DE102008018964A1 - Polyester mixture, useful in molded article, foil or foam, which are useful in e.g. electronic and packaging industry, comprises polyhydroxyalkanoate, polyester, optical- or natural-fibers, glass beads, compatibilizer and nucleation agent - Google Patents

Polyester mixture, useful in molded article, foil or foam, which are useful in e.g. electronic and packaging industry, comprises polyhydroxyalkanoate, polyester, optical- or natural-fibers, glass beads, compatibilizer and nucleation agent Download PDF

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DE102008018964A1
DE102008018964A1 DE200810018964 DE102008018964A DE102008018964A1 DE 102008018964 A1 DE102008018964 A1 DE 102008018964A1 DE 200810018964 DE200810018964 DE 200810018964 DE 102008018964 A DE102008018964 A DE 102008018964A DE 102008018964 A1 DE102008018964 A1 DE 102008018964A1
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C08K7/20—Glass
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
    • 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

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  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
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Abstract

Polyester mixture (I) comprises: 40-70 wt.% of polyhydroxyalkanoate and/or polylactic acid; biodegradable polyester (10-30 wt.%); optical- or natural-fibers (5-30 wt.%); glass beads (3-10 wt.%); compatibilizer (0-3 wt.%); and nucleation agent (0-1 wt.%).

Description

Die vorliegende Erfindung betrifft Polyestermischungen, enthaltend

  • I) 40 bis 70 Gew.-% Polyhydroxyalkanoat und/oder Polymilchsäure;
  • II) 10 bis 30 Gew.-%, eines biologisch abbaubaren, aliphatisch-aromatischen Polyesters,
  • III) 5 bis 30 Gew.-% Glas- oder Naturfasern,
  • IV) 3 bis 10 Gew.-% Glaskugeln,
  • V) 0 bis 3.0 Gew.-% Verträglichkeitsvermittler und
  • VI) 0–1.0 Gew.-% Nukleierungsmittel.
The present invention relates to polyester blends containing
  • I) 40 to 70% by weight of polyhydroxyalkanoate and / or polylactic acid;
  • II) 10 to 30% by weight of a biodegradable, aliphatic-aromatic polyester,
  • III) 5 to 30% by weight of glass or natural fibers,
  • IV) 3 to 10 wt .-% glass beads,
  • V) 0 to 3.0 wt .-% compatibilizer and
  • VI) 0-1.0 wt .-% nucleating agent.

Weiterhin betrifft die Erfindung Formteile, Folien oder Schäume die aus diesen Mischungen hergestellt werden können sowie deren Verwendung.Farther the invention relates to moldings, films or foams can be prepared from these mixtures and their Use.

Polyhydroxyalkanoate und Polymilchsäure sind interessante biologisch abbaubare Biopolymere. Poly-4-hydroxybutyrate sind von der Fa. Metabolix bekannt. Poly-3-hydroxybutyrate werden beispielsweise von der Fa. PHB Industrial unter dem Markennamen Biocycle® und von der Fa. Tianan unter Enmat® vertrieben. Polymilchsäure ist beispielsweise von der Fa. NatureWorks im Handel erhältlich. All diese Produkte weisen eine Dichte von größer 1.23 g/cm3 auf. Weiterhin sind diese Materialen relativ spröde, sodass sie ohne weitere Komponenten wie beispielsweise Zähmodifizierer im Kraftfahrzeugbau, in der Elektronik oder in der Verpackungsindustrie nicht eingesetzt werden können. Versucht man die negativen Eigenschaften der Biopolymere durch Zugabe von biologisch abbaubaren Polyestern und Glasfasern zu verbessern, steigt die Dichte noch weiter an.Polyhydroxyalkanoates and polylactic acid are interesting biodegradable biopolymers. Poly-4-hydroxybutyrates are known from the company Metabolix. Poly-3-hydroxybutyrate are sold for example by the company. PHB Industrial under the brand name Biocycle ® and from the Fa. Tianan under Enmat ®. Polylactic acid is commercially available, for example, from NatureWorks. All of these products have a density of greater than 1.23g / cm 3. Furthermore, these materials are relatively brittle, so they can not be used without further components such as toughening modifiers in the automotive industry, in electronics or in the packaging industry. If one tries to improve the negative properties of the biopolymers by adding biodegradable polyesters and glass fibers, the density increases even further.

Besonders im Kraftfahrzeugbau ist man bemüht, die Dichte der verwendeten Materialien zu verringern, um den Kraftstoffverbrauch der Fahrzeuge zu drosseln.Especially in the automotive industry, it is endeavored to increase the density of the used Reduce materials to fuel consumption of vehicles to throttle.

Es wurde nun gefunden, dass durch Zusatz von 3 bis 10 Gew.-% hohlen Glaskugeln die Dichte der Polyestermischungen sich auf die im Kraftfahrzeugbau üblicherweise verwendeten Materialien – wie beispielsweise mit Talk gefülltes Polypropylen reduzieren lässt, ohne dass die Anwendungseigenschaften der Polyestermischungen schlechter werden.It has now been found that by addition of 3 to 10 wt .-% hollow Glass spheres the density of the polyester mixtures are usually on the automotive industry used materials - such as filled with talc Polypropylene can be reduced without affecting the application properties the polyester blends get worse.

Unter Polyhydroxyalkanoaten werden in erster Linie Poly-4-hydroxybutyrate und Poly-3-hydroxybutyrate verstanden, weiterhin sind Copolyester der vorgenannten Hydroxybutyrate mit 3-Hydroxyvaleraten umfasst. Poly-4-hydroxybutyrate sind insbesondere von der Fa. Metabolix bekannt. Poly-3-hydroxybutyrate werden beispielsweise von der Fa. PHB Industrial unter dem Markennamen Biocycle® und von der Fa. Tianan unter dem Namen Enmat® vertrieben.Polyhydroxyalkanoates are understood as meaning primarily poly-4-hydroxybutyrates and poly-3-hydroxybutyrates, furthermore copolyesters of the abovementioned hydroxybutyrates with 3-hydroxyvalerates are included. Poly-4-hydroxybutyrates are known in particular from the company Metabolix. Poly-3-hydroxybutyrate are sold for example by the company. PHB Industrial under the brand name Biocycle ® and by the company. Tianan under the name Enmat ®.

Polymilchsäure ist beispielsweise von der Fa. NatureWorks im Handel erhältlich.polylactic acid is for example available from the company NatureWorks commercially.

Die verwendeten Polyhydroxyalkanoate und/oder Polymilchsäuren weisen in der Regel ein Molekulargewicht Mw von 100.000 bis 1.000.000 und vorzugsweise von 450.000 bis 650.000 auf. Das Zahlenmittel Mn beträgt in der Regel 50.000 bis 500.000 und vorzugsweise 200.000 bis 350.000.The polyhydroxyalkanoates and / or polylactic acids used generally have a molecular weight M w of from 100,000 to 1,000,000 and preferably from 450,000 to 650,000. The number average M n is usually 50,000 to 500,000, and preferably 200,000 to 350,000.

Die Polyhydroxyalkanoate und/oder Polymilchsäuren werden in den Mischungen in einer Konzentration von 40 bis 70 Gew.-%, bevorzugt von 50 bis 60 Gew.-% und insbesondere bevorzugt von 55 bis 60 Gew.-% bezogen auf die Komponenten I) bis VI) eingesetzt.The Polyhydroxyalkanoates and / or polylactic acids are used in the mixtures in a concentration of 40 to 70 wt .-%, preferably from 50 to 60 wt .-% and particularly preferably from 55 to 60 wt .-% based used on the components I) to VI).

Als biologisch abbaubare Polyester (Komponente II) können aliphatische oder aromatisch-aliphatische Polyester eingesetzt werden wie sie beispielsweise in der WO 92/09654 und WO 96/1 51 73 beschrieben werden. Bevorzugte Bausteine der Polyester sind:

  • • aliphatische Dicarbonsäuren wie Bernsteinsäure, Adipinsäure oder Sebacinsäure, deren Ester bildende Derivate oder Mischungen davon;
  • • gegebenenfalls aromatische Dicarbonsäuren wie Terephthalsäure oder deren Ester bildende Derivate, und
  • • als Diolkomponente 1,4-Butandiol oder 1,3-Propandiol.
As biodegradable polyesters (component II) it is possible to use aliphatic or aromatic-aliphatic polyesters, as described, for example, in US Pat WO 92/09654 and WO 96/1 51 73 to be discribed. Preferred building blocks of the polyesters are:
  • Aliphatic dicarboxylic acids such as succinic acid, adipic acid or sebacic acid, their ester-forming derivatives or mixtures thereof;
  • Optionally aromatic dicarboxylic acids such as terephthalic acid or its ester-forming derivatives, and
  • As diol component 1,4-butanediol or 1,3-propanediol.

Bevorzugte biologisch abbaubare Polyester (Komponente II) sind Ecoflex® (BASF Aktiengesellschaft), Esstar Bio® und Origo Bi® (Novamont), Bionolle® (Shows Highpolymers).Preferred biodegradable polyester (component II) are Ecoflex ® (BASF Aktiengesellschaft), Eastar Bio ® and origo Bi ® (Novamont), Bionolle ® (shows High Polymers).

Komponente II) wird in der Regel in einer Konzentration von 10 bis 30 Gew.-%, bevorzugt von 15 bis 25 Gew.-% und insbesondere bevorzugt von 20 bis 25 Gew.-% bezogen auf die Komponenten I) bis VI) eingesetzt.Component II) is usually in a concentration of 10 to 30 wt .-%, preferably from 15 to 25 wt .-% and particularly preferably from 20 to 25 wt .-% based on the components I) to VI) used.

Um beispielsweise das Elastizitätsmodul zu erhöhen, werden der Reaktionsmischung Fasern wie Glas oder Naturfasern (Komponente III) zugegeben. Die Fasern weisen in der Regel einen Durchmesser von 1 bis 20 μm auf. Typische Naturfasern sind Hanf, Sisal oder Cellulose. Bevorzugt werden jedoch Glasfasern eingesetzt, die zwar eine hohe Dichte aufweisen, aber das Elastizitätsmodul sehr effizient vergrößern. Die Glasfasern werden üblicherweise in einer Konzentration von 5 bis 30 und bevorzugt von 10 bis 15 Gew.-% bezogen auf die Komponenten I) bis VI) eingesetzt.Around for example, to increase the modulus of elasticity, the reaction mixture fibers such as glass or natural fibers (component III) was added. The fibers usually have a diameter from 1 to 20 μm. Typical natural fibers are hemp, sisal or cellulose. However, preference is given to using glass fibers which Although have a high density, but the modulus of elasticity increase very efficiently. The glass fibers are usually in a concentration of 5 to 30 and preferably from 10 to 15 % By weight, based on components I) to VI).

Um die Dichte der Polyestermischung zu verringern, werden den Polyestermischungen, Glashohlkörper (Komponente IV), die mit Luft oder Inertgas gefüllt sind, zugesetzt. Die Glashohlkörper weisen in der Regel eine Dichte von kleiner 0,9 g/cm3 und vorzugsweise von kleiner 0,7 g/cm3 auf. Der durchschnittliche Durchmesser der Hohlkörper beträgt üblicherweise 10 bis 50 μm, bevorzugt 20 bis 40 μm.In order to reduce the density of the polyester mixture, the polyester mixtures, hollow glass body (component IV), which are filled with air or inert gas, are added. The glass hollow bodies generally have a density of less than 0.9 g / cm 3 and preferably less than 0.7 g / cm 3 . The average diameter of the hollow body is usually 10 to 50 microns, preferably 20 to 40 microns.

Die Glashohlkörper werden in einer Konzentration in einer Konzentration von 3 bis 10 und bevorzugt von 5 bis 8 Gew.-% bezogen auf die Komponenten I) bis VI) eingesetzt.The Glass cavities are in concentration in one concentration from 3 to 10 and preferably from 5 to 8 wt .-% based on the components I) to VI) used.

Weiterhin hat es sich als vorteilhaft erwiesen einen Verträglichkeitsvermittler (Komponente V) zuzugeben. Besonders vorteilhaft haben sich Epoxidgruppen-haltiges Copolymer auf Basis Styrol, Acrylsäureester und/oder Methacrylsäureester als geeignet erwiesen. Die Epoxidgruppen tragenden Einheiten sind vorzugsweise Glycidyl(meth)acrylate. Als vorteilhaft haben sich Copolymere mit einem Glycidylmethacrylat-Anteil von größer 20, besonders bevorzugt von größer 30 und insbesondere bevorzugt von größer 50 Gew.-% des Copolymers erwiesen wie sie beispielsweise von Fa. Johnson Polymer unter der Marke Joncryl® ADR 4368 vertrieben werden. Das mittlere Molekulargewicht der Polymere beträgt vorzugsweise 2000 bis 20.000, insbesondere 4000 bis 12.000.Furthermore, it has proved to be advantageous to add a compatibilizer (component V). Particularly advantageous epoxy group-containing copolymer based on styrene, acrylic acid esters and / or methacrylic esters have proven to be suitable. The epoxy groups bearing units are preferably glycidyl (meth) acrylates. An advantageous are copolymers having a glycidyl methacrylate content of greater than 20, more preferably greater than 30 and especially preferably of greater than 50 proved wt .-% of the copolymer such as are marketed, for example, by Fa. Johnson Polymer under the trademark Joncryl ® ADR 4368th The average molecular weight of the polymers is preferably 2,000 to 20,000, in particular 4,000 to 12,000.

Komponente V) wird häufig in einer Konzentration von 0.5 bis 3 und bevorzugt von 1.0 bis 1.5 Gew.-% bezogen auf die Komponenten I) bis VI) eingesetzt.component V) is often in a concentration of 0.5 to 3 and preferably from 1.0 to 1.5% by weight, based on the components I) to VI) used.

Weiterhin können der erfindungsgemäßen Mischung folgende Additive zugesetzt werden:

  • • Nukleierungsmittel (Komponente VI) wie Talkum, Kreide, Ruß, Graphit, Calcium- oder Zinkstearat, Poly-D-Milchsäure, N,N'ethylen-bis-12-hydroxystearamid, Polyglykolsäure, und insbesondere Bornitrid (Boronid SX der Fa. ESK Ceramics GmbH & Co.KG). Nukleierungsmittel werden in einer Konzentration von 0.2 bis 1 und bevorzugt von 0.4 bis 0.6 Gew.-% bezogen auf die Komponenten I) bis VI) eingesetzt.
  • • Gleit- und Antiblockmittel,
  • • Wachse,
  • • Antistatika,
  • • Weitere Kompatibilizer wie Silane, Maleinsäureanhydrid, Fumarsäureanhydrid, Isocyanate, Disäurechloride,
  • • Antifog-Mittel,
  • • UV-Stabilisatoren oder
  • • Farbstoffe
  • • bis zu 50 Gew.-% organische Füllstoffe wie Polymere aus nachwachsenden Rohstoffen, z. B.: Stärke, Cerealien, oder Polycaprolacton.
Furthermore, the following additives can be added to the mixture according to the invention:
  • Nucleating agent (component VI) such as talc, chalk, carbon black, graphite, calcium or zinc stearate, poly-D-lactic acid, N, N'-ethylene-bis-12-hydroxystearamide, polyglycolic acid, and in particular boron nitride (Boronid SX from ESK Ceramics GmbH & Co.KG). Nucleating agents are used in a concentration of 0.2 to 1 and preferably from 0.4 to 0.6 wt .-% based on the components I) to VI).
  • Lubricants and antiblocking agents,
  • • waxes,
  • • antistatic agents,
  • Other compatibilizers such as silanes, maleic anhydride, fumaric anhydride, isocyanates, diacid chlorides,
  • Antifogging agent,
  • • UV stabilizers or
  • • dyes
  • Up to 50% by weight of organic fillers such as polymers of renewable raw materials, eg. For example: starch, cereals, or polycaprolactone.

Schließlich kann es von Vorteil sein, der Polyestermischung weitere Polymere zuzumischen, um das Eigenschaftsprofil der Mischungen noch weiter zu verbessern. Beispiele für die weiteren Polymere sind: Polyolefine, Styrolcopolymere wie beispielsweise Styrol/Butadien-Copolymere, ASA, ABS; Polyamide, Polyester, die nicht biologisch abbaubar sind wie PBT oder PET. Besonders bevorzugt ist Polypropylen. Diese Polymere können in einer Konzentration von 1 bis 15 und vorzugsweise 5 bis 10 Gew.-% bezogen auf die Komponenten I) bis VI) eingesetzt werden.After all it may be advantageous, the polyester blend more polymers to add to the property profile of the mixtures even further to improve. Examples of the other polymers are: Polyolefins, styrene copolymers such as styrene / butadiene copolymers, ASA, ABS; Polyamides, polyesters that are not biodegradable like PBT or PET. Particularly preferred is polypropylene. These polymers can in a concentration of 1 to 15 and preferably 5 to 10 wt .-% based on the components I) to VI) can be used.

Aus den erfindungsgemäßen Polyestermischungen lassen sich Formteile, Folien oder Schäume herstellen, die sich hervorragend für den Einsatz im Kraftfahrzeugbau, in der Elektronik oder in der Verpackungsindustrie eignen. Im Gegensatz zu den herkömmlichen Materialien bestehen die erfindungsgemäßen Formteile, Folien oder Schäume zum überwiegenden Teil aus nachwachsenden Rohstoffen.Out Let the polyester mixtures of the invention moldings, foils or foams are produced that are Excellent for use in automotive engineering, in the Electronics or in the packaging industry. In contrast to the conventional materials consist of the invention Moldings, foils or foams for the most part Part of renewable raw materials.

BeispieleExamples

Beispiel 1example 1

Die einzelnen Komponenten wurden in der Konzentration, die unten in der angefügten Tabelle in einem Doppelschneckenextruder ZSK 30 bei 150 Umdrehungen pro Minute und einem Durchsatz von 10 kg/h bei 150°C gemischt. Die Komponenten wurden separat zugegeben, die Komponenten I), III) und IV) wurden über einen „hot feed" zugegeben. Zusammensetzung der Polyestermischung: Komponente Eingesetztes Material Konzentr. [Gew.-%] I) Biocycle® 1000: Poly-3-hydroxybutyrate der Fa. PHB-Industrial S.A. 57.6 II) Ecoflex® FBX 7011 von BASF Aktiengesellschaft 22.9 IV) Glasfasern DS 3185E-10N der Fa. Owens Corning 10.0 IIV) Glashohlkörper der Fa. 3M specialty materials 8.0 V) Joncryl® ADR 4368S der Fa Johnson Polymers 1.0 VI) Bornitrid Roronid SX der Fa. ESK Ceramics GmbH 0.5 The individual components were mixed at the concentration noted below in the attached table in a ZSK 30 twin-screw extruder at 150 rpm and a throughput of 10 kg / h at 150 ° C. The components were added separately, the components I), III) and IV) were added via a "hot feed" composition of the polyester mixture: component Used material Conc. [Wt .-%] I) Biocycle ® 1000: poly-3-hydroxybutyrate of the company PHB Industrial SA. 57.6 II) Ecoflex ® FBX 7011 by BASF Aktiengesellschaft 22.9 IV) Glass fibers DS 3185E-10N from Owens Corning 10.0 IIA) Glass hollow body of the company 3M specialty materials 8.0 V) Joncryl ® ADR 4368S Fa Johnson Polymers 1.0 VI) Boron nitride Roronid SX from ESK Ceramics GmbH 0.5

Angewendete Untersuchungsmethoden:Applied examination methods:

  • • die Dichte wurde nach ISO 1183 bestimmt• the density has decreased ISO 1183 certainly
  • • das Elastizitätsmodul, die Bruchfestigkeit und die Bruchdehnung nach ISO 527-2 • the modulus of elasticity, the breaking strength and the elongation at break after ISO 527-2
  • • die Schlagbiegeversuche (Charpy) nach ISO 179/1eA u. ISO 179/1eU bei 23°C• the impact tests (Charpy) after ISO 179 / 1eA u. ISO 179 / 1eU at 23 ° C
  • • Schlagzähigkeit (Izod) nach ASTM 0256• Toughness (Izod) according to ASTM 0256
  • • Formbeständigkeitstemperatur (HDT) nach ISO 75-2 • Heat distortion temperature (HDT) after ISO 75-2

Untersuchungexamination Beispiel 1example 1 Vergleichsbeispiel*Comparative Example * Dichte [g/cm3]Density [g / cm 3 ] 1.231.23 1.231.23 Elastizitätsmodul [mPA]modulus of elasticity [MPa] 45204520 42004200 Bruchfestigkeit [mPA]breaking strength [MPa] 3333 2929 Bruchdehnung [%]elongation [%] 1,51.5 4.34.3 Schlagzähigkeit (Charpy) [KJ/m2]Impact strength (Charpy) [KJ / m 2 ] 1414 4141 Kerbschlagzähigkeit (Charpy) [KJ/m2]Impact Strength (Charpy) [KJ / m 2 ] 3.23.2 3.33.3 Schlagzähigkeit (Izod) [J/m]impact strength (Izod) [y / m] 3636 3838 HDT/A [°C]HDT / A [° C] 113113 9090 HDT/B [°C]HDT / B [° C] 146146 142142

  • * 60 Gew.-% Polypropylen (Prime Polypro) und 40 Gew.-% Talkum* 60% by weight polypropylene (Prime Polypro) and 40% by weight of talc

Ein Formteil das mit einer erfindungsgemäßen Polyestermischung (Beispiel 1) hergestellt wurde, weist ein ähnliches Eigenschaftsprofil auf wie das bisher im Kraftfahrzeugbau üblicherweise eingesetzte Polypropylen mit 40 Gew.-% Füllstoff (Talkum; Vergleichsbeispiel). Im Gegensatz zu den herkömmlichen Materialien besteht die erfindungsgemäße Mischung überwiegend aus nachwachsenden Rohstoffen.One Molded with a polyester blend according to the invention (Example 1) has a similar property profile on as the previously used in the automotive industry usually Polypropylene with 40% by weight of filler (talc, comparative example). In contrast to the conventional materials, the inventive mixture predominantly from renewable raw materials.

ZITATE ENTHALTEN IN DER BESCHREIBUNGQUOTES INCLUDE IN THE DESCRIPTION

Diese Liste der vom Anmelder aufgeführten Dokumente wurde automatisiert erzeugt und ist ausschließlich zur besseren Information des Lesers aufgenommen. Die Liste ist nicht Bestandteil der deutschen Patent- bzw. Gebrauchsmusteranmeldung. Das DPMA übernimmt keinerlei Haftung für etwaige Fehler oder Auslassungen.This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Zitierte PatentliteraturCited patent literature

  • - WO 92/09654 [0010] WO 92/09654 [0010]
  • - WO 96/15173 [0010] WO 96/15173 [0010]

Zitierte Nicht-PatentliteraturCited non-patent literature

  • - ISO 1183 [0021] - ISO 1183 [0021]
  • - ISO 527-2 [0021] - ISO 527-2 [0021]
  • - ISO 179/1eA [0021] - ISO 179 / 1eA [0021]
  • - ISO 179/1eU [0021] - ISO 179 / 1eU [0021]
  • - ISO 75-2 [0021] - ISO 75-2 [0021]

Claims (8)

Polyestermischung, enthaltend I) 40 bis 70 Gew.-% Polyhydroxyalkanoat und/oder einer Polymilchsäure; II) 10 bis 30 Gew.-%, eines biologisch abbaubaren Polyesters, III) 5 bis 30 Gew.-% Glas- oder Naturfasern, IV) 3 bis 10 Gew.-% Glaskugeln, V) 0 bis 3.0 Gew.-% Verträglichkeitsvermittler und VI) 0 bis 1.0 Gew.-% Nukleierungsmittel.Polyester blend containing I) 40 to 70% by weight of polyhydroxyalkanoate and / or a polylactic acid; II) 10 to 30% by weight of a biodegradable polyester, III) 5 to 30% by weight glass or natural fibers, IV) 3 to 10% by weight Glass beads, V) 0 to 3.0% by weight of compatibilizer and VI) 0 to 1.0 wt .-% nucleating agent. Polyestermischung nach Anspruch 1, wobei Komponente I) ein Poly-3-hydroxybutyrat oder Poly-4-hydroxybutyrat ist.A polyester blend according to claim 1, wherein component I) is a poly-3-hydroxybutyrate or poly-4-hydroxybutyrate. Polyestermischung nach Anspruch 1, wobei in Komponente II): • aliphatische Dicarbonsäure wie Bernsteinsäure, Adipinsäure oder Sebacinsäure, deren Ester bildende Derivate oder Mischungen davon bedeutet; • gegebenenfalls aromatische Dicarbonsäure wie Terephthalsäure oder deren Ester bildende Derivate bedeutet, und • als Diolkomponente 1,4-Butandiol oder 1,3-Propandiol eingesetzt werden.A polyester blend according to claim 1, wherein in component II): Aliphatic dicarboxylic acid, such as succinic acid, Adipic acid or sebacic acid, their esters forming Derivatives or mixtures thereof; • possibly aromatic dicarboxylic acid such as terephthalic acid or their esters are forming derivatives, and • when Diol component 1,4-butanediol or 1,3-propanediol can be used. Polyestermischung nach Anspruch 1, wobei Komponente III) Glasfasern bedeuten.A polyester blend according to claim 1, wherein component III) mean glass fibers. Polyestermischung nach Anspruch 1, wobei Komponente IV) mit Inertgas oder Luft gefüllte Glaskugeln sind.A polyester blend according to claim 1, wherein component IV) are glass balls filled with inert gas or air. Polyestermischung nach Anspruch 1, wobei Komponente V) ein polymeres Glycidyl(meth)acrylat oder ein Copolymer aus Styrol und Glycidyl(meth)acrylat bedeutet.A polyester blend according to claim 1, wherein component V) a polymeric glycidyl (meth) acrylate or a copolymer of styrene and glycidyl (meth) acrylate. Formteile, Folien oder Schäume enthaltend Polymermischungen gemäß den Ansprüchen 1 bis 6.Containing moldings, foils or foams Polymer blends according to the claims 1 to 6. Verwendung der Formteile, Folien oder Schäume gemäß Anspruch 7 im Kraftfahrzeugbau, in der Elektronik oder Verpackungsindustrie.Use of molded parts, foils or foams according to claim 7 in the automotive industry, in electronics or packaging industry.
DE200810018964 2007-07-20 2008-04-16 Polyester mixture, useful in molded article, foil or foam, which are useful in e.g. electronic and packaging industry, comprises polyhydroxyalkanoate, polyester, optical- or natural-fibers, glass beads, compatibilizer and nucleation agent Withdrawn DE102008018964A1 (en)

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DE102008035530A1 (en) * 2008-07-29 2010-02-04 Volkswagen Ag Producing a biopolymer-molded part, useful in motor vehicle, comprises converting a biopolymer or its blend into melts, mixing the melts with a blowing agent or precursor and injecting the mixture into a cavity of molding apparatus
WO2010086345A1 (en) 2009-01-30 2010-08-05 Wincor Nixdorf International Gmbh Device and method for the payment and/or withdrawal of banknotes having a first face value and of banknotes having a second face value
CN101955638A (en) * 2010-09-21 2011-01-26 浙江大学宁波理工学院 Plant fiber-reinforced polylactic acid foam material and preparation method thereof
WO2011086030A3 (en) * 2010-01-14 2011-09-09 Basf Se Method for producing expandable granulates containing polylactic acid
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WO2012116515A1 (en) * 2011-02-28 2012-09-07 江苏锦禾高新科技股份有限公司 Degradable plastic and manufacturing method thereof
EP2759569A1 (en) * 2013-01-24 2014-07-30 So.F.Ter. Tecnopolimeri Srl A polyactic acid-based composition, a process for processing a polylactic acid based composition into a moulded article
EP3036277A1 (en) * 2013-08-20 2016-06-29 Tepha, Inc. Closed cell foams including poly-4-hydroxybutyrate and copolymers thereof
US11806447B2 (en) 2013-11-05 2023-11-07 Tepha, Inc. Compositions and devices of poly-4-hydroxybutyrate

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Cited By (19)

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DE102008035530A1 (en) * 2008-07-29 2010-02-04 Volkswagen Ag Producing a biopolymer-molded part, useful in motor vehicle, comprises converting a biopolymer or its blend into melts, mixing the melts with a blowing agent or precursor and injecting the mixture into a cavity of molding apparatus
US8240450B2 (en) 2009-01-30 2012-08-14 Wincor Nixdorf International Gmbh Apparatus and method for depositing and/or dispensing at least banknotes having a first denomination and banknotes having a second denomination
WO2010086345A1 (en) 2009-01-30 2010-08-05 Wincor Nixdorf International Gmbh Device and method for the payment and/or withdrawal of banknotes having a first face value and of banknotes having a second face value
DE102009006810A1 (en) 2009-01-30 2010-08-05 Wincor Nixdorf International Gmbh Apparatus and method for depositing and / or disbursing at least banknotes of a first denomination and banknotes of a second denomination
US9212270B2 (en) 2010-01-14 2015-12-15 Basf Se Method for producing expandable granulates containing polylactic acid
US10253150B2 (en) 2010-01-14 2019-04-09 Basf Se Method for producing expandable granulates containing polylactic acid
JP2015165033A (en) * 2010-01-14 2015-09-17 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Method for manufacturing foamable polylactic acid-containing granules
WO2011086030A3 (en) * 2010-01-14 2011-09-09 Basf Se Method for producing expandable granulates containing polylactic acid
CN101955638B (en) * 2010-09-21 2012-07-04 浙江大学宁波理工学院 Plant fiber-reinforced polylactic acid foam material and preparation method thereof
CN101955638A (en) * 2010-09-21 2011-01-26 浙江大学宁波理工学院 Plant fiber-reinforced polylactic acid foam material and preparation method thereof
WO2012055796A1 (en) * 2010-10-27 2012-05-03 Basf Se Use of polymer blends for producing slit film tapes
WO2012116515A1 (en) * 2011-02-28 2012-09-07 江苏锦禾高新科技股份有限公司 Degradable plastic and manufacturing method thereof
US9051466B2 (en) 2011-02-28 2015-06-09 Jiangsu Jinhe Hi-Tech Co., Ltd. Degradable plastic and manufacturing method thereof
EP2759569A1 (en) * 2013-01-24 2014-07-30 So.F.Ter. Tecnopolimeri Srl A polyactic acid-based composition, a process for processing a polylactic acid based composition into a moulded article
EP3036277A1 (en) * 2013-08-20 2016-06-29 Tepha, Inc. Closed cell foams including poly-4-hydroxybutyrate and copolymers thereof
US10689498B2 (en) 2013-08-20 2020-06-23 Tepha, Inc. Closed cell foams including poly-4-hydroxybutyrate and copolymers thereof
EP3036277B1 (en) * 2013-08-20 2021-05-26 Tepha, Inc. Closed cell foams including poly-4-hydroxybutyrate and copolymers thereof
US11292885B1 (en) 2013-08-20 2022-04-05 Tepha, Inc. Closed cell foams including poly-4-hydroxybutyrate and copolymers thereof
US11806447B2 (en) 2013-11-05 2023-11-07 Tepha, Inc. Compositions and devices of poly-4-hydroxybutyrate

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