WO1998007782A1 - Materiaux biodegradables thermoplastiquement deformables pour emballages de produits alimentaires - Google Patents

Materiaux biodegradables thermoplastiquement deformables pour emballages de produits alimentaires Download PDF

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Publication number
WO1998007782A1
WO1998007782A1 PCT/DE1997/001725 DE9701725W WO9807782A1 WO 1998007782 A1 WO1998007782 A1 WO 1998007782A1 DE 9701725 W DE9701725 W DE 9701725W WO 9807782 A1 WO9807782 A1 WO 9807782A1
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WO
WIPO (PCT)
Prior art keywords
starch
esters
acids
compositions according
molding compositions
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/DE1997/001725
Other languages
German (de)
English (en)
Inventor
Inno Rapthel
Christel Rom
Hartmut Stoye
Rolf Kakuschke
Dieter Weiwad
Kerstin Reichwald
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.)
Dow Olefinverbund GmbH
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
Publication of WO1998007782A1 publication Critical patent/WO1998007782A1/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
    • 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
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable

Definitions

  • the invention relates to molding compositions for the production of biodegradable or compostable thermoplastically deformable materials, which are particularly suitable for use in the field of food packaging, fast food, etc. and from biodegradable or compostable blends, in particular from starch esters and polyesters and other biological compatible additives exist.
  • biodegradable materials show that the use of such materials is possible in many areas. However, it is still difficult to cover the wide range of properties known for conventional plastics with new, environmentally compatible materials. In addition, there are often costs that are too high to prevent their widespread use.
  • Blends of starch or starch derivatives and synthetic polymers are generally known (including DE 42 37 535).
  • Copolymers used include: EVOH, poly- ⁇ -caprolactone, polyhydroxybutyric acid, ethyl cellulose, special polyamides or polyester amides. '
  • starch or low-substituted starch derivatives are usually the main component in these blends, there are a number of application problems for the products made from them:
  • the plasticizers used are mostly hydrophilic and migrate very quickly in the aqueous medium. This in turn prohibits applications in the food sector.
  • DE 4114185 proposes a coester with longer-chain fatty acids, which is processed using plasticizers, such as ethyl citrate, glycerol acetate and lactic acid esters.
  • EP 0638609 proposes a blend of starch acetate (DS 1, 8-2.6) and polyethylene glycol (MG 200-2000) using various auxiliaries.
  • DE 4443539 proposes blends of starch esters and polyalkylene carbonates.
  • the solution proposed there with plasticizer mixtures of polyalkylene glycols as the primary plasticizer for starch acetate and a second, secondary plasticizer component for determining the compatibility between the two polymer components brings considerable advantages with regard to the mechanical properties and the water resistance of the products. These variants are not yet satisfactory in terms of plasticizer migration and heat resistance
  • the invention is therefore based on the object of providing materials which are biodegradable and thermoplastically processable at an economically justifiable cost and which are suitable for applications in the open air area and / or in the ground due to lower migration values for applications in the food sector or due to their improved weather stability and increased heat resistance
  • the blends according to the invention consist of starch esters based on starches which have an amylopectin content of 20-80%, preferably starch acetate with a degree of substitution 1.5-2.6, preferably 1.8-2, and aliphatic polycarbonates with or without addition of oxydicarboxylic acids and / or oxytricarboxylic acids with 2 to 10 carbon atoms in a ratio of 100: 2 to 1000: 1 starch ester to polyfunctional carboxylic acid using plasticizers and customary additives.
  • plasticizers for starch acetate instead of the usual plasticizers for starch acetate, so-called secondary plasticizers for starch acetate are used, which at the same time act as a compatibilizer.
  • Such secondary plasticizers are preferably biologically compatible compounds.
  • Esters of polyols with aliphatic monocarboxylic acids or esters of polyfunctional carboxylic acids with short-chain alkanols are well suited.
  • the weight ratio of the carboxylate groups to the CH, CH 2 and CH 3 groups can be between 1 • 0.5 to 1 4, preferably between 1 1 to 1 2.
  • These include, for example, citric acid t ⁇ alkyl (-ethyl or -butyl) ester, glycennecarboxylate (-t ⁇ butyrate), adipic acid ester with Ci - to C -alcohols, T ethyie ⁇ gyikolt ⁇ acetat
  • the aliphatic polycarbonates are polymers containing carbonic acid ester groups, the chemical structure of the formula
  • polyethylene, polypropylene and polybutylene carbonate are particularly favorable.
  • PEC polyethylene carbonate
  • polypropylene carbonate (PPC) and polybutylene carbonate (PBC) offers u. a. in the case of moldings which are to have certain mechanical properties over relatively long periods (2-8 years), but which can then be left to decay, for example, in the base.
  • the mixtures according to the invention can also contain conventional fillers and pigments such as, for. B. talc, chalk, titanium dioxide, cellulose powder or starch in the order of 0-30% based on the total mass.
  • the ratio of starch ester to aliphatic polycarbonates can be 5:95 to 95: 5.
  • the proportion of additives and plasticizers should be 0 to 15% by mass, preferably 3 to 12% by mass.
  • the solid components are placed in a high-speed mixer and to be used during the intensive ven mixing the liquid components are added by spraying. These mixtures can then be extruded and granulated. It is also possible to meter the plasticizer component directly into the extrusion process or to add all the subcomponents separately. Granules produced in this way can be processed at temperatures of 130 ° C to 180 ° C on conventional injection molding machines. The resulting products are largely insensitive to water, although they still have a water absorption of 5 - 10%.
  • transparent objects can also be shaped, for example.
  • the amounts of polyalkylene carbonates used can be varied to a lesser extent in other areas, and those of the other blend components mentioned.
  • a high heat resistance is achieved by keeping the plasticizer content low.
  • An advantage of the procedure proposed here is that the mixtures described can still be processed very well and also show good mechanical characteristics.
  • Table 2 contains some of the key parameters of the examples given. The characteristic values were based on the abovementioned. Specimens determined as follows:
  • PEG 400 polyethylene glycol
  • Ball indentation hardness 30 "[N / mm 2 ] 70 59 38 56 62 51 25 29 61 48

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)

Abstract

Les matériaux selon l'invention sont constitués par des mélanges d'esters d'amidon et de polycarbonates linéaires ou ramifiés aliphatiques dans un rapport compris entre 5:95 et 95:5. A la place des plastifiants usuels pour les esters d'amidon, on utilise des plastifiants dits secondaires qui ont en même temps la fonction d'auxiliaires de compatibilité. Les mélanges obtenus se distinguent principalement par des indices de migration avantageux.
PCT/DE1997/001725 1996-08-20 1997-08-11 Materiaux biodegradables thermoplastiquement deformables pour emballages de produits alimentaires Ceased WO1998007782A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19633476.4 1996-08-20
DE19633476A DE19633476A1 (de) 1996-08-20 1996-08-20 Bioabbaubare thermoplastisch verformbare Materialien für Lebensmittelverpackungen

Publications (1)

Publication Number Publication Date
WO1998007782A1 true WO1998007782A1 (fr) 1998-02-26

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ID=7803080

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE1997/001725 Ceased WO1998007782A1 (fr) 1996-08-20 1997-08-11 Materiaux biodegradables thermoplastiquement deformables pour emballages de produits alimentaires

Country Status (2)

Country Link
DE (1) DE19633476A1 (fr)
WO (1) WO1998007782A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100360610C (zh) * 2005-10-20 2008-01-09 中山大学 可降解塑料组合物及其制备方法
CN100365064C (zh) * 2005-10-20 2008-01-30 中山大学 全降解聚甲基乙撑碳酸酯/乙烯乙烯醇共聚物复合发泡材料及其制备方法
US20120183779A1 (en) * 2011-01-18 2012-07-19 Sk Innovation Co., Ltd. Multilayer film
US8795745B2 (en) 2008-10-13 2014-08-05 Roquette Freres Thermoplastic or elastomeric compositions based on esters of a starchy material and method for preparing such compositions
CN113214615A (zh) * 2021-06-03 2021-08-06 中国科学院长春应用化学研究所 一种三元完全生物降解薄膜及其制备方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19822979A1 (de) 1998-05-25 1999-12-02 Kalle Nalo Gmbh & Co Kg Folie mit Stärke oder Stärkederivaten und Polyesterurethanen sowie Verfahren zu ihrer Herstellung
EP1869127A1 (fr) * 2005-03-24 2007-12-26 Madrisano Catinari Materiau en plastique biodegradable
CN102020838A (zh) * 2010-11-11 2011-04-20 中山大学 一种可完全降解的聚甲基乙撑碳酸酯共混材料及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1950028A1 (de) * 1969-02-28 1970-09-17 Owens Illinois Inc Elektrofotografische Druck- oder Kopiervorrichtung
DE1951949A1 (de) * 1969-10-15 1971-04-29 Westfaelische Metall Industrie Verfahren zur Herstellung von Parabolreflektoren,insbesondere fuer Kraftfahrzeugscheinwerfer
DE1961348A1 (de) * 1969-12-06 1971-10-21 Hueck Fa E Verfahren zur Befestigung einer Eckumlenkung an Fenster- oder Tuerrahmenprofilen und Eckumlenkung
EP0638609A2 (fr) * 1993-08-04 1995-02-15 Buna Gmbh Matériaux thermoformables biodégradables dérivés d'esters d'amidon
WO1996017888A1 (fr) * 1994-12-07 1996-06-13 Buna Sow Leuna Olefinverbund Gmbh Materiaux thermoplastiques deformables biodegradables et emballages en ces materiaux

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4228016C1 (de) * 1992-08-24 1994-03-31 Biotec Biolog Naturverpack Verfahren zum Herstellen von biologisch abbaubaren Folien aus pflanzlichen Rohstoffen
DE4411051C2 (de) * 1994-03-30 1998-04-09 Buna Sow Leuna Olefinverb Gmbh Einwegbehälter für Nahrungsmittel, insbesondere für Trinkwasser
DE19519495A1 (de) * 1995-05-27 1996-11-28 Reynolds Tobacco Gmbh Verpackung aus thermoplastischem Werkstoff mit vollständiger biologischer Abbaubarkeit, vorzugsweise für Tabakwaren
DE4443539A1 (de) * 1994-12-07 1996-06-13 Buna Sow Leuna Olefinverb Gmbh Bioabbaubare thermoplastisch verformbare Materialien
DE19516361A1 (de) * 1995-05-04 1996-11-07 Buna Sow Leuna Olefinverb Gmbh Biologisch abbaubarer Verpackungswerkstoff

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1950028A1 (de) * 1969-02-28 1970-09-17 Owens Illinois Inc Elektrofotografische Druck- oder Kopiervorrichtung
DE1951949A1 (de) * 1969-10-15 1971-04-29 Westfaelische Metall Industrie Verfahren zur Herstellung von Parabolreflektoren,insbesondere fuer Kraftfahrzeugscheinwerfer
DE1961348A1 (de) * 1969-12-06 1971-10-21 Hueck Fa E Verfahren zur Befestigung einer Eckumlenkung an Fenster- oder Tuerrahmenprofilen und Eckumlenkung
EP0638609A2 (fr) * 1993-08-04 1995-02-15 Buna Gmbh Matériaux thermoformables biodégradables dérivés d'esters d'amidon
WO1996017888A1 (fr) * 1994-12-07 1996-06-13 Buna Sow Leuna Olefinverbund Gmbh Materiaux thermoplastiques deformables biodegradables et emballages en ces materiaux

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100360610C (zh) * 2005-10-20 2008-01-09 中山大学 可降解塑料组合物及其制备方法
CN100365064C (zh) * 2005-10-20 2008-01-30 中山大学 全降解聚甲基乙撑碳酸酯/乙烯乙烯醇共聚物复合发泡材料及其制备方法
US8795745B2 (en) 2008-10-13 2014-08-05 Roquette Freres Thermoplastic or elastomeric compositions based on esters of a starchy material and method for preparing such compositions
US20120183779A1 (en) * 2011-01-18 2012-07-19 Sk Innovation Co., Ltd. Multilayer film
US9050743B2 (en) * 2011-01-18 2015-06-09 Sk Innovation Co., Ltd. Multilayer film
CN113214615A (zh) * 2021-06-03 2021-08-06 中国科学院长春应用化学研究所 一种三元完全生物降解薄膜及其制备方法
CN113214615B (zh) * 2021-06-03 2023-10-13 中国科学院长春应用化学研究所 一种三元完全生物降解薄膜及其制备方法

Also Published As

Publication number Publication date
DE19633476A1 (de) 1998-02-26

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