arabic gum, guar, pectin, carboxymethyl cellulose and xanthan, to name just a few examples.
  • Suitable lactones or other reaction partners for the polysaccharide are, in particular, caprolactone, dilactide and diglicidyl lactone (2-glycolic acid), corresponding to lactams, such as, for example, caprolactam or carboxylic acids, such as, in particular, formic acid.
  • linear bifunctional alcohols such as, for example, ethylene glycol, hexadiol or preferably butanediol and / or optionally cycloaliphatic, bifunctional alcohols, such as, for example, cyclohexanedimethanol and additionally optionally small amounts of higher-functionality alcohols, such as, for example, 1, 2, 3-propanetriol or neopenthyl glycol, and also from linear bifunctional acids, such as, for example, succinic acid or adipic acid and / or optionally cycloaliphatic bifunctional acids, such as, for example, cyclohexanedicarboxylic acid and / or optionally aromatic bifunctional acids, such as, for example, terephthalic acid or isophthalic acid or naphthalenedicarboxylic acid and additionally optionally small amounts of higher-functional acids or such as trimellitic acid
  • aromatic acids making up no more than 50% by weight, based on all acids.
  • the acids can also be used in the form of derivatives, such as acid chlorides or esters;
  • an ester fraction from linear bifunctional alcohols such as, for example, ethylene glycol, butanediol, hexanediol, preferably butanediol and / or cycloaliphatic bifunctional alcohols, such as, for example, cyclohexanedimethanol and additionally optionally small amounts of higher-functional alcohols, such as, for example, 1,2,3-propanetriol or neopentyl glycol and from linear bifunctional acids, such as, for example, succinic acid or adipic acid and / or optionally cycloaliphatic bifunctional acids, such as, for example, cyclohexanedicarboxylic acid and additionally optionally small amounts of higher-functional acids, such as, for example, trimellitic acid or
  • H a carbon portion which is produced from aromatic bifunctional phenols, preferably bisphenol A and carbonate donors, for example phosgene,
  • ester fraction F) and / or G) is at least 70% by weight, based on the sum of F), G) and H);
  • linear and / or cycloaliphatic bifunctional alcohols such as, for example, ethylene glycol, hexanediol, butanediol, preferably butanediol, cyclohexanedimethanol, and additionally, if appropriate, small amounts of higher-functional alcohols, for example 1,2,3-propanetriol or
  • adipic acid preferably adipic acid and additionally optionally small amounts of higher functional acids, e.g. Trimellitic acid, or
  • ester content I) and / or K) is at least 20% by weight, based on the sum of I), K), L) and M).
  • Dialcohols such as ethylene glycol, 1,4-butanediol, 1,3-propanediol,
  • 1, 6-hexanediol, diethylene glycol and others and / or dicarboxylic acid such as oxalic acid, succinic acid, adipic acid and others. also in the form of their respective esters (methyl, ethyl, etc.), and / or hydroxycarboxylic acids and lactones, such as caprolactone and others.
  • aminocarboxylic acids such as aminocaproic acid etc. and / or mixtures (1: 1 salts) of dicarboxylic acids such as adipic acid, succinic acid etc. and diamines such as hexamethylenediamine, diaminobutane etc.
  • both hydroxyl- or acid-terminated polyesters with molecular weights between 200 and 10,000 can be used as the ester-forming component.
  • aliphatic polyesters such as polycaprolactone, polylactic acid, polyhydroxybutyric acid, polyhydroxybenzoic acid, polyhydroxybutyric acid / hydroxivaleric acid copolymers and mixtures thereof.
  • Statistical copolyesters of aliphatic and aromatic dicarboxylic acids with a proportion, for example of approximately 35-55 mol, are also suitable for mixing with the polysaccharides, such as starch, such as in particular TPS.
  • % with an aromatic acid such as, for example, terephthalic acid, polyalcylene terephthalates and polyethylene terephthalates, for example, having been found to be suitable copolyesters for mixing with TPS.
  • the proportions by weight of the polysaccharides or their derivatives, such as starch or thermoplastic starch and the at least two other biodegradable plastics, can be varied within a wide range.
  • the proportion of polysaccharide or the derivative can vary between 5 and 90% by weight.
  • the content of a mixture of at least two other biodegradable polymers is between 10 and 95% by weight.
  • the mixing ratio of the different biodegradable polymers can be set freely depending on the requirements. Using native starch and thermoplastic starch, some examples of polymer mixtures proposed according to the invention are to be mentioned, which are listed in the table below.
  • Starch native potato starch dried 3.5% H20: Plasticizer la - lf Bayer Polymer according to the list below.
  • thermoplastic starch starch + plasticizer ⁇ 0.1%
  • Polyamide 1 Bayer BAK 1095 polyester amide MFI 2.5 150 ° C
  • polyester 1 BASF ZK 242/108 copolyester of aliphatic diols and aliphatic / aromatic dicarboxylic acids MVR 3.0 at 190 ° C / 2.16 kg;
  • the individual components ie the polysaccharide or derivative thereof, such as the starch or thermoplastic starch and the two further polymer components
  • a mixing unit such as a kneader or extruder
  • the components can be added before Enter into the mixing unit to be compounded.
  • Mixing or kneading in the extruder is carried out in accordance with generally customary process conditions, such as those used in plastics processing. manufacturing industry are known for mixing or compounding polymers. It is essential that a melt that is as homogeneous as possible is produced without, however, choosing an excessively high temperature in order to avoid any decomposition of the at least three polymer components.
  • the polysaccharide with one further polymer component in the sense of a compounder before this compound is then mixed with the second, further polymer component in an extruder to form the ternary polymer mixture.
  • thermoplastic starch with the one further polymer
  • the polysaccharide such as, for example, the starch or, in particular, the thermoplastic starch with the one further polymer
  • WO97 / 48764 where, for example, starch or a starch derivative with an aliphatic polyester, a copolyester with aliphatic and aromatic blocks Polyester amide, a polyester urethane, a polyethylene oxide, a polymer or a poly glycol and / or mixtures thereof is mixed at a water content of ⁇ 5% by weight, preferably ⁇ 1% by weight, so that a largely homogeneous mixture of Starch with which another polymer is formed.
  • the starch / polymer mixture compounded in this way is then subsequently mixed with the second further polymer, the miscibility between the compound and the additional further polymer being only partial so that the layer-like structure desired according to the invention is achieved in the molded article or extrudate to be produced can be.
  • the miscibility between the polysaccharide and the one other polymer component can also be achieved by adding a corresponding phase mediator which enables at least partial miscibility at the phase boundary of the two polymers.
  • this phase mediator can have two blocks, one block being soluble or miscible in the polysaccharide and the second block being correspondingly soluble in the further polymer component or miscible with it.
  • This phase mediator can of course also be added if the polysaccharide or the derivative thereof and the at least two further polymer components are admixed to a mixing unit such as an extruder or kneader without prior compounding, ie the phase mediator is effective when the at least three components mentioned are mixed.
  • the miscibility of the polysaccharide with one of the two further polymer components can be adjusted by a suitable choice of the phase mediator, while the miscibility with the other of the two further polymer components is only insufficient.
  • further additives and aggregates either in a pre-compounding of one or the other component or to add them directly into the mixing unit, which are any suitable plasticizers, plasticizers, fillers, degassing aids, mold release additives, etc. can.
  • the advantage of the present invention is that the melt produced in this way can be processed to a quasi single-layer film, for example by bubble extrusion, slot extrusion, etc.
  • the properties of the film produced correspond to those of a multilayer film, such as has been produced by coextrusion.
  • FIG. 1 a cross section through a film produced according to the invention is shown schematically in FIG.
  • the film shown in cross section in FIG. 1 is one made from thermoplastic starch, polyester amide and polycaprolactone, corresponding to Example 1 from the table above.
  • the individual layers correspond to the different mixture components and alternate irregularly. Partial compatibility can be recognized by the black dots, i.e. at these points, the proportions of a mixed component are distributed in a second mixed component.
  • Injection molded parts, extrudates and foils produced by means of polymer mixtures proposed according to the invention have excellent biodegradability due to the multilayer structure, which is why they are able to make a significant contribution to the acute waste problem.
  • foils are made made from a polymer mixture proposed according to the invention, excellently suitable for a wide variety of applications in agriculture, for example for covering fields, films of this type can either be composted after they have been used or else plowed into the ground in the field.
  • Such polymer mixtures are also suitable for the production of composting bags, composting waste containers, etc.
  • containers and bottles, for example can be produced from the polymer mixture proposed according to the invention by means of blow molding.
  • the degradation rate and the physical properties can be influenced by the selection of the polymer components.
  • the polymer mixtures according to the invention are also suitable for the production of textile products, for example for the production of fibers, monofilaments, flat structures, such as fabrics, felts, nonwovens, so-called backsheets, textile composites, flakes, wadding, and also linear structures, such as for example threads, yarns, ropes, lines etc.
  • the polymer mixtures according to the invention are suitable for the production of hygiene articles such as diapers, bandages, incontinence products and bed liners.
  • the fibers according to the invention are also suitable for producing filter materials, such as cigarette filters in particular.
  • the majority of the polymer mixtures proposed according to the invention such as in particular containing cellulose derivatives, starch derivatives and / or thermoplastic starch and a copoly- Esters or and / or a polyester amide and / or a polyester urethane are also suitable as an adhesive or can also be used as coatings, for example for the impregnation of textile fabrics.
  • polysaccharide or a derivative thereof such as starch or thermoplastic starch
  • flexible packaging consisting of paper and a film made from the material according to the invention, by calendering the paper with the film laminated at an elevated temperature.
  • This combination of paper and bioplastic film is easily printable, biodegradable and suitable for the production of flexible packaging in the food and non-food sectors.
  • High-quality wallpapers are produced by coating with a PVC plastisol in a screen printing or gravure printing process.
  • PVC polyvinyl chloride
  • the emissions and environmental problems of products containing PVC are well known.
  • Blown or flat films can be produced from the polymer mixtures according to the invention in a layer thickness of 80-120 ⁇ m customary for wallpaper coating, which coating may optionally contain fillers and other additives which are bonded to the wallpaper paper by heat sealing in a calendering tool and then be printed several times, as is known.
  • folding roads are usually made from metal materials, rarely from plastic. Theoretically, folding roads should be resumed after the exercise or use, but this is not done in practice because the folding roads are distorted after heavy traffic, especially heavy trucks and armored vehicles, and are therefore unusable for further use. In order to reduce the environmental impact in this case as well, folding lines are advantageously produced from the proposed, high-strength, biodegradable materials.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un matériau polymère biodégradable qui se caractérise par au moins un polysaccharide et/ou un dérivé d'un polysaccharide, ainsi qu'au moins par deux autres polymères d'une cristallinité différente qui ne peuvent pas se mélanger complètement l'un avec l'autre. Au moins un des composants polymères présente, de préférence, une cristallinité élevée. En outre, le polysaccharide ou son dérivé peut être mélangé de façon au moins presque homogène avec au moins un des deux autres composants polymères.
PCT/IB1999/001866 1998-12-23 1999-11-23 Materiaux polymeres biodegradables ou melanges de polymeres ternaires a base de polysaccharide ou d'un derive de polysaccharide Ceased WO2000039212A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU10709/00A AU1070900A (en) 1998-12-23 1999-11-23 Biodegradable polymer materials or ternary polymer mixtures on a polysaccharide or polysaccharide derivative basis

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH2546/98 1998-12-23
CH254698 1998-12-23

Publications (1)

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WO2000039212A1 true WO2000039212A1 (fr) 2000-07-06

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003022540A1 (fr) * 2001-08-16 2003-03-20 Alexander Maksimow Procede de fabrication d'objets essentiellement biodegradables
EP1382642A1 (fr) * 2002-07-15 2004-01-21 Rockwool International A/S Composition de liant aqueux sans formaldehyde pour fibres minérales
US9334360B2 (en) 2011-07-15 2016-05-10 Sabic Global Technologies B.V. Color-stabilized biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof
EP2497797B1 (fr) 2007-10-22 2016-09-14 BIOTEC Biologische Naturverpackungen GmbH & Co. KG Matériau polymère et son procédé d'élaboration
CN110066499A (zh) * 2019-04-04 2019-07-30 李志鹏 基于纳米技术可生物降解的包装材料
WO2020156970A1 (fr) * 2019-01-30 2020-08-06 Basf Se Procédé de production de mélanges d'amidon
CN112715636A (zh) * 2020-12-29 2021-04-30 江苏优普保鲜技术有限公司 小龙虾虾尾镀冰衣用密着剂及其在小龙虾虾尾镀冰衣上的应用方法

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WO1992020740A1 (fr) * 1991-05-18 1992-11-26 Ivan Tomka Melange polymere pour la fabrication de feuilles
WO1993000399A1 (fr) * 1991-06-26 1993-01-07 The Procter & Gamble Company Films biodegradables impermeables au liquide
EP0596437A2 (fr) * 1992-11-06 1994-05-11 Bio-tec Biologische Naturverpackungen GmbH Mélange de polymères biodégradable
WO1997048764A1 (fr) * 1996-06-20 1997-12-24 Biotec Biologische Naturverpackungen Gmbh Materiau biodegradable forme essentiellement d'amidon thermoplastique ou a base d'amidon thermoplastique

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WO1992019680A1 (fr) * 1991-05-03 1992-11-12 Novamont S.P.A. Compositions polymeres biodegradables a base d'amidon et de polymeres thermoplastiques
WO1992020740A1 (fr) * 1991-05-18 1992-11-26 Ivan Tomka Melange polymere pour la fabrication de feuilles
WO1993000399A1 (fr) * 1991-06-26 1993-01-07 The Procter & Gamble Company Films biodegradables impermeables au liquide
EP0596437A2 (fr) * 1992-11-06 1994-05-11 Bio-tec Biologische Naturverpackungen GmbH Mélange de polymères biodégradable
WO1997048764A1 (fr) * 1996-06-20 1997-12-24 Biotec Biologische Naturverpackungen Gmbh Materiau biodegradable forme essentiellement d'amidon thermoplastique ou a base d'amidon thermoplastique

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WO2003022540A1 (fr) * 2001-08-16 2003-03-20 Alexander Maksimow Procede de fabrication d'objets essentiellement biodegradables
EP1382642A1 (fr) * 2002-07-15 2004-01-21 Rockwool International A/S Composition de liant aqueux sans formaldehyde pour fibres minérales
WO2004007615A1 (fr) * 2002-07-15 2004-01-22 Rockwool International A/S Composition de liant aqueuse sans formaldehyde pour fibres minerales
EA007495B1 (ru) * 2002-07-15 2006-10-27 Роквул Интернэшнл А/С Композиция водного связующего для минеральных волокон, не содержащая формальдегида
CN1313538C (zh) * 2002-07-15 2007-05-02 罗克伍尔国际公司 用于矿物纤维的无甲醛含水粘合剂组合物
AU2003250055B2 (en) * 2002-07-15 2009-09-10 Rockwool International A/S Formaldehyde-free aqueous binder composition for mineral fibers
EP2497797B2 (fr) † 2007-10-22 2022-07-13 BIOTEC Biologische Naturverpackungen GmbH & Co. KG Matériau polymère et son procédé d'élaboration
EP2497797B1 (fr) 2007-10-22 2016-09-14 BIOTEC Biologische Naturverpackungen GmbH & Co. KG Matériau polymère et son procédé d'élaboration
US9334360B2 (en) 2011-07-15 2016-05-10 Sabic Global Technologies B.V. Color-stabilized biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof
WO2020156970A1 (fr) * 2019-01-30 2020-08-06 Basf Se Procédé de production de mélanges d'amidon
CN110066499A (zh) * 2019-04-04 2019-07-30 李志鹏 基于纳米技术可生物降解的包装材料
CN112715636A (zh) * 2020-12-29 2021-04-30 江苏优普保鲜技术有限公司 小龙虾虾尾镀冰衣用密着剂及其在小龙虾虾尾镀冰衣上的应用方法
CN112715636B (zh) * 2020-12-29 2024-04-12 南通华普生物科技有限公司 小龙虾虾尾镀冰衣用密着剂及其在小龙虾虾尾镀冰衣上的应用方法

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