EP0848725A1 - Polyester biodegradable, materiaux constitues de ce polyester et procede de fabrication associe - Google Patents

Polyester biodegradable, materiaux constitues de ce polyester et procede de fabrication associe

Info

Publication number
EP0848725A1
EP0848725A1 EP96931768A EP96931768A EP0848725A1 EP 0848725 A1 EP0848725 A1 EP 0848725A1 EP 96931768 A EP96931768 A EP 96931768A EP 96931768 A EP96931768 A EP 96931768A EP 0848725 A1 EP0848725 A1 EP 0848725A1
Authority
EP
European Patent Office
Prior art keywords
polycarboxylic acid
aliphatic
polyester
condensed
diisocyanate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP96931768A
Other languages
German (de)
English (en)
Inventor
Wolf-Dieter Deckwer
Rolf Joachim MÜLLER
Uwe Witt
Hans-Jürgen ARNING
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.)
Huels AG
Original Assignee
Huels AG
Chemische Werke Huels AG
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 Huels AG, Chemische Werke Huels AG filed Critical Huels AG
Publication of EP0848725A1 publication Critical patent/EP0848725A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2230/00—Compositions for preparing biodegradable polymers

Definitions

  • the invention relates to biodegradable copolyesters from aliphatic and aromatic dicarboxylic acids with high molar masses (in particular in the form of a material or material) as well as materials from the polyester and a manufacturing process.
  • thermoplastic plastic materials that can be biodegraded by microorganisms have increasingly been developed in recent years.
  • First approaches to blends of conventional olefinic polymers with starch [Krupp et al. in environments. Be. Technol. , 26 (1992) 193-198] had good application properties, but were only partially degradable, since only the starch fraction was metabolized by microorganisms.
  • Biodegradable materials that are used directly or after suitable modification [Utz et al., Investigations on the use of biodegradable plastics in the packaging sector, (1991), BMFT Research Report No.
  • 01-zv 8904] obtained from biogenic polymers are generally completely biodegradable, but often have serious disadvantages with regard to processing and application .
  • plasticized starch materials are not water-resistant.
  • significant disadvantages of such natural materials can be seen above all in the limited variability and reproducibility of the material properties.
  • polyesters and polyamides can be achieved by increasing the molar mass by linking them with diisocyanates, bisoxiranes or peroxides [DE-A-1 495 714.3, DE-A- 2 011 678.3].
  • diisocyanates bisoxiranes or peroxides
  • EP-A-0 572 256 Diisocyanates are added to this material in amounts of 0.1 to 5%.
  • the thermal properties of the aliphatic polyester remain largely unaffected by such a modification.
  • German patent application (1) 95 08 737.2 it could be shown that it is possible to produce statistical copolyesters from aliphatic dicarboxylic acids and terephthalic acid as well as various aliphatic dicarboxylic acids and terephthalic acid as well as various aliphatic diols which have sufficient processing and usage properties have, on the other hand, but are also biodegradable.
  • An essential structural criterion of these materials is that the proportion of neighboring dicarboxylic acid units is kept small in order to ensure the biodegradability of the copolyesters.
  • These copolyesters produced by conventional melt condensation can be processed into molded parts by extrusion.
  • melt viscosities require high molar masses of the copolyesters. In principle, this is achieved by increasing the molar masses of the copolyesters by raising the temperature, further reducing the pressure and significantly longer reaction times. Polycondensation times. For industrial purposes, however, this process is not practical, particularly for copolyesters, because of the long reaction times and the thermal stress on the materials.
  • the task that led to the present invention was to develop a material that has both good processing and application properties, but can also be degraded by ubiquitous microorganisms.
  • biodegradable polyesters in particular in the form of a work material or material
  • polyesters on the one hand consist of polyol and aromatic polycarboxylic acid and (ii) on the other hand consist of polyol and aliphatic polycarboxylic acid, wherein more than 90% of the units according to (i) are directly linked to none or at most one further unit according to (i), characterized that the polyesters have been produced using a diisocyanate as an additional monomer component, the isocyanate being used in a smaller amount compared to each of the other monomer components.
  • the polyesters according to the invention can be prepared by adding 0.1 to 5% by weight and in particular 0.5 to 2% by weight bifunctional isocyanates based on the polyester, for example after the condensation of the aliphatic / aromatic copolyesters inflicts the melt.
  • Aliphatic, cycloaliphatic or aromatic diisocyanates in particular hexamethylene diisocyanate, can be used as diisocyanates.
  • the polyester according to the invention can have a proportion which goes back to the aromatic polycarboxylic acid as a monomer component, from 3 to 65 and in particular 35 to 55 mol% (based on total acid in the form of monomer components). This feature is advantageous for biodegradability.
  • the polyester according to the invention can have been produced in that the polyester with
  • an aliphatic diol in particular C 2 -g-diol, preferably 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol or 1,6-hexanediol,
  • An aromatic dicarboxylic acid preferably terephthalic acid
  • polyester of the invention can be prepared by condensing the polyester in the form of its methyl ester with the aid of aromatic dicarboxylic acids and / or aliphatic dicarboxylic acids.
  • the additives customary in the art for improving the hydrolytic stability may have been added to the polycondensate, for example phosphorus compounds; for the prior art, compare, for example, EP-A-0 572 256.
  • the polyester according to the invention can be produced by
  • step (i) it can be condensed with an excess of polyol.
  • the procedure can also be such that (a) the diisocyanate is melted or (b) the melt and the diisocyanate are placed in a separate reactor and condensed therein to the end product.
  • step (i) it is possible to condense to a precursor with molecular weights of 5,000 to 60,000 g / mol and preferably 20,000 to 50,000 g / mol.
  • step (ii) it is also possible to condense to an end product with molar masses of 60,000 to 350,000 g / mol and in particular 100,000 to 250,000 g / mol.
  • Polyesters according to the invention can be characterized by melting points of 40 to 155 ° C. and in particular 90 to 155 ° C. Polyesters according to the invention can be distinguished by high melt viscosities.
  • an essential advantage of the polyesters according to the invention is that the thermal properties, the processing and mechanical properties and the rate of biodegradation are established within wide limits and adapt to the particular application to let. This flexibility is guaranteed by a possible variation of the monomer components and their proportions, as well as the further parameters mentioned above.
  • the polyesters according to the invention differ from those of German patent application (1) 95 08 737.2 in that they are precondensed polyesters.
  • biodegradability of the polyesters according to the invention reference can be made to the aforementioned German patent application.
  • coupling with the aid of diisocyanates ensures biodegradability by microorganisms.
  • Powdery polyester according to the invention is applied to an agar plate with a complex medium and inoculated with a microorganism consortium which is capable of biodegrading polyester according to German patent application (1) 95 08 737.2 (pre-polyester) , so also clearly clear areas around the microorganism colonies occur in the polyesters according to the invention, for example at an incubation temperature of 55 ° C. within 7 days; for the degradation test compare Augusta et al. in Appl. Microbiol. Biotechnol., 39 (1993) 673-678.
  • the present invention relates to a material made from a biodegradable polyester according to the invention in the form of
  • Molded parts preferably injection molded, extruded or foamed molded parts, in particular blown films, extruded films, coextruded films, blown articles, thermoformed articles, foamed articles or monofilament materials.
  • Polyesters according to the invention can be produced, for example, by thermoplastic processes, such as pressing, extrusion, coextrusion, injection molding, melt spinning, deep-drawing, foaming or blow molding, to give flat material, for example films, or molded parts, or by suitable methods to give foamed molded parts, laminates, filamentous materials , Fibers or composite materials.
  • thermoplastic processes such as pressing, extrusion, coextrusion, injection molding, melt spinning, deep-drawing, foaming or blow molding, to give flat material, for example films, or molded parts, or by suitable methods to give foamed molded parts, laminates, filamentous materials , Fibers or composite materials.
  • polyesters according to the invention are chain-lengthened polymers which have significantly higher melt viscosities than the non-chain-lengthened copolyesters of the prior art, the polyesters according to the invention are particularly suitable for processing methods for which high melt viscosities are desired, for example for blow molding lien procedure.
  • Materials according to the invention can have a high mechanical strength. This mechanical strength can be increased by stretching at temperatures below the melting point.
  • the material according to the invention can contain conventional inorganic or organic fillers which do not impair biodegradation be added, preferably silica gel, titanium dioxide, talc, starch and / or cellulose.
  • the invention finally relates to a process for the production of biodegradable polyesters which are degraded in the natural environment with the action of microorganisms and which are high molecular weight statistical copolyesters which use an aliphatic polyol, one aromatic polycarboxylic acid and at the same time an aliphatic polycarboxylic acid are produced as monomer components and have constituent repeating units or repeating units which
  • the preliminary product is condensed to the end product with a diisocyanate as an additional monomer component, the diisocyanate being used in a smaller amount than any of the other monomer components.
  • Agar plates are prepared with 20 ml medium in each case using customary sterile methods.
  • Polymer The polymer in question is dissolved in 1% chloroform and sprayed onto the agar plate in the form of fine particles using a fine nozzle. To remove the chloroform, the plate is left open for some time under the Cleanbench.
  • Organism Isolate (CH2 / 5) from enrichment culture with non-chain-length degradable copolymers from compost at 60 ° C.
  • the organism is transferred from an agar plate with a non-chain-extended copolyester with an inoculation loop to the agar plate with the material to be tested and incubated at 55 ° C.
  • the formation of farms around the organism cultures, in which no polymer material can be seen, is characterized by an average farm diameter.
  • Films with a thickness of 120 ⁇ m are produced from the materials according to the invention (diameter 2.5 cm).
  • the films are biologically contaminated as follows:
  • the films are placed on an agar plate with the synthetic mineral medium described above or a complex medium from a compost eluate.
  • the inoculation takes place before the films are placed by spreading out the screened microorganism consortia on the agar plate.
  • the incubation temperature is 55 ° C.
  • the percentage weight loss of the films is determined.
  • the films are introduced into a reactor which is externally thermostatted to 60 ° C. and filled with mature compost material (60% moisture) (for better recovery of the fragments, the films are enclosed in polyethylene nets).
  • the reactor is gassed with preheated and water vapor-saturated air during the test period. The percentage weight loss of the films is determined. Melt viscosity determination by MFI measurements
  • Measuring temperature 150 - 220 ° C
  • Example 1 Synthesis of poly [(tetramethylene hexanedioate) -co- (tetramethylene terephthalate)]
  • the pressure is then gradually reduced to about 0.1 hPa and the base polymer is condensed under GPC control to a molar mass of 50,000 g / mol.
  • the vacuum is released and 0.5 g of phosphorous acid is stirred into the melt.
  • 15 g of hexamethylene diisocyanate are then added directly to the melt at 200 ° C. with stirring. The viscosity of the melt increases significantly within a few minutes.
  • the copolyester is then extended, cooled and granulated.
  • a white, flexible material is obtained with a weight-average molar mass of 168,500 g / mol and a melting point of 109 ° C. Films of this material produced by extrusion typically have tensile strengths of 25 N / mm and elongations at break of 900%.
  • Example 2 Synthesis of poly [(tetramethylene hexanedioate) -co- (tetramethylene terephthalate)]
  • 35.83 g of 1,4-butanediol, 30.89 g of dimethyl terephthalate (DMT), 34.87 g of adipic acid and 0.025 g of tetraisopropyl orthotitanate and 0.025 g of triphenyl phosphate are condensed as in Example 1 to a molar mass of 48000 g / mol.
  • a 250 ml three-necked flask serves as the polymerization reactor. After the addition of 0.05 g of phosphorous acid, the copolyester is extended, cooled and granulated.
  • a white, flexible material is obtained with a weight-average molar mass of 232300 g / mol and a melting point of 107 ° C.
  • Films of this material produced by melt pressing typically have tensile strengths of 16 N / mm and elongations at break of 600%.
  • Compost test (a) (% weight loss) after 4 weeks 38 + 13 31 5 after 8 weeks 78 + 7 71 11
  • Nozzle gap width 0.8 mm
  • Trigger height 1.5 m
  • Granules from Example 1 with an MFI (190 / 21.5) of 3.75 g / 10 min are processed to blown films at a speed of 2-3 m / min and with an inflation ratio of 1: 2 on the system described above.
  • the films obtained in this way show transparency and strength properties comparable to those of the LDPE with significantly higher extensibility.

Abstract

L'invention concerne des polyesters biodégradables détruits par des micro-organismes dans un environnement naturel. Ces polyesters sont des copolyesters statistiques de haut PM, produits par l'utilisation d'un polyol aliphatique, d'un acide polycarboxylique aromatique et simultanément d'un acide polycarboxylique aliphatique comme composants monomères. Ils comportent des motifs constitutionnels répétitifs ou récurrents, constitués d'une part (i) d'un polyol et d'un acide polycarboxylique aromatique et d'autre part (ii) d'un polyol et d'un acide polycarboxylique aliphatique, où plus de 90 % des motifs selon (i) ne sont liés directement à aucun autre motif ou au maximum à un seul autre motif selon (i). Ces polyesters sont produits à l'aide d'un di-isocyanate comme composant monomère supplémentaire, l'isocyanate étant employé en plus faible quantité que chacun des autres composants monomères. L'invention concerne en outre des matériaux constitués de ce polyester biodégradable et un procédé de fabrication desdits polyesters.
EP96931768A 1995-09-05 1996-09-04 Polyester biodegradable, materiaux constitues de ce polyester et procede de fabrication associe Withdrawn EP0848725A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19532771 1995-09-05
DE19532771A DE19532771A1 (de) 1995-09-05 1995-09-05 Biologisch abbaubarer Polyester, Werkstoffe aus dem Polyester und Herstellungsverfahren
PCT/EP1996/003879 WO1997009364A1 (fr) 1995-09-05 1996-09-04 Polyester biodegradable, materiaux constitues de ce polyester et procede de fabrication associe

Publications (1)

Publication Number Publication Date
EP0848725A1 true EP0848725A1 (fr) 1998-06-24

Family

ID=7771329

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96931768A Withdrawn EP0848725A1 (fr) 1995-09-05 1996-09-04 Polyester biodegradable, materiaux constitues de ce polyester et procede de fabrication associe

Country Status (6)

Country Link
US (1) US6150490A (fr)
EP (1) EP0848725A1 (fr)
JP (1) JP2000501121A (fr)
AU (1) AU7083896A (fr)
DE (1) DE19532771A1 (fr)
WO (1) WO1997009364A1 (fr)

Families Citing this family (11)

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Publication number Priority date Publication date Assignee Title
DE19817883C1 (de) * 1998-04-08 1999-11-25 Monofil Technik Gmbh Mähfaden
US6573340B1 (en) 2000-08-23 2003-06-03 Biotec Biologische Naturverpackungen Gmbh & Co. Kg Biodegradable polymer films and sheets suitable for use as laminate coatings as well as wraps and other packaging materials
US7241832B2 (en) * 2002-03-01 2007-07-10 bio-tec Biologische Naturverpackungen GmbH & Co., KG Biodegradable polymer blends for use in making films, sheets and other articles of manufacture
US7297394B2 (en) 2002-03-01 2007-11-20 Bio-Tec Biologische Naturverpackungen Gmbh & Co. Kg Biodegradable films and sheets suitable for use as coatings, wraps and packaging materials
US7172814B2 (en) * 2003-06-03 2007-02-06 Bio-Tec Biologische Naturverpackungen Gmbh & Co Fibrous sheets coated or impregnated with biodegradable polymers or polymers blends
EP1721935B1 (fr) * 2004-03-04 2010-09-08 Unitika Ltd. Composition de resine polyester biodegradable, procede pour la fabrication de celle-ci, et mousse et moulage obtenus a partir de celle-ci
KR100701622B1 (ko) 2005-02-24 2007-03-30 이규득 생분해성 지방족/방향족 코폴리에스테르 중합체 및 그 제조방법
ITMI20050452A1 (it) * 2005-03-18 2006-09-19 Novamont Spa Poliestere biodegradabile alifatico-aromatico
DE102005053068B4 (de) * 2005-11-04 2017-05-11 Basf Se Sebazinsäurehaltige Polyester und Polyestermischung, Verfahren zu deren Herstellung sowie ein Verzweigerbatch und die Verwendung der Polyestermischung
DE102013226031A1 (de) * 2013-12-16 2015-06-18 Tesa Se Biologisch abbaubarer Haftklebstoff auf Basis von Polyester-Polyurethan
CN114539777B (zh) * 2022-01-27 2022-09-02 广东顶峰精密技术有限公司 一种用于多层印制线路板和覆铜板压合工艺的缓冲垫的制备方法

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Also Published As

Publication number Publication date
DE19532771A1 (de) 1997-03-06
US6150490A (en) 2000-11-21
JP2000501121A (ja) 2000-02-02
WO1997009364A1 (fr) 1997-03-13
AU7083896A (en) 1997-03-27

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