+

WO1999032555A1 - Melanges de polymeres a base d'amidon derive - Google Patents

Melanges de polymeres a base d'amidon derive Download PDF

Info

Publication number
WO1999032555A1
WO1999032555A1 PCT/DE1998/003601 DE9803601W WO9932555A1 WO 1999032555 A1 WO1999032555 A1 WO 1999032555A1 DE 9803601 W DE9803601 W DE 9803601W WO 9932555 A1 WO9932555 A1 WO 9932555A1
Authority
WO
WIPO (PCT)
Prior art keywords
esters
groups
starch
blends according
component
Prior art date
Application number
PCT/DE1998/003601
Other languages
German (de)
English (en)
Inventor
Inno Rapthel
Rolf Kakuschke
Hartmut Stoye
Jens-Peter Wiegner
Wolfgang Drechsel
Original Assignee
Buna Sow Leuna Olefinverbund 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
Application filed by Buna Sow Leuna Olefinverbund Gmbh filed Critical Buna Sow Leuna Olefinverbund Gmbh
Priority to EP98963389A priority Critical patent/EP1051443A1/fr
Publication of WO1999032555A1 publication Critical patent/WO1999032555A1/fr

Links

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
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • 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
    • C08L3/04—Starch derivatives, e.g. crosslinked derivatives
    • C08L3/06—Esters
    • 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
    • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
    • 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 invention relates to polymer blends based on starch esters and synthetic biodegradable materials, primarily for use in the injection molding field.
  • the use of the first group which primarily includes starch, cellulose and lignin, is more economical in terms of sustainable economic development, since it is a matter of renewable raw materials that can also be produced and processed locally.
  • the disadvantage of this product group is a structure that is predetermined by nature, which often only allows limited uses. To a certain extent, this can be counteracted by devating (e.g. cellulose acetate, starch acetate, lignin sulfate).
  • devating e.g. cellulose acetate, starch acetate, lignin sulfate.
  • a property modification is also possible by adding plasticizers, which is absolutely necessary for thermoplastic processing of this product group in many cases (EP 0638609).
  • synthetic petroleum-based polymers have the advantage that their properties can be varied within a wide range by combining a relatively large number of monomer building blocks (amides, esters, ethers) which can be used by microorganisms.
  • monomer building blocks amides, esters, ethers
  • stabilizing elements such as e.g. B. aromatic components.
  • they are mostly very soft and elastic, but not very dimensionally stable.
  • thermoplastic starch and ethylene-vinyl alcohol copolymers (inter alia EP 0722 980), polycaprolactone (J09194692), polyvinyl acetate
  • thermoplastic starch derivatives such as. B. starch diacetate can be used.
  • Blends with favorable combinations of properties require either good compatibility of the blend components or the help of a compatibility agent.
  • high stiffness is a basic property of starch acetate (EP 683609) as a modified natural product. Products made from it, however, are too brittle for many applications, especially when using starches with amylopectin contents ⁇ 50%, due to their relatively low impact resistance.
  • Blend production from starch esters and synthetic biodegradable materials based on ester, ether or amide bonds does bring certain effects with regard to the dimensional stability of the synthetic products.
  • a good impact resistance of the blends is, however, due to the insufficient compatibility of most of the polymers available on the basis mentioned with the named starch esters only reached when the synthetic component contains more than 50%. At such concentrations, however, the modulus of elasticity of such blends is already very low.
  • the object of the invention is to develop biodegradable or compostable injection molding materials based on renewable raw materials, which are characterized by high rigidity and good flexibility.
  • the object is achieved in that a blend of 40 to 80% by weight of a starch ester, the starting amylose content of which is 20 to 100%, preferably a starch acetate with a degree of substitution of 1.5 to 2.6, preferably 2.0 to 2.4 and 20 to 50 wt .-% of a biodegradable polyester and / or polyester amide and / or polyether ester with primarily aliphatic building blocks and 5 to 20% of a plasticizing component, which simultaneously performs a compatibility-imparting function between the two polymers.
  • a starch ester the starting amylose content of which is 20 to 100%, preferably a starch acetate with a degree of substitution of 1.5 to 2.6, preferably 2.0 to 2.4 and 20 to 50 wt .-% of a biodegradable polyester and / or polyester amide and / or polyether ester with primarily aliphatic building blocks and 5 to 20% of a plasticizing component, which simultaneously performs a compatibility-imparting function between the
  • Suitable synthetic blend components are only those which have a crystallinity of at most 40%, preferably have a largely X-ray amorphous structure.
  • Polyether polyols with molecular weights from 100 to 2000, preferably from 200 to 600 g / mol. These esters are characterized by a batch ratio of carbonate: diol component of 1: 0.6 to 1: 1.3, preferably of 1: 0.8 to 1: 1.1.
  • the OH number can vary from 200 to 600, preferably from 250 to 400.
  • starch acetate it is expedient for starch acetate to be mixed with the plasticizing / phase-imparting components in a high-speed mixer. Fillers of an inorganic or organic type can also be added to this mixture. However, just like the synthetic blend component, they can be added to the extruder via a separate metering unit. It is favorable to use a twin-shaft kneader, which ensures a good distribution of the blend component as well as the auxiliary and fillers in the starch acetate matrix.
  • Table 2 contains some of the key parameters of the sample materials listed.
  • the characteristic values were determined on ISO standard rods with the dimensions 80mm x 10mm x 4mm or measured on shoulder bars according to DIN 53455. The characteristic values were determined as follows:
  • the migration was tested according to EC directive 9318, EEC (implementation according to ASU B 80.30 -1-3 EG) for 1 hour at 70 ° C in water.
  • PEG polyethylene glycol
  • ADB Adipic acid dibutyl ester

Landscapes

  • 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)
  • Biological Depolymerization Polymers (AREA)

Abstract

L'invention concerne des mélanges de polymères à base d'esters d'amidon et de matières biodégradables synthétiques. Ces mélanges sont principalement utilisés dans le domaine du moulage par injection et se distinguent par une grande rigidité et une bonne flexibilité. Ces mélanges sont constitués de 40 à 80 % en poids d'un ester d'amidon, de préférence, d'un acétate d'amidon ayant un degré de substitution de 1,5 à 2,6 et 20 à 50 % en poids d'un polyester et/ou d'un polyesteramide et/ou d'un ester de polyéther biodégradable ayant principalement des éléments aliphatiques et 5 à 20 % d'un constituant plastifiant qui a simultanément une fonction établissant la compatibilité entre les deux polymères. On utilise des esters et des esters oligomères de la composition suivante: constituant acide: acide carbonique et/ou acide dicarbonique avec n groupes CH2 (n = 0 à 6); constituant alcool: alcool aliphatique avec n groupes CH2 (n = 1 à 6) et/ou dioles aliphatiques avec n groupes CH2 (n = 1 à 6) et/ou polyoles de polyéther ayant des masses molaires de 100 à 2000 g/mol. Ces esters se caractérisent par un rapport carbonate/constituant diol de 0,6 à 1:1,3. Le nombre hydroxyle peut varier de 200 à 600.
PCT/DE1998/003601 1997-12-20 1998-12-08 Melanges de polymeres a base d'amidon derive WO1999032555A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP98963389A EP1051443A1 (fr) 1997-12-20 1998-12-08 Melanges de polymeres a base d'amidon derive

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1997157147 DE19757147A1 (de) 1997-12-20 1997-12-20 Polymerblends auf Basis derivatisierter Stärke
DE19757147.6 1997-12-20

Publications (1)

Publication Number Publication Date
WO1999032555A1 true WO1999032555A1 (fr) 1999-07-01

Family

ID=7852927

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE1998/003601 WO1999032555A1 (fr) 1997-12-20 1998-12-08 Melanges de polymeres a base d'amidon derive

Country Status (3)

Country Link
EP (1) EP1051443A1 (fr)
DE (1) DE19757147A1 (fr)
WO (1) WO1999032555A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120029112A1 (en) * 2010-07-28 2012-02-02 Hallstar Innovations Corp. Biopolymer Compositions Having Improved Impact Resistance

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5496557A (en) * 1978-01-17 1979-07-31 Teijin Ltd Polyester resin composition
WO1994007953A1 (fr) * 1992-10-07 1994-04-14 Parke, Davis & Company Melanges d'ester d'amidon et de polyesters lineaires
WO1995004108A1 (fr) * 1993-07-27 1995-02-09 Evercorn, Inc. Produits moulables biodegradables et pellicules comprenant des melanges d'esters d'amidon et de polyesters

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3914022A1 (de) * 1989-04-28 1990-10-31 Aeterna Lichte Gmbh & Co Kg Biologisch abbaubare kunststoffmaterialien
DE9219021U1 (de) * 1991-05-03 1997-02-27 Novamont S.P.A., Mailand/Milano Biologisch abbaubare Polymer-Zusammensetzung auf der Basis von Stärke und thermoplastischen Polymeren
DE4117628C3 (de) * 1991-05-29 1999-02-11 Inventa Ag Verfahren und Vorrichtung zur Herstellung von Stärkeschmelze sowie nach diesem Verfahren erhältliche Produkte
US5256711A (en) * 1991-10-04 1993-10-26 Director-General Of Agency Of Industrial Science Starch-containing biodegradable plastic and method of producing same
DE4133335C2 (de) * 1991-10-08 1995-11-02 Inventa Ag Stärkemischung, Verfahren zu ihrer Herstellung sowie Verwendung derselben
DE4424415A1 (de) * 1993-08-04 1996-01-18 Buna Gmbh Bioabbaubare, thermoplastische verformbare Materialien
DE4429269A1 (de) * 1994-08-18 1996-02-22 K & S Bio Pack Entwicklung Verfahren zur Herstellung von Gegenständen aus thermoplastischer Amylose, Formmasse zur Durchführung des Verfahrens sowie Formteil
DE19624641A1 (de) * 1996-06-20 1998-01-08 Biotec Biolog Naturverpack Biologisch abbaubarer Werkstoff, bestehend im wesentlichen aus oder auf Basis thermoplastischer Stärke

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5496557A (en) * 1978-01-17 1979-07-31 Teijin Ltd Polyester resin composition
WO1994007953A1 (fr) * 1992-10-07 1994-04-14 Parke, Davis & Company Melanges d'ester d'amidon et de polyesters lineaires
WO1995004108A1 (fr) * 1993-07-27 1995-02-09 Evercorn, Inc. Produits moulables biodegradables et pellicules comprenant des melanges d'esters d'amidon et de polyesters

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 7925, Derwent World Patents Index; AN 66750B *
PATENT ABSTRACTS OF JAPAN vol. 3, no. 118 (C - 060) 4 October 1979 (1979-10-04) *

Also Published As

Publication number Publication date
DE19757147A1 (de) 1999-06-24
EP1051443A1 (fr) 2000-11-15

Similar Documents

Publication Publication Date Title
DE69433252T2 (de) Schmelzverarbeitbare bioabbaubare Zusammensetzungen und daraus hergestellte Artikel
DE60125396T2 (de) Geformte weich elastomer/hard polyester zusammensetzung mit shalldämpfenden eingeschaften
EP2497797B2 (fr) Matériau polymère et son procédé d'élaboration
EP0773972B1 (fr) Corps moule constitue d'un materiau composite a base d'acetate de cellulose et de fibres cellulosiques naturelles d'armature, son procede de fabrication et son utilisation
EP1656423B1 (fr) Melange de polyester biodegradable
EP0596437B1 (fr) Mélange de polymères biodégradable
EP1838784B1 (fr) Melanges de polyesters biodegradables
EP2212378B1 (fr) Materiau polymere et son procede d'elaboration
EP2953997B1 (fr) Matériau composite microstructuré, son procédé de fabrication, corps façonné réalisé dans ce matériau et applications correspondantes
EP2954008B1 (fr) Composés polymères thermoplastiques contenant des lignines de bas poids moléculaire, procédés de fabrication de ces composés, corps façonnés et utilisations
DE102010038627A1 (de) Umweltfreundliche Polypropylen-Polymilchsäurekomposit-Zusammensetzung
DE102017003340A1 (de) Biologisch abbaubare Folie
EP1428852B1 (fr) Composition de liant pulvérulent sans formaldéhyde, ainsi que son utilisation pour lier des substrats par réticulation thermique
DE102018211722B4 (de) Polypropylen-Verbundharzzusammensetzung mit silylierter mikrofibrillierter Cellulose, Verfahren zur Herstellung eines Fahrzeuginnenmaterials unter Verwendung derselben und Fahrzeugsäulenverkleidung unter Verwendung derselben
DE102010031892B4 (de) Faserverstärkte Verbundstoffe, Verfahren zu deren Herstellung sowie deren Verwendung
KR102393643B1 (ko) 표면처리된 부산석고를 포함하는 생분해성 필름 조성물 및 이의 제조방법
DE2257571C2 (de) Polyesterformmasse
WO1999032555A1 (fr) Melanges de polymeres a base d'amidon derive
DE102018005741B4 (de) Polyesterharzzusammensetzung und unter Verwendung derselben hergestellter Gegenstand
EP0638609B1 (fr) Matériaux thermoformables biodégradables dérivés d'esters d'amidon
WO2020115221A1 (fr) Procédé de production d'un (co)polyester
WO2001094470A1 (fr) Matiere de moulage biodegradable tres rigide et coulante
EP4471088A2 (fr) Composition polymère contenant de l'amidon de pois
DE102013103614A1 (de) Polymerzusammensetzung
EP2380915B1 (fr) Matériau à base d'amidon thermoplastique et résistant à la déformation dans l'eau et son procédé de fabrication

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1998963389

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1998963389

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1998963389

Country of ref document: EP

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载