WO1996007687A1 - Polyester biodegradable et materiau fabrique en un tel polyester - Google Patents

Polyester biodegradable et materiau fabrique en un tel polyester Download PDF

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Publication number
WO1996007687A1
WO1996007687A1 PCT/EP1995/002722 EP9502722W WO9607687A1 WO 1996007687 A1 WO1996007687 A1 WO 1996007687A1 EP 9502722 W EP9502722 W EP 9502722W WO 9607687 A1 WO9607687 A1 WO 9607687A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyester
acid
mol
aliphatic
aromatic
Prior art date
Application number
PCT/EP1995/002722
Other languages
German (de)
English (en)
Inventor
Uwe Witt
Rolf-Joachim MÜLLER
Wolf-Dieter Deckwer
Original Assignee
Hüls 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
Priority claimed from DE19944432161 external-priority patent/DE4432161A1/de
Priority claimed from DE19508737A external-priority patent/DE19508737A1/de
Application filed by Hüls Ag filed Critical Hüls Ag
Priority to EP95944721A priority Critical patent/EP0779907A1/fr
Priority to JP8509147A priority patent/JPH10505620A/ja
Publication of WO1996007687A1 publication Critical patent/WO1996007687A1/fr

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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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids

Definitions

  • the invention relates to biodegradable polyesters (in particular in the form of a material or material) and materials made from the polyester.
  • Polyesters are part of the state of the art.
  • EP-A-0 007 445 describes a mixed polyester based on 1,4-butanediol and terephthalic acid, 10 to 30 mol% of the terephthalic acid being a mixture of 20 to 80 mol% of adipic acid, 10 up to 60 mol% glutaric acid and 10 to 40 mol% succinic acid are replaced and the percentages add up to 100.
  • These known mixed polyesters are intended for the production of molded parts by injection molding or extrusion.
  • EP-A-0 028 687 also describes copolyesters composed of 40 to 85 mol% terephthalic acid (which can be replaced up to 50% by other dicarboxylic acids, for example sebacic acid), 60 to 15 mol% adipic acid and C 2 _g- Alkane diols such as butylene glycol. These known copolyesters are in the form of hot-melt adhesives or powder coating agents provided so that the question of their biodegradability does not arise. For the production and use of these known copolyesters, EP-A-0 028 687 refers to much older prior art.
  • polymeric materials can undergo biodegradation.
  • Mainly materials that are obtained directly or after modification from naturally occurring polymers are to be mentioned here, for example polyhydroxyalkanoates, such as polyhydroxybutyrate, plastic celluloses, cellulose esters, plastic starches, chitosan and pullulan.
  • polyhydroxyalkanoates such as polyhydroxybutyrate
  • plastic celluloses such as polyhydroxybutyrate
  • plastic starches such as polyhydroxybutyrate
  • chitosan and pullulan a targeted variation of the polymer composition or the structure, as is desirable on the part of the polymer application, is difficult and often only possible to a very limited extent due to the natural synthesis process.
  • polyesters represent an important class within these materials. Synthetic polyesters which contain only aliphatic monomers have a relatively good biodegradability, and because of their material properties, they can be used only to an extremely limited extent; see Witt et al. in Macrom. Chem. Phys., 195 (1994) 793-802. Aromatic polyesters, on the other hand, show no biodegradation with good material properties.
  • An object of the present invention is to synthesize copolymers (in particular in the form of a material or material) which at the same time have biodegradability and good thermal and mechanical properties. This goal is achieved by producing synthetic copolymers with a defined composition.
  • the object on which the invention is based is thus achieved by a biodegradable Dissolvable polyester, which is degraded in the natural environment under the influence of microorganisms, for example according to DIN 53739D or ASTM D5338-92, the polyester being characterized in that the polyester consists of an aliphatic polyol and an aromatic polycarboxylic acid as well ⁇ at the time an aliphatic polycarboxylic acid was produced as a monomer component and has constitutional repeating units or recurring units which
  • the polyester according to the invention can have a molecular weight of 1,000 to 70,000 g / mol.
  • the polyester according to the invention can have a melting point of 40 to 150 ° C. and in particular 90 to 150 ° C.
  • polyester according to the invention can be made from
  • An aromatic dicarboxylic acid preferably terephthalic acid, and - an aliphatic preferably adipic acid or sebacic acid, have been condensed.
  • the invention further relates to a polyester with a proportion based on an aromatic dicarboxylic acid as a monomer component of 3 to 65 and in particular 35 to 55 mol% (based on total acid content).
  • Another object of the present invention is to provide a work material or a material which at the same time has biodegradability and good thermal and mechanical properties.
  • This object is achieved according to the invention by a material made from a biodegradable polyester according to the invention, the material being in the form of flat material, in particular foils, single filaments, filamentous material or molded parts, in particular injection molded, extruded or foamed molded parts.
  • Filamentous material can be in the form of fibers, felt or fabric.
  • the material according to the invention can be a composite material.
  • Foils in particular packaging foils, for example for packaging fresh goods in retail, or for pre-packaged goods in retail, such as outer packaging (bundling of individual packaging), "skin packaging” (for small parts, such as nails), blister packaging ( Films on cardboard carriers, for example for coated tablets), protective packaging or transparent films, for example as a florist's requirement; Composting bags, in particular for household waste (for example 10 1) or garden waste (for example 100 1); Films in the medical field, for example for or as disposable clothing or gloves; Foils as or in the form of baby diapers; "Big Bag", in particular large-volume bags, for example for bulk goods, such as fertilizers or animal feed; Cover foils, for example in agriculture; Labels; or weather balloons; furthermore transport packaging, clothes bags, building foils or bed pads;
  • Tree nets for example to protect crops from birds; Covering nets for floors, for example against soil erosion; Nets for food packaging, for example for vegetables or fruit; Nets for selling trees or shrubs, such as Christmas trees; Fishing nets; Household wipes, such as wipes; Diaper pads; Fleece in the hygiene and cosmetics sector; Medical fleece; Extractor filters; Car interior filter; Filters for the food sector, for example for breweries; Filters for aquariums and ponds;
  • molded parts in particular disposable tableware; Food packaging, for example yoghurt cups, bottles or tubes; Cosmetic packaging, for example bottles or tubes; Bag closures; Disposable items in the medical field, for example syringes or spatulas; Plastic parts for fireworks; Plastic ammunition, for example for military purposes; Cemetery and burial requirements, for example grave containers, grave lights or coffin applications; Golf tees; Pellets for controlled release, for example for fertilizer or crop protection; Carrier body for drinking water treatment; Plant pots; Support rods, for example for garden centers; Support parts for earthworks, for example when planting slopes;
  • Composite paper cans for example for snacks, milk powder or raisins; coated papers, for example with improved moisture resistance;
  • Cloths for example made of fibers according to the invention in combination with natural fibers;
  • Press fiber mats for example as "adhesives", also in the form of plant pots or for car interior trims;
  • Fiber composite for example furniture parts or load-bearing car interior linings;
  • foamed materials especially packaging chips; Packaging foam body; Plant pots; Floor aerators; Disposable tableware; Packaging trays, for example for meat, fruit, eggs or ampoules; or upholstery material.
  • the monomer components specified in Table 1 are suitable, which are either available in large quantities and inexpensively by known petrochemical processes or at least partly by biotechnological ones Processes from renewable raw materials are accessible (1,3-propanediol, 2,3-butanediol, adipic and sebacic acid).
  • polyester copolymers The synthesis of the polyester copolymers was carried out as described in Examples 1-9 and leads to polycondensates of structural formula 1.
  • PTA (x 3, y 4) poly [(trimethylene hexanedioate-co-trimethylene terephthalate)]
  • PTS poly [(trimethylene-decanedioate-co-trimethylene-terephthalate)]
  • the thermal properties are characterized by the melting points (see Table 2).
  • the melting behavior became dependent the proportion of terephthalic acid examined in more detail.
  • a terephthalic acid content of approx. 30 mol% (based on the acid content in the copolyester) there are melting points and material properties that correspond to those of the pure aliphatic polyester (e.g. SP36: Saturated polyester made of 1,3-propanediol and adipic acid.
  • SP3i ⁇ Saturated polyester from 1,3-propanediol and sebacic acid).
  • Polyester foams (25 mm 0, 100 microns thickness) were treated in 100 ml liquid volume at 25 ° C with stirring and air supply. A corresponding mineral salt medium and an earth or compost eluate were added. As shown in Fig. 2, PTA and PTS copolyesters are well degraded up to a terephthalic acid content of 30% in the specified aquatic system. A breakdown of the statistical copolyesters with terephthalic acid components> 30 mol% (based on the acid component) could not be observed in the aquatic system. Obviously, the presence of the microbial mixed culture and the mineral salts is not sufficient for microbial degradation in the observed period.
  • Polyesters with purely aliphatic acids can be completely biodegraded.
  • the degradation results shown under 4. show that this is also possible if the proportion is aromatic
  • Dicarboxylic acid does not exceed a certain value.
  • investigations were carried out with model oligomers, 1, 3- as the diol.
  • Propanediol was used because of its middle position and terephthalic acid.
  • the synthesis of these oligo-trimethylene terephthalates or poly-trimethylene terephthalates (PTMT) is in example
  • Table 3 shows the average molecular weights (determined by GPC with
  • PTMT 1 10.2 ⁇ 0.1 0.0 87.1 97.3 PTMT 2 16.3 ⁇ 0.1 2.5 78.8 97.4 PTMT 3 23.2 ⁇ 0.1 4.0 74, 9 102.2
  • the distribution of the oligomers in PTMT 1 - 3 was examined by gel permeation chromatography before and after degradation.
  • the molecular weights Mps obtained from the GPC refer to polystyrene as the calibration standard.
  • mass spectroscopy after GPC fractionation, a complete assignment of all polymerization products (MH + MS ) was obtained.
  • the peak assignment obtained in this way is given in Table 5 and Fig. 6 shows the chromatogram for the synthesized oligomer mixture PTMT3 before it is used in degradation studies.
  • the peak CD occurring at an elution time of 8.84 min is cyclic
  • the copolyester is cooled under vacuum, repeatedly dissolved in chloroform and precipitated in ice-cold methanol (technical grade), and then dried in vacuo for 24 hours.
  • Example 8 0.165 mol of 1,4-butanediol, 0.045 mol of dimethyl terephthalate (DMT), 0.105 mol of adipic acid and 0.04 g of zinc acetate dihydrate are condensed as in Example 1.
  • Example 8
  • the resistance to hydrolysis at room temperature is determined on the statistical copolyesters prepared in Examples 1-4. Polyester films are sterilized with ethanol and shaken in sterile water at room temperature (150 rpm). No changes in weight loss and chain splitting (determined by GPC measurements) can be observed in the examined period of 3 months. In addition, the resistance to hydrolysis at 60 ° C. is determined on the statistical copolyesters prepared in Examples 1-4. Polyester films are sterilized with ethanol and shaken in sterile water at 60 ° C (150 rpm). The statistical copolyesters PTS (41/59) and PTS (56/44) showed no weight loss after 10 weeks, the PTA (39/61) and PTA (43/57) 3.5% and 6% weight loss, respectively.
  • the degradability of the statistical copolyesters is checked in an earth digging test (DIN 53739D).
  • DIN 53739D earth digging test
  • test specimens with a wall thickness of 100 mm and a diameter of 25 mm are welded into polyethylene nets and buried in soil with 60% relative humidity.
  • the test is carried out at approx. 20 ° C.
  • the mass loss of the samples is determined at time intervals, ie the percentage loss in weight of the polyester film.
  • a test specimen is taken at every time interval, with dist. Washed water and dried in vacuo for 24 h. This removed specimen is then not used again in the burial test, but is available for analytical investigations.
  • the test was carried out with the following polymeric materials: PTA (39/61), PTA (43/57), PTS (41/57) and PTS (56/44). The results are Fig. 3 can be seen.
  • the degradability of the statistical copolyesters is checked in a composting at 60 ° C and 60% relative humidity.
  • the specimen dimensions, burials and withdrawals correspond to the earth digging.
  • the compost based on green waste comes from the post-rotting phase and was taken from the Watenbüttel composting plant (Braunschweig). The results are shown in Fig. 4.
  • the mass loss is plotted against the time (in weeks) in the diagrams.
  • the copolyesters PTA (39/61) and PTS (41/59) with lower terephthalic acid content, can no longer be isolated after 7 - 8 weeks.
  • the PTS (43/57) showed a weight loss of 14%. No weight loss in the excavation
  • Example 10 shows that there is no hydrolytic influence at room temperature in the observed period for the polyesters examined. One can speak of a microbial degradation.
  • Example 10 illustrates that the hydrolytic influence at 60 ° C. fulfills a function that supports microbial degradation. This influence is more pronounced with adipic acid as an aliphatic dicarboxylic acid component than with sebacic acid as an aliphatic dicarboxylic acid component.
  • 0.131 mol of 1,3-propanediol, 0.131 mol of DMT and 0.04 g of zinc acetate dihydrate are each condensed with 20, 50 and 100 mol% excess of 1,3-propanediol in the melt at 210 ° C. under a nitrogen atmosphere and normal pressure .
  • the oligomers are ground, washed successively with water and diethyl ether and dried in vacuo for 24 h.
  • the aromatic oligomers listed in Table 3 result.
  • the degradation of the obgomer is examined in a modified storm test.
  • the only carbon source are the PTMT oligomers.
  • 1% by volume of a compost eluate serves as the degradation culture and a mineral salt medium according to DIN 53739C serves as the nutrient source.
  • the test is carried out at 25 ° C., an air supply of approx. 2 l / h and in 100 ml of liquid volume.
  • 0.161 mol of 1,2-ethanediol, 0, 161 mol of DMT and 0.04 g of zinc acetate dihydrate are condensed with 100 mol% excess of I, 2-Ethandioiin the melt at 210 * C, under a nitrogen atmosphere and at normal pressure.
  • the oligomer is ground, washed successively with water and diethyl ether and dried in vacuo for 24 h.
  • 0.111 mol of 1, 4-butanediol, 0.111 mol DMT and 0.04 g of zinc acetate dihydrate are condensed with 100 mol% excess of i.4-Butandioiin the melt at 210 * C, under a nitrogen atmosphere and at normal pressure.
  • the oligomer is ground, washed successively with water and diethyl ether and dried in vacuo for 24 h.

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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)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne un polyester biodégradable (notamment sous forme d'un matériau), susceptible de se décomposer dans un environnement naturel sous l'influence de micro-organismes tels que spécifiés, par exemple, dans DIN 53739D ou ASTM D5338-92, caractérisé en ce qu'il est produit à partir d'un polyol aliphatique et d'un acide polycarboxylique aromatique et, en même temps, d'un acide polycarboxylique aliphatique, en tant que composants monomères, et en ce qu'il présente des motifs répétés ou récurrents structuraux formés (i) d'une part, de polyol et d'acide polycarboxylique aromatique et, (ii) d'autre part, de polyol et d'acide polycarboxylique aliphatique, plus de 90 % des motifs selon (i) n'étant directement liés à aucun autre motif ou étant directement liés au maximum à un autre motif selon (i).
PCT/EP1995/002722 1994-09-09 1995-07-12 Polyester biodegradable et materiau fabrique en un tel polyester WO1996007687A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP95944721A EP0779907A1 (fr) 1994-09-09 1995-07-12 Polyester biodegradable et materiau fabrique en un tel polyester
JP8509147A JPH10505620A (ja) 1994-09-09 1995-07-12 生物学的に分解可能なポリエステルおよび該ポリエステルからなる材料

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19944432161 DE4432161A1 (de) 1994-09-09 1994-09-09 Biologisch abbaubare Polyester-Copolymere mit aromatischen Anteilen
DEP4432161.9 1994-09-09
DE19508737A DE19508737A1 (de) 1995-03-10 1995-03-10 Biologisch abbaubarer Polyester und Werkstoff daraus
DE19508737.2 1995-03-10

Publications (1)

Publication Number Publication Date
WO1996007687A1 true WO1996007687A1 (fr) 1996-03-14

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1995/002722 WO1996007687A1 (fr) 1994-09-09 1995-07-12 Polyester biodegradable et materiau fabrique en un tel polyester

Country Status (3)

Country Link
EP (1) EP0779907A1 (fr)
JP (1) JPH10505620A (fr)
WO (1) WO1996007687A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0820698A1 (fr) * 1996-07-26 1998-01-28 Wolff Walsrode Ag Enveloppes pour saucisses étirées biaxialement, biodégradables et compostables
WO1998014414A1 (fr) * 1996-09-30 1998-04-09 Basf Aktiengesellschaft Engrais sous conditionnement pelliculaire a liberation ciblee de substances nutritives
WO2000068303A1 (fr) * 1999-05-10 2000-11-16 Basf Aktiengesellschaft Particules de mousse polyester biodegradables
EP1074604A2 (fr) 1999-08-03 2001-02-07 Basf Aktiengesellschaft Milieux biodégradables pour ameublir le sol
US6573308B1 (en) 1999-08-11 2003-06-03 Basf Aktiengesellschaft Biologically degradable foamed material particles
CN100429256C (zh) * 2004-12-30 2008-10-29 中国石油化工股份有限公司 可生物降解的线性无规共聚酯及其制备方法和应用
US8273850B2 (en) 2008-12-15 2012-09-25 E I Du Pont De Nemours And Company Polyester compositions from biologically-derived materials
US10336925B2 (en) 2015-09-08 2019-07-02 Resinate Materials Group, Inc. Polyester polyols for reactive hot-melt adhesives
US10729492B2 (en) 2009-04-21 2020-08-04 Boston Scientific Scimed Inc. Methods and devices for access across adjacent tissue layers

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002256098A (ja) * 2001-03-02 2002-09-11 Jsp Corp ポリエステル系樹脂発泡体及びその製造方法
US7888405B2 (en) * 2004-01-30 2011-02-15 E. I. Du Pont De Nemours And Company Aliphatic-aromatic polyesters, and articles made therefrom
JP2008500424A (ja) * 2004-05-25 2008-01-10 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 酵素処理によって脂肪族−芳香族コポリエステルの生分解を促進する方法
CN101146855A (zh) 2005-03-25 2008-03-19 株式会社钟化 热塑性树脂发泡粒子、其成型体及该发泡粒子的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0028687A1 (fr) * 1979-11-13 1981-05-20 Chemische Werke Hüls Ag Procédé pour préparer des polyesters linéaires de poids moléculaire élevé
WO1991002015A1 (fr) * 1989-08-08 1991-02-21 The Pennsylvania Research Corporation Polyesters hydrodegradables
EP0569143A2 (fr) * 1992-05-08 1993-11-10 Showa Highpolymer Co., Ltd. Matériaux de ficelage à base de polyester sous forme de ruban

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0028687A1 (fr) * 1979-11-13 1981-05-20 Chemische Werke Hüls Ag Procédé pour préparer des polyesters linéaires de poids moléculaire élevé
WO1991002015A1 (fr) * 1989-08-08 1991-02-21 The Pennsylvania Research Corporation Polyesters hydrodegradables
EP0569143A2 (fr) * 1992-05-08 1993-11-10 Showa Highpolymer Co., Ltd. Matériaux de ficelage à base de polyester sous forme de ruban

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0820698A1 (fr) * 1996-07-26 1998-01-28 Wolff Walsrode Ag Enveloppes pour saucisses étirées biaxialement, biodégradables et compostables
US5928739A (en) * 1996-07-26 1999-07-27 Wolff Walsrode Ag Biaxially stretched, biodegradable and compostable sausage casing
WO1998014414A1 (fr) * 1996-09-30 1998-04-09 Basf Aktiengesellschaft Engrais sous conditionnement pelliculaire a liberation ciblee de substances nutritives
WO2000068303A1 (fr) * 1999-05-10 2000-11-16 Basf Aktiengesellschaft Particules de mousse polyester biodegradables
US6458858B1 (en) 1999-05-10 2002-10-01 Basf Aktiengesellschaft Biodegradable polyester material particles
EP1074604A2 (fr) 1999-08-03 2001-02-07 Basf Aktiengesellschaft Milieux biodégradables pour ameublir le sol
EP1074604A3 (fr) * 1999-08-03 2002-07-03 Basf Aktiengesellschaft Milieux biodégradables pour ameublir le sol
US6573308B1 (en) 1999-08-11 2003-06-03 Basf Aktiengesellschaft Biologically degradable foamed material particles
CN100429256C (zh) * 2004-12-30 2008-10-29 中国石油化工股份有限公司 可生物降解的线性无规共聚酯及其制备方法和应用
US8273850B2 (en) 2008-12-15 2012-09-25 E I Du Pont De Nemours And Company Polyester compositions from biologically-derived materials
US10729492B2 (en) 2009-04-21 2020-08-04 Boston Scientific Scimed Inc. Methods and devices for access across adjacent tissue layers
US10336925B2 (en) 2015-09-08 2019-07-02 Resinate Materials Group, Inc. Polyester polyols for reactive hot-melt adhesives

Also Published As

Publication number Publication date
EP0779907A1 (fr) 1997-06-25
JPH10505620A (ja) 1998-06-02

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