WO2001094468A2 - Matiere de moulage biodegradable tres coulante, son mode de production et son utilisation - Google Patents

Matiere de moulage biodegradable tres coulante, son mode de production et son utilisation Download PDF

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Publication number
WO2001094468A2
WO2001094468A2 PCT/EP2001/005967 EP0105967W WO0194468A2 WO 2001094468 A2 WO2001094468 A2 WO 2001094468A2 EP 0105967 W EP0105967 W EP 0105967W WO 0194468 A2 WO0194468 A2 WO 0194468A2
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WO
WIPO (PCT)
Prior art keywords
acid
acids
bifunctional
aliphatic
optionally
Prior art date
Application number
PCT/EP2001/005967
Other languages
German (de)
English (en)
Other versions
WO2001094468A3 (fr
Inventor
Michael Voigt
Ralf Timmermann
Kurt Jeschke
Wolfgang Schulz-Schlitte
Original Assignee
Bayer Aktiengesellschaft
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 Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to AU2001274067A priority Critical patent/AU2001274067A1/en
Publication of WO2001094468A2 publication Critical patent/WO2001094468A2/fr
Publication of WO2001094468A3 publication Critical patent/WO2001094468A3/fr

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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
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/12—Polyester-amides
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/44—Polyester-amides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C08L69/005—Polyester-carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0059—Degradable
    • B29K2995/006—Bio-degradable, e.g. bioabsorbable, bioresorbable or bioerodible

Definitions

  • Biodegradable molding compound with very good flowability as well as its production and use
  • the invention relates to biodegradable molding composition with very good flow properties and to the production and use thereof.
  • Biodegradable plastics are already known in a wide variety. There are approaches based on renewable raw materials (WO-A 9407940, WO-A 9923161, JP-A 07206773) as well as approaches based on synthetic raw materials in petrochemicals (WO-A 9615173, WO-A 9615174, WO-A 9615175,
  • the present invention therefore describes biodegradable molding compositions, the stiffness of which is increased by the addition of special mineral fillers with a light intrinsic color such that, for example, practical, disposable cutlery in white coloring can be produced from them by injection molding. Furthermore, the invention describes biodegradable molding compositions with which very large flow path / wall thickness ratios are achieved in the injection molding process.
  • the filling pressure can be used as a practice-relevant parameter for determining the flowability of plastic melts (S. Anders, K. Salewski, R. Steinbüchel, L. Rupprecht, Kunststoffe 81, 336 (1991)).
  • the melt index (MFI) and the volume flow index (MVR) are not very suitable for characterizing the flowability of plastic melts under practical conditions, since the measurements of MFI and MVR are usually carried out at shear rates of 1 to 10 1 / s and thus do not include the area in which a possible structural viscosity affects.
  • both viscosity functions obtained under analytical conditions on the viscometer and the determinations of the filling pressures during the real process of specimen production on the injection molding machine can be used.
  • molding compounds that can be used to achieve comparable processing properties in fields of application, such as thin-walled plant pots, as with materials already established in these applications, such as polypropylene or polystyrene.
  • Matrix-filler combinations based on biodegradable polymers, preferably polyester amides, with mineral fillers or fillers of natural origin have now been found, which have a pronounced structural viscosity. Due to their excellent flowability, the materials are particularly suitable for the production of thin-walled molded parts using the injection molding process.
  • the application relates to biodegradable molding compositions containing 20 to 100 parts by weight, preferably 50 to 80 parts by weight, of one or more biodegradable polymers (A) and 0 to 80 parts by weight, preferably 20 to 50 parts by weight.
  • biodegradable molding compositions containing at least one biodegradable polymer (A) are preferred for thin-wall technology, preferably selected from:
  • aliphatic bifunctional alcohols preferably linear C 2 to C 10 dialcohols such as, for example, ethanediol, butanediol, hexanediol or particularly preferably butanediol and / or optionally cycloaliphatic bifunctional alcohols, preferably having 5 or 6 C atoms in the cycloaliphatic ring, such as, for example, cyclohexanedimethanol, and / or partially or completely instead of the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofura or copolymers thereof
  • acid- and alcohol-functionalized building blocks preferably with 2 to 12 carbon atoms in the alkyl chain, for example hydroxybutyric acid, hydroxyvaleric acid, lactic acid, or their derivatives, for example ⁇ -caprolactone or dilactide,
  • aromatic acids making up no more than 50% by weight, based on all acids.
  • aliphatic bifunctional alcohols preferably linear C 2 to C 10 dialcohols such as, for example, ethanediol, butanediol, hexanediol, particularly preferably butanediol and / or optionally cycloaliphatic bifunctional alcohols, preferably with a C 5 - or C 6 -cycloaliphatic ring, such as, for example, cyclohexanedimethanol, and / or partially or completely, instead of the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights up to 4000, preferably up to 1000, and / or optionally low
  • Amounts of branched bifunctional alcohols preferably C 3 -C 12 alkyl diols, such as neopentyl glycol, and additionally optionally small amounts of higher-functional alcohols, preferably C 3 -C 12 alkyl polyols, such as 1,2,3-propanetriol or trimethylol propane, and from aliphatic bifunctional acids, preferably C 2 -C 12 alkyl dicar - Bonic acids, such as, for example, and preferably succinic acid, adipic acid, and / or optionally aromatic bifunctional acids, such as, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and, if appropriate, small amounts of higher-functional acids, such as trimellitic acid or
  • acid- and alcohol-functionalized building blocks preferably with 2 to 12 carbon atoms, for example hydroxybutyric acid, hydroxyvaleric acid, lactic acid, or their derivatives, for example ⁇ -caprolactone or dilactide,
  • aromatic acids making up no more than 50% by weight, based on all acids
  • ester fraction c) and / or d) is at least 75% by weight, based on the sum of c), d) and e).
  • aliphatic bifunctional alcohols preferably linear C 2 to C 10 dialcohols such as, for example, ethanediol, butanediol, hexanediol or particularly preferably butanediol and / or optionally cycloaliphatic bifunctional alcohols, preferably having 5 to 8 carbon atoms in the cycloaliphatic ring, such as, for example Cyclohexanedimethanol, and / or partially or completely instead of the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights up to 4000, preferably up to 1000, and / or optionally small amounts of branched bifunctional alcohols, preferably with C 2 -C 12 alkyl dicarboxylic acids, such as neopentyl glycol and additionally, if appropriate, small amounts of higher functional alcohols such as 1,
  • acid- and alcohol-functionalized building blocks preferably with 2 to 12 carbon atoms in the alkyl chain, for example hydroxybutyric acid, Hydroxyvaleric acid, lactic acid, or their derivatives, for example ⁇ -caprolactone or dilactide,
  • aromatic acids making up no more than 50% by weight, based on all acids
  • ester fraction f) and / or g) is at least 70% by weight, based on the sum of f), g) and h);
  • aliphatic bifunctional alcohols preferably linear C 2 to C 10 -
  • Dialcohols such as ethanediol, butanediol, hexanediol, particularly preferably butanediol, and / or optionally cycloaliphatic bifunctional alcohols, preferably having 5 to 8 carbon atoms, such as cyclohexanedimethanol, and / or partially or completely instead of the diols, monomeric or oligomeric polyols based on ethylene glycol , Propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights up to 4000, preferably up to 1000, and / or optionally small amounts of branched bifunctional alcohols, preferably C 3 -C 12 alkyldiols, such as as neopentyl glycol and, if necessary, small amounts of higher functional alcohols, preferably C 3 -C 12 alkyl polyols, such as 1,2,3-propanetriol, trimethylolpropane, and
  • acid- and alcohol-functionalized building blocks preferably with 2 to 12 carbon atoms in the carbon chain, for example hydroxybutyric acid, hydroxyvaleric acid, lactic acid, or their derivatives, for example ⁇ -caprolactone or dilactide,
  • aromatic acids making up no more than 50% by weight, based on all acids
  • an amide portion of aliphatic and / or cycloaliphatic bifunctional and / or optionally small amounts of branched bifunctional amines linear aliphatic C 2 to C 10 diamines are preferred, and additionally optionally small amounts of higher functional amines, among the amines preferably hexamethylenediamine, isophoronediamine and particularly preferably hexamethylenediamine, and also branched from linear and / or cycloaliphatic bifunctional acids, preferably with 2 to 12 carbon atoms in the alkyl chain or C 5 - or C 6 ring in the case of cycloaliphatic acids, preferably adipic acid, and / or small amounts bifunctional and / or optionally aromatic bifunctional acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and in addition, if appropriate, small amounts of higher-functional acids, preferably having 2 to 10 carbon atoms, or
  • the ester fraction i) and / or k) is at least 30% by weight, based on the sum of i), k), 1) and m), preferably the weight fraction of the ester structures is 30 to 70% by weight, the fraction of Amide structures is 70 to 30 wt .-%
  • acids can also be used in the form of derivatives such as acid chlorides or esters, both as monomeric and as oligomeric esters;
  • the synthesis of the biodegradable polyesteramides according to the invention can be carried out either by the "polyamide method” by stoichiometric mixing of the starting components, if appropriate with the addition of water and subsequent removal of water from the reaction mixture, or by the “polyester method” by stoichiometric mixing of the starting components and addition an excess of diol with esterification of the acid groups and subsequent transesterification or transamidation of these esters. In this second case, the excess diol is distilled off in addition to water.
  • the synthesis according to the described "polyester method” is preferred.
  • the polycondensation can be further accelerated by using known catalysts. Both the known phosphorus compounds, which accelerate the polyamide synthesis, and acidic or organometallic catalysts for the esterification, as well as combinations of the two, are used to accelerate the known catalysts. Both the known phosphorus compounds, which accelerate the polyamide synthesis, and acidic or organometallic catalysts for the esterification, as well as combinations of the two, are used to accelerate the known catalysts. Both the known phosphorus compounds, which accelerate the polyamide synthesis, and acidic or organometallic catalysts for the esterification, as well as combinations of the two, are used to accelerate the
  • Lysine lysine derivatives or other amidically branching products such as, for example, aminoethylaminoethanol, which both accelerate the condensation and lead to branched products (see, for example, DE-A 3831709).
  • polyesters, polyester carbonates and polyester urethanes are generally known or is carried out analogously by known processes (cf. for example EP-A 304 787, WO-A 95/12629, WO-A 93/13154, EP-A 682 054, EP -A 593 975).
  • the polyesters, polyester urethanes, polyester carbonates or polyester amides according to the invention can further contain 0.1 to 5% by weight, preferably 0.1 to 1% by weight, of branching agents (cf. also description of the polymers).
  • branching agents can e.g. trifunctional alcohols such as trimethylolpropane or glycerin, tetta-functional alcohols such as pentaerythritol, trifunctional carboxylic acids such as citric acid.
  • the branching agents increase the melt viscosity of the polyester amides according to the invention to such an extent that extrusion blow molding with these polymers is possible.
  • the biodegradable / compostable polyester urethanes, polyesters, polyester carbonates and polyester amides generally have a molecular weight of at least 10,000 g / mol and generally have a statistical distribution of the starting materials in the polymer. In the case of a typical polymer structure, possibly from c) and d) and from e), a completely statistical distribution of the monomer units is not always to be expected. Polyester amides are preferred. An aliphatic polyesteramide with an average molecular weight of 20,000 ⁇ M w ⁇ 100,000, preferably 30,000 ⁇ M w ⁇ 7,000 (as determined via GPC scattered light coupling) is particularly preferred.
  • Filler (B) and its adaptation to the matrix by surface modification.
  • Silicate minerals with a strongly anisotropic morphology have proven to be particularly suitable; mica, talc, wollastonite and kaolin or combinations of these silicate types are preferred, mica is particularly preferred, in particular those of the phlogopite series and wollastonite and combinations of the two.
  • mechanical property levels can be achieved with polyester amides, which are comparable to those of conventional polypropylene and unreinforced polystyrene types.
  • native or modified, renewable raw materials (C) can be used as fillers and modifiers.
  • Products which contain undigested polysaccharides are preferred with regard to the good flowability.
  • undigested polysaccharides such as starch or cellulose
  • examples of this are native flour or milling products from agricultural residues, such as Olive kernel flour or walnut shell flour.
  • chemically modified digested polysaccharides such as e.g. Cellulose or starch derivatives.
  • flow aids (D) has proven itself, which have no negative impact on the mechanical properties, for example due to softening or embrittlement.
  • Waxes and / or water Waxes and / or water.
  • low-migration ester and amide waxes and, on the other hand, low-migration silicones are preferred.
  • additives (E) from the group of stabilizers (hydrolysis, UV / light, antimicrobial), the mold release agents, the Nucleating agents, antiblocking agents, colorants, tolerance improvers and plasticizers are used.
  • melt viscosities at temperatures of 110 to 260 ° C preferably from 130 to
  • the biodegradable, structurally viscous molding compositions according to the invention can be produced by a process which is characterized in that the polymeric matrix is heated above its melting point and by mechanical mixing on a single- or multi-screw extruder, on a kneader, preferably according to Buss, a dispersion kneader, a stamp kneader or a roller mixer is mixed intensively with the fillers and additives and discharged and granulated continuously or discontinuously.
  • the molding compositions according to the invention are used for the production of moldings by the injection molding process, preferably for the production of thin-walled moldings with wall thicknesses from 2 mm to 0.01 mm, preferably from 1 mm to 0.05 mm and particularly preferably from 0.8 mm to 0.1 mm, used.
  • molded parts that can be produced particularly advantageously from the molding compositions according to the invention are plant pots, disposable cutlery, housing components, foam bodies with film hinges and packaging. example 1
  • Polyester amides produced by the polyester process from AH salt, adipic acid, butanediol, diethylene glycol and a branching agent ( ⁇ 1% by weight), with an ester / amide ratio of 60/40 and an M w of 58,600 g / mol ( determined via GPC scattered light coupling), 20% by weight of Kemira Mica 40S mica and 0.8% by weight of Loxiol EP 728 is produced on a twin-screw extruder and then processed into test specimens.
  • the filling pressure found in the production of standard tensile bars at a melt temperature of 190 ° C and a mold temperature of 50 ° C is 132 bar.
  • the flow path / wall thickness ratio that can be achieved at an injection pressure of 1500 bar is 320. At an injection pressure of 640 bar, a flow path
  • the filling pressure found in the production of standard tensile bars at a melt temperature of 190 ° C and a mold temperature of 50 ° C is 149 bar.
  • the shear viscosities found in the rheometer indicate a pronounced structural viscosity:

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Materials For Medical Uses (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

L'invention concerne des matières de moulage biodégradables très fluides, leur mode de production et leur utilisation.
PCT/EP2001/005967 2000-06-06 2001-05-25 Matiere de moulage biodegradable tres coulante, son mode de production et son utilisation WO2001094468A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001274067A AU2001274067A1 (en) 2000-06-06 2001-05-25 Biodegradable molding materials exhibiting very good flowability and the production and use thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10027905.8 2000-06-06
DE2000127905 DE10027905A1 (de) 2000-06-06 2000-06-06 Biologisch abbaubare Formmassen mit sehr guter Fließfähigkeit sowie deren Herstellung und Verwendung

Publications (2)

Publication Number Publication Date
WO2001094468A2 true WO2001094468A2 (fr) 2001-12-13
WO2001094468A3 WO2001094468A3 (fr) 2002-05-02

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AU (1) AU2001274067A1 (fr)
DE (1) DE10027905A1 (fr)
WO (1) WO2001094468A2 (fr)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0569149A2 (fr) * 1992-05-08 1993-11-10 Showa Highpolymer Co., Ltd. Articles en polyester moulés par injection
EP0596437A2 (fr) * 1992-11-06 1994-05-11 Bio-tec Biologische Naturverpackungen GmbH Mélange de polymères biodégradable
DE4418634A1 (de) * 1993-09-14 1995-03-16 Fujitsu Ltd Aus bioabbaubarem Harz geformter Artikel
WO1996006886A1 (fr) * 1994-08-27 1996-03-07 Metraplast H. Jung Gmbh Materiau biodegradable a base de matieres premieres regenerees et son procede de fabrication
WO1996031561A1 (fr) * 1995-04-07 1996-10-10 Biotec Biologische Naturverpackungen Gmbh Melange polymere biodegradable
EP0765911A2 (fr) * 1995-09-26 1997-04-02 Bayer Ag Matières plastiques biodégradables renforcées
WO1999028371A1 (fr) * 1997-12-03 1999-06-10 Bayer Aktiengesellschaft Polyetheresteramides
WO1999035179A1 (fr) * 1998-01-10 1999-07-15 Bayer Aktiengesellschaft Polyesteramides biodegradables a segments polyesters et polyamides en blocs
WO1999042514A1 (fr) * 1998-02-19 1999-08-26 Bayer Aktiengesellschaft Polyesteramides biodegradables a structures aromatiques aliphatiques

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08244781A (ja) * 1995-03-03 1996-09-24 Toppan Printing Co Ltd 容器及び容器の製造方法並びにプリフォーム

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0569149A2 (fr) * 1992-05-08 1993-11-10 Showa Highpolymer Co., Ltd. Articles en polyester moulés par injection
EP0596437A2 (fr) * 1992-11-06 1994-05-11 Bio-tec Biologische Naturverpackungen GmbH Mélange de polymères biodégradable
DE4418634A1 (de) * 1993-09-14 1995-03-16 Fujitsu Ltd Aus bioabbaubarem Harz geformter Artikel
WO1996006886A1 (fr) * 1994-08-27 1996-03-07 Metraplast H. Jung Gmbh Materiau biodegradable a base de matieres premieres regenerees et son procede de fabrication
WO1996031561A1 (fr) * 1995-04-07 1996-10-10 Biotec Biologische Naturverpackungen Gmbh Melange polymere biodegradable
EP0765911A2 (fr) * 1995-09-26 1997-04-02 Bayer Ag Matières plastiques biodégradables renforcées
WO1999028371A1 (fr) * 1997-12-03 1999-06-10 Bayer Aktiengesellschaft Polyetheresteramides
WO1999035179A1 (fr) * 1998-01-10 1999-07-15 Bayer Aktiengesellschaft Polyesteramides biodegradables a segments polyesters et polyamides en blocs
WO1999042514A1 (fr) * 1998-02-19 1999-08-26 Bayer Aktiengesellschaft Polyesteramides biodegradables a structures aromatiques aliphatiques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch, Week 199701 Derwent Publications Ltd., London, GB; Class A14, AN 1997-002074 XP002178077 & JP 08 244781 A (TOPPAN PRINTING CO LTD), 24. September 1996 (1996-09-24) *

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DE10027905A1 (de) 2001-12-13
AU2001274067A1 (en) 2001-12-17
WO2001094468A3 (fr) 2002-05-02

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