CA2337469A1

CA2337469A1 - Biodegradable molding materials with high specific thickness

Info

Publication number: CA2337469A1
Application number: CA002337469A
Authority: CA
Inventors: Michael Voigt; Wolfgang Schulz-Schlitte
Original assignee: Individual
Current assignee: Bayer AG
Priority date: 1998-07-18
Filing date: 1999-07-07
Publication date: 2000-01-27
Also published as: DE19832456A1; WO2000004082A1; JP2002520467A; EP1098930A1; ZA200007767B; AU5032899A; IL140528A0

Abstract

Biodegradable molding materials containing: A) 1-55 % by weight of at least one biodegradable polymer and B) 45-99 % by weight of at least one metal and/or mineral filling material.

Description

2 PCT/EP99/04744 Biodegradable Moulding Compositions with High Sgecific Density The present invention relates to materials with a high specific density and areas of application in which lead is widely used on account of its high specific density and ductility. Of particular importance in this connection is the replacement of conventional lead shot and angling weights, which contribute to a considerable extent to contamination of the ground and water with poisonous lead compounds.
In many practical applications it is necessary to use materials having a high specific density. Lead or its alloys are normally used in such applications, which include for example projectiles, weighting fillers for bullets, shot and angling weights, in particular for deep sea fishing. Lead has for a long time been the medium of choice in the aforementioned applications on account of its high density, cheap availability and simple processability. The considerable disadvantage of lasting environmental contamination and damage was ignored or disregarded on account of the lack of ecologically and economically viable alternatives.
There have therefore been no lack of attempts in the past to develop ecologically practicable variants, as a result of which although it was indeed possible to reduce emissions - in particular to reduce lead emissions - this was offset by an increase in the proportion of non-degradable residues in the environment.
A series of applications (JP 07018170, JP 09105021, JP 08158161) describes the production of conventional thermoplastics filled with metals (e.g. stainless steel) or with minerals (e.g. barium sulfate, magnetite, titanium dioxide) with densities of 1.2 to 2 g/cm3 and their use in the extrusion and co-extrusion of monofilaments and multifilaments. Densities of this order of magnitude are however not sufficient for applications such as e.g. shot or angling weights. Materials of higher density are described in Japanese Application No. 54025950 (2.7 g/cm3) and in US Patent Specification 5,665,808 (> 7 g/cm3); however, in this case too lead is again used in a mould encapsulated by a non-degradable matrix (polyester); provided the composite arrangement is maintained the surrounding matrix should reduce corrosion by lead and contamination of the environment with poisonous lead compounds. This solution is however only an apparent solution since contamination by poisonous lead compounds persists over a very long period and is not suppressed. The aim of replacing lead is described in JP 02185540, where a density of 4.68 g/cm' is achieved with a mixture of iron powder and plasticiser powders in polyamide-6.
EP-A 0641836 describes materials with densities of 8-12 g/cm3, which are said to be achieved by filling a non-biodegradable two-component matrix consisting of thermoplastics and an elastomer, with tungsten powder. However, the mixtures disclosed in the examples have, with a degree of filling with tungsten of 67.5 wt.%, densities of only ca. 3 g/cm' and not 9.5 g/cm3 as stated. The disadvantage of these compounds is also that they do not degrade under normal environmental conditions and thus constitute a long-term contamination of the environment. In WO

lead-free formulations are described that substantially consist of two metal components and one polymer component, the polymer component being a non-biodegradable phenol formaldehyde resin or a polymethyl methacrylate. The materials described in WO 9508653 are processed into moulded parts only by compacting and sintering of powders and powder mixtures and cannot be obtained or injection moulded via a conventional extrusion process.
The claimed moulding compositions according to the invention are characterised, in contrast to the aforedescribed materials, by complete biodegradability of the matrix that is used.
It has also surprisingly been found that the injection moulding process described as having disadvantages in US-A 5665808 on account of the toughness qualities and good flow properties of the matrices that are used provides in a trouble-free manner completely filled void-free moulded parts even at pin gate sizes of < 1 mm, which parts can also be removed from the mould without any difficulty and without using further aids that might have to be applied directly to the tool. Also, in the production of granules suitable for the injection moulding, instead of the multi-stage

-3-process described in US-A 5665808 for producing granules or a powder suitable for the compacting, only a one-stage compounding process without any pretreatment of the fillers is required.
The moulding compositions according to the invention thus permit a trouble-free incorporation process and a likewise problem-free processing in conventional injection moulding machines without having to use significant amounts of processing aids. As a result of the permanent passivation of the surfaces of the filler particles that are exposed to environmental influences after the biodegradation of the matrix (for example when using tungsten) or as a result of a complete breakdown to naturally occurring, non-toxic compounds (for example when using iron), the metallic fillers or their mineral, high-density compounds that are used no longer represent a potential environmental threat.
1 S The present invention accordingly provides biodegradable moulding compositions containing A) 1- 55 wt.% of at least one biodegradable polymer, and B) 45 - 99 wt.% of at least one metallic and/or mineral filler.
The thermoplastic moulding compositions preferably have a density > 2 g/cm3, measured according to ISO 1183. Particularly preferred is a density of 2 -16 g/cm3, especially a density of S -15 g/cm3. Further preferred density ranges are 5 -7 g/cm' and 12 - 14 g/cm3.
Component A
Suitable biodegradable and compostable polymers that can be used as matrix for the high-density moulding compositions according to the invention are aliphatic or partially aromatic polyesters, thermoplastic aliphatic or partially aromatic polyester WO 00/04082 PCf/EP99/04744

-4-urethanes, aliphatic or aliphatic-aromatic polyester carbonates, and aliphatic or partially aromatic polyester amides.
The following polymers are preferred:
S
aliphatic or partially aromatic polyesters of A) aliphatic bifunctional alcohols, preferably linear CZ to C,a dihydric alcohols such as for example ethanediol, butanediol, hexanediol or, particularly preferably, butanediol, and/or optionally cycloaliphatic bifunctional alcohols, preferably with 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, tetrahydrofuran or copolymers thereof with molecular weights of up to 4000, preferably up to 1000, and/or optionally minor amounts of branched bifunctional alcohols, preferably C,-C,Z alkyl diols, such as for example neopentyl glycol, and in addition optionally minor amounts of higher functional alcohols such as for example 1,2,3-propanetriol or trimethylolpropane, as well as minor amounts of aliphatic bifunctional acids, preferably CZ-C,z alkyldicarboxylic 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 in addition optionally minor amounts of higher functional acids such as for example trimellitic acid, or of B) acid-functionalised and alcohol-functionalised building blocks, preferably with 2 to 12 C atoms in the alkyl chain, for example hydroxybutyric acid, hydroxyvaleric acid, lactic acid, or their derivatives, for example E-caprolactone or dilactide, or a mixture and/or a copolymer formed from A and B,

-5-wherein the proportion of the aromatic acids is not more than 50 wt.% referred to all acids.
S Aliphatic or partially aromatic polyester urethanes of C) aliphatic bifunctional alcohols, preferably linear CZ to C,°
dihydric alcohols such as for example ethanediol, butanediol, hexanediol, particularly preferably butanediol, and/or optionally cycloaliphatic bifunctional alcohols, preferably with a CS or C6 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 minor amounts of branched 1 S bifunctional alcohols, preferably C3-C,2 alkyl diols, such as for example neopentyl glycol, and in addition optionally minor amounts of higher functional alcohols, preferably C3 C,2 alkylpolyols, such as for example 1,2,3-propanetriol or trimethylolpropane, as well as of aliphatic bifunctional acids, preferably CZ-C,2 alkyldicarboxylic 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 in addition optionally minor amounts of higher functional acids such as for example trimellitic acid, or of D) acid-functionalised and alcohol-functionalised building blocks, preferably with 2 to 12 C atoms, for example hydroxybutyric acid, hydroxyvaleric acid, lactic acid, or their derivatives, for example E-caprolactone or dilactide, or a mixture and/or a copolymer of C and D,

-6-wherein the proportion of the aromatic acids is not more than 50 wt.% referred to all acids;
E) of the reaction product of C and/or D with aliphatic and/or cycloaliphatic bifunctional and in addition optionally higher functional isocyanates, preferably with 1 to 12 C atoms or 5 to 8 C atoms in the case of cycloaliphatic isocyanates, for example tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, optionally in addition with linear and/or branched and/or cycloaliphatic bifunctional and/or higher functional alcohols, preferably C3-C,2 alkyl diols or alkyl polyols, or with 5 to 8 C atoms in the case of cycloaliphatic alcohols, for example ethanediol, hexanediol, butanediol, cyclohexanedimethanol, and/or optionally in addition with linear and/or branched and/or cycloaliphatic bifunctional and/or higher functional amines and/or aminoalcohols with preferably 2 to 12 C atoms in the alkyl chain, for example ethylenediamine or amino ethanol, and/or optionally further modified amines or alcohols, such as for example ethylenediaminoethanesulfonic acid, as free acid or as a salt, wherein the proportion of the ester C) and/or D) is at least 75 wt.% referred to the sum of C), D) and E).
Aliphatic or aliphatic-aromatic polyester carbonates of F) aliphatic bifunctional alcohols, preferably linear CZ to C,°
dihydric alcohols such as for example ethanediol, butanediol, hexanediol or, particularly preferably, butanediol, and/or optionally cycloaliphatic bifunctional alcohols, preferably with 5 to 8 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, tetrahydrofuran or copolymers thereof with molecular weights of up to 4000, preferably up to 1000, and/or optionally minor amounts of branched bifunctional alcohols, preferably with C2-C,Z alkyldicarboxylic acids, such as for example neopentyl glycol, and in addition optionally minor amounts of higher functional alcohols such as for example 1,2,3-propanetriol, trimethylolpropane, as well as of aliphatic bifunctional 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 in addition optionally minor amounts of higher functional acids such as for example trimellitic acid, or of G) acid-functionalised and alcohol-functionalised building blocks, preferably with 2 to 12 C atoms in the alkyl chain, for example hydroxybutyric acid, hydroxyvaleric acid, lactic acid, or their derivatives, for example E-caprolactone or dilactide, 1 S or a mixture and/or a copolymer of F and G, wherein the proportion of the aromatic acids is not more than 50 wt.% referred to all acids, H) a carbonate fraction that is formed from aromatic bifunctional phenols, preferably bisphenol A, and carbonate donors, for example phosgene, or a carbonate fraction that is formed from aliphatic carbonic acid esters or their derivatives such as for example chlorocarbonic acid esters, or aliphatic carboxylic acids or their derivatives such as for example salts and carbonate donors, for example phosgene, wherein the ester fraction F) and/or G) is at least 70 wt.%, referred to the sum of F), G) and H);
aliphatic or partially aromatic polyester amides of WO 00/04082 PCf/EP99/04744 _g-I) aliphatic bifunctional alcohols, preferably linear CZ to C,°
dihydric alcohols, for example ethanediol, butanediol, hexanediol, particularly preferably butanediol, and/or optionally cycloaliphatic bifunctional alcohols, preferably with 5 to 8 C atoms, such as for example cyclohexaaedimethanol, 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 of up to 4000, preferably up to 1000, and/or optionally minor amounts of branched bifunctional alcohols, preferably C; C,2 alkyl diols, such as for example neopentyl glycol, and in addition optionally minor amounts of higher functional alcohols, preferably C,-C,z alkylpolyols, such as for example 1,2,3-propanetriol, trimethylolpropane, as well as of aliphatic bifunctional acids, preferably with 2 to 12 C atoms in the allryl chain, 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 in addition optionally minor amounts of higher functional acids such as for example trimellitic acid, or of K) acid-functionalised and alcohol-functionalised building blocks, preferably with 2 to 12 C atoms in the carbon chain, for example hydroxybutyric acid, hydroxyvaleric acid, lactic acid, or their derivatives, for example E-caprolactone or dilactide, or a mixture and/or a copolymer of I) and K), wherein the proportion of the aromatic acids is not more than 50 wt.% referred to all acids, L) an amide fraction of aliphatic and/or cycloaliphatic bifunctional and/or optionally minor amounts of branched bifunctional amines, preferably linear aliphatic CZ-C,° diamines, and in addition optionally minor amounts of higher functional amines, preferably hexamethylenediamine, isophorone diamine and particularly preferably hexamethylenediamine, as well as of linear and/or cycloaliphadc bifunctional acids, preferably with 2 to 12 C
atoms in the alkyl chain or a CS- or C6 ring in the case of cycloaliphatic acids, preferably adipic acid and/or optionally minor amounts of branched bifunctional and/or optionally aromatic bifunctional acids such as for example terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and in addition optionally minor amounts of higher functional acids, preferably with 2 to 10 C atoms, or of lVl~ an amide fraction formed from acid-functionalised and amine-functionalised building blocks, preferably with 4 to 20 C atoms in the cycloaliphatic chain, preferably w-laurinlactam, E-caprolactam, particularly preferably E
caprolactam, or a mixture of L) and IVj] as amide fraction, wherein the ester fraction >) and/or K) is at least 30 wt.% referred to the sum of )~, K), L), and 1V>7, and preferably the weight proportion of the ester structures is 30 to 70 wt.%, and the proportion of the amide structures is 70 to 30 wt.%.
All acids may also be used in the form of derivatives such as for example acid chlorides or esters, the latter being in the form of both monomeric and oligomeric esters.
The polyester amides and the further polymers are particularly preferably built up from the aforementioned, preferred and particularly preferred aliphatic acid building blocks and amine blocks and/or cycloaliphatic acid-functionalised and alcohol-functionalised and/or acid-functionalised and amine-functionalised building blocks.

Particularly preferred are polyester amides containing as alcohol component, ethanediol, butanediol, diethylene glycol or hexanediol, or a mixture thereof with at least two of the components and optionally with polyethylene glycol, and as acid component, succinic acid and/or adipic acid, and s-caprolactam and/or adipic hexamethylenediamine.
Glycerol, trimethylolpropane or pentaerythritol may preferably be used as branching agent.
The synthesis of the biodegradable polyester amides according to the invention may be carried out according to the "polyamide method" by stoichiometric mixing of the starting components, optionally with the addition of water followed by the removal of water from the reaction mixture, as well as by the "polyester method" by stoichiometric mixing of the starting components as well as the addition of an excess of diol with esterification of the acid groups and subsequent transesterification or transamidation of these esters. In the latter case water as well as the excess of diol is distilled off. The synthesis is preferably carried out according to the aforedescribed "polyester method".
The polycondensation may furthermore be accelerated by using known catalysts.
It is possible to use the known phosphorus compounds that accelerate the polyamide synthesis, as well as acidic or organometallic catalysts for the esterification, or also combinations of the two, in order to accelerate the polycondensation.
Care should be taken to ensure that the catalysts do not have an adverse effect on either the biodegradability, compostability or the quality of the resulting compost.
In addition the polycondensation to form polyester amides can be influenced by using lysine, lysine derivatives or other amidically-branching products such as for example aminoethylaminoethanol, which both accelerate the condensation and also lead to branched products (see for example DE 3831709).

The production of polyesters, polyester carbonates and polyester urethanes is generally known and is carried out in an analogous manner by known processes (see for example EP-A 304 787, WO 95/12629, WO 93/13154, EP-A 682 054, EP-A 593 975).
The polyesters, polyester urethanes, polyester carbonates or polyester amides according to the invention may in addition contain 0.1 to 5 wt.%, preferably 0.1 to 1 wt.%, of branching agents (see also the description of the polymers). These branching agents may for example be trifunctional alcohols such as trimethylolpropane or glycerol, tetrafunctional alcohols such as pentaerythritol, or trifimctional 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 moulding with these polymers is possible. The biodegradability of these materials is not thereby affected.
The biodegradable/compostable polyester urethanes, polyesters, polyester carbonates and polyester amides as a rule have a molecular weight of at least 10,000 g/mole and generally have a statistical distribution of the starting substances in the polymer. In the case of a polyurethane-type polymer structure, possibly formed from C) and D) as well as from E), a completely statistical distribution of the monomer building blocks cannot always be expected.
Component B
As high-density fillers there may for example be used iron powder, iron oxides, iron alloys (e.g. ferrotitanium, ferromolybdenum, ferromanganese) tungsten, tungsten carbide, ferrotungsten, molybdenum, manganese, cobalt, copper, zinc, tin or bismuth, or combinations thereof.

Combinations of powders with particle size ratios of 1 : > 6 permit for example higher volume filling levels to be achieved than in the case of a cubic closest packing with only one type of particle, while retaining the flowability.
The combination of various particle sizes and powders of different metals moreover permits the mechanical properties of the resultant moulded articles to be suitably adapted. In particular the brittleness of bullet cores and shot can be matched to the property profile of lead as regards inelastic deformation and brittle cracking on impact on game, or on the target in shooting ranges and rifle ranges.
The biodegradable/completely compostable polyester urethanes, polyesters, polyester carbonates and polyester amides according to the invention may contain conventional additives. Thus, modifying agents and/or fillers and reinforcing agents and/or processing aids such as for example nucleating agents, plasticisers, mould release agents, flame retardants, impact modifiers, colouring agents, stabilisers or other conventional additives used in the thermoplastics sector may be employed, in which connection it should be ensured that the complete compostability is not adversely affected or the remaining substances, for example mineral auxiliary substances, in the compost are harmless. In general up to 5 wt.%, preferably up to 3 wt.% (referred to A and B) of additives may be added.
Suitable fillers and reinforcing agents according to the invention may be minerals such as for example kaolin, chalk, gypsum, limestone or talcum, or natural materials such as for example starch or modified starch, cellulose or cellulose derivatives or cellulose products, sawdust, or natural fibres such as for example hemp, flax, sisal, rape or ramie.
The biodegradable/completely compostable polyester urethanes, polyesters, polyester carbonates and polyester amides according to the invention may also be blended with further blending partners, for example thermoplastic starch, in which connection it should be ensured that the complete compostability is not adversely affected or the remaining substances, for example mineral auxiliary substances, in the compost are harmless.
The invention furthermore provides a process for producing the moulding compositions according to the invention, wherein the components of the moulding compositions according to the invention are added to an extruder, kneader or mixer in a conventional manner via a hopper and/or ancillary screw device, the matrix is melted by applying shear forces and thermal energy and is thoroughly mixed with the fillers, and the mouldable compounding granules are thus obtained in only one extrusion or mixing step. A sinking of the fillers in the melt, which are specifically very much denser compared to the matrix, is not observed.
The invention furthermore provides for the use of the moulding compositions to produce moulded bodies, sheets, fibres, extrudates and constituents of ballistic projectiles, angling weights, angling hooks and constituents thereof, sound insulating materials, thermally conducting components for electronic equipment, structural parts and housing constituents for electromagnetic shielding of electrical equipment, electrically conducting moulded parts of arbitrary shapes, as well as magnetic moulded parts of free shape and design as well as the objects produced themselves.

Examples Ezample 1 A compound consisting of 19.6 wt.% of polyester amide (produced from 617 g of adipic acid, 487 g of adipic hexamethylenediamine, 226 g of diethylene glycol, 181 g of butanediol together with titanium tetraisopropylate as catalyst, rire, of a 1 wt.% solution in m-cresol at 20°C is 2.7), 80 wt.% of tungsten powder (technical batch W4676 from H.C. Starck GmbH & Co. KG, Goslar, Germany) and 0.4 wt.%
of Loxiol EP 728 (Henkel KGaA, Diisseldorf, Germany) is produced in a ZSK 32 double-screw extruder from Wemer & Pfleiderer and processed as granules by injection moulding. The compound has a density of 4.58 g/cm', a modulus of elasticity of 700 MPa measured in the tensile test according to ISO 527, and an elongation at break of 90%. In the Izod impact test (ISO 180/1C) the test body does not break at room temperature.
Example 2 A compound consisting of 49.6 wt.% of polyester amide according to Example 1, 50 wt.% of copper powder FFL-2 (Norddtsch. Refinery) and 0.4% of Loxiol EP 728 is produced like the compound in Example 1 and processed by injection moulding.
The material has a density of 2.04 g/cm3, a modulus of elasticity of 680 MPa and an elongation at break of 49%. In the Izod impact test the test body does not break at room temperature.
Ezample 3 A compound consisting of 9 wt.% of polyester amide according to Example 1 and 91 wt.% of iron powder MPD 2002 (Mannesmann Demag AG) is produced and processed as described in Examples 1 and 2.

The material has a density of 5.08 g/cm', a modulus of elasticity of 2870 MPa, an elongation at break of 1.4%, and an impact strength of 16 kJ/mz.
Ezample 4 A density of 12.9 g/cm' is achieved with a compound consisting of 3 wt.% of polyester amide according to Example 1 and 97 wt.% of tungsten powder (technical batch W4676 from H.C. Starck GmbH & Co. KG, Goslar, Germany). The material has a modulus of elasticity of 2730 MPa, an elongation at break of 3.8%, and an impact strength of 17 kJ/m2.

Claims

Patent Claims

1. Biodegradable moulding compositions containing:

A) 1 - 55 wt.% of at least one biodegradable polymer, and B) 45 - 99 wt.% of at least one metallic and/or mineral filler.

2. Moulding compositions according to claim 1, wherein the biodegradable polymers are selected from the group comprising aliphatic or partially aromatic polyesters, thermoplastic aliphatic or partially aromatic polyester urethanes, aliphatic or aliphatic-aromatic polyester carbonates, and aliphatic or partially aromatic polyester amides.

3. Moulding composition according to claim 1, wherein the biodegradable polymer is selected from the following groups:

aliphatic or partially aromatic polyesters containing A) aliphatic bifunctional alcohols and/or optionally cycloaliphatic bifunctional alcohols 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 of up to 4000 and/or optionally minor amounts of branched bifunctional alcohols and in addition optionally minor amounts of higher functional alcohols as well as aliphatic bifunctional acids and/or optionally aromatic bifimctional acids and in addition optionally minor amounts of higher functional acids, or B) acid-functionalised and alcohol-functionalised building blocks, or a mixture and/or a copolymer formed from A and B, wherein the proportion of the aromatic acids is not more than 50 wt.%
referred to all acids;

aliphatic or partially aromatic polyester urethanes containing C) aliphatic bifunctional alcohols, and/or optionally cycloaliphatic bifunctional alcohols, 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 and/or optionally minor amounts of branched bifunctional alcohols and in addition optionally minor amounts of higher functional alcohols as well as of aliphatic bifunctional acids and/or optionally aromatic bifunctional acids and in addition optionally minor amounts of higher functional acids or D) acid-functionalised and alcohol-functionalised building blocks, or a mixture and/or a copolymer of C and D, wherein the proportion of the aromatic acids is not more than 50 wt.%
referred to all acids;

E) of the reaction product of C and/or D with aliphatic and/or cycloaliphatic bifunctional and in addition optionally higher functional isocyanates, optionally in addition with linear and/or branched and/or cycloaliphatic bifunctional and/or higher functional alcohols and/or optionally in addition with linear and/or branched and/or cycloaliphatic bifunctional and/or higher functional amines and/or aminoalcohols and/or optionally further modified amines or alcohols, wherein the proportion of the ester C) and/or D) is at least 75 wt.% referred to the sum of C), D) and E);

aliphatic or aliphatic-aromatic polyester carbonates containing F) aliphatic bifunctional alcohols and/or optionally cycloaliphatic bifunctional alcohols 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 of up to 4000 and/or optionally minor amounts of branched bifunctional alcohols and in addition optionally minor amounts of higher functional alcohols, as well as aliphatic bifunctional acids and/or optionally aromatic bifunctional acids and in addition optionally minor amounts of higher functional acids or G) acid-functionalised and alcohol-functionalised building blocks, or a mixture and/or a copolymer of F and G, wherein the proportion of the aromatic acids is not more than 50 wt.%
referred to all acids, H) a carbonate fraction that is obtained from aromatic bifunctional phenols and carbonate donors, or a carbonate fraction that is formed from aliphatic carbonic acid esters or their derivatives or aliphatic carboxylic acids or their derivatives and carbonate donors wherein the ester fraction F) and/or G) is at least 70 wt.%, referred to the sum of F), G) and H);

aliphatic or partially aromatic polyester amides containing I) aliphatic bifunctional alcohols and/or optionally cycloaliphatic bifunctional alcohols 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 of up to 4000 and/or optionally minor amounts of branched bifunctional alcohols, and in addition optionally minor amounts of higher functional alcohols as well as of aliphatic bifunctional acids and/or optionally aromatic bifunctional acids and in addition optionally minor amounts of higher functional acids or K) acid-functionalised and alcohol-functionalised building blocks, or a mixture and/or a copolymer formed of I) and K), wherein the proportion of the aromatic acids is not more than 50 wt.%
referred to all acids, L) an amide fraction of aliphatic and/or cycloaliphatic bifunctional and/or optionally minor amounts of branched bifunctional amines, and in addition optionally minor amounts of higher functional amines as well as of linear and/or cycloaliphatic bifunctional acids and/or optionally minor amounts of branched bifunctional and/or optionally aromatic bifunctional acids and in addition optionally minor amounts of higher functional acids, or M) an amide fraction formed from acid-functionalised and amine-functionalised building blocks, or a mixture of L) and M) as amide fraction, wherein the ester fraction I) and/or K) is at least 30 wt.% referred to the sum of I), K), L) and M).

4. Moulding composition according to claim 3, wherein the biodegradable polymer is selected from the following groups:

aliphatic or partially aromatic polyesters containing A) aliphatic linear C2 to C10 dihydric alcohols and/or optionally cycloaliphatic bifunctional alcohols, preferably with 5 or 6 C atoms in the cycloaliphatic ring 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 of 4000, and/or optionally minor amounts of branched C3-C12 alkyl diols and in addition optionally minor amounts of higher functional alcohols, as well as C2-C12 alkyldicarboxylic acids and/or optionally aromatic bifunctional acids selected from terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and in addition optionally minor amounts of higher functional acids, or B) acid-functionalised and alcohol-functionalised building blocks with 2 to 12 C atoms in the alkyl chain, or a mixture and/or a copolymer formed from A and B, wherein the proportion of the aromatic acids is not more than 50 wt.%
referred to all acids;

aliphatic or partially aromatic polyester urethanes containing C) aliphatic linear C2 to C10 dihydric alcohols and/or optionally cycloaliphatic bifunctional alcohols with a C5 or C6 cycloaliphatic ring 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, and/or optionally minor amounts of branched C3-C12 alkyl diols and in addition optionally minor amounts of C3-C12 alkylpolyols as well as of aliphatic C2-C12 alkyldicarboxylic acids and/or optionally aromatic bifunctional acids selected from terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and in addition optionally minor amounts of higher functional acids or D) acid-functionalised and alcohol-functionalised building blocks with 2 to 12 C atoms, or a mixture and/or a copolymer of C and D, wherein the proportion of the aromatic acids is not more than 50 wt.%
referred to all acids;

E) of the reaction product of C and/or D with aliphatic and/or cycloaliphatic bifunctional and in addition optionally higher functional isocyanates, preferably with 1 to 12 C atoms or 5 to 8 C
atoms in the case of cycloaliphatic isocyanates, optionally in addition with linear and/or branched and/or cycloaliphatic bifunctional C2-C12 alkyl diols or alkyl polyols, or with 5 to 8 C atoms in the case of cycloaliphatic alcohols and/or optionally in addition with linear and/or branched and/or cycloaliphatic bifunctional and/or higher functional amines and/or aminoalcohols with 2 to 12 C atoms in the alkyl chain and/or optionally further modified amines or alcohols, wherein the proportion of the ester C) and/or D) is at least 75 wt.% referred to the sum of C), D) and E);

aliphatic or aliphatic-aromatic polyester carbonates containing F) aliphatic linear C2 to C10 dihydric alcohols and/or optionally cycloaliphatic bifunctional alcohols with 5 to 8 C atoms in the cycloaliphatic ring 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 of up to 4000 and/or optionally minor amounts of branched C2-C12 alkyldicarboxylic acids and in addition optionally minor amounts of higher functional alcohols as well as aliphatic bifunctional acids selected from succinic acid, adipic acid and/or optionally aromatic bifunctional acids selected from terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and in addition optionally minor amounts of higher functional acids, or G) acid-functionalised and alcohol-functionalised building blocks with 2 to 12 C atoms in the alkyl chain, or a mixture and/or a copolymer of F and G, wherein the proportion of the aromatic acids is not more than 50 wt.%
referred to all acids, H) a carbonate fraction that is obtained from bisphenol A and carbonate donors, or a carbonate fraction that is obtained from aliphatic carbonic acid esters or their derivatives or aliphatic carboxylic acids or their derivatives such as for example salts and carbonate donors, wherein the ester fraction F) and/or G) is at least 70 wt.%, referred to the sum of F), G) and H);

aliphatic or partially aromatic polyester amides containing I) aliphatic linear C2 to C10 dihydric alcohols and/or optionally cycloaliphatic bifunctional alcohols with 5 to 8 C atoms 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 of up to 4000 and/or optionally minor amounts of branched C3-C12 alkyl diols and in addition optionally minor amounts of C3-C12 alkylpolyols as well as of aliphatic bifunctional acids with 2 to 12 C atoms in the alkyl chain and/or optionally aromatic bifunctional acids selected from terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and in addition optionally minor amounts of higher functional acids or K) acid-functionalised and alcohol-functionalised building blocks with 2 to 12 C atoms in the carbon chain, or a mixture and/or a copolymer formed of I) and K), wherein the proportion of the aromatic acids is not more than 50 wt.%
referred to all acids, L) an amide fraction of aliphatic and/or optionally minor amounts of branched C2-C10 diamines and in addition optionally minor amounts of higher functional amines as well as of linear and/or cycloaliphatic bifunctional acids with 2 to 12 C atoms in the alkyl chain or a C5- or C6- ring in the case of cycloaliphatic acids and/or optionally minor amounts of branched bifunctional and/or optionally aromatic bifunctional acids selected from terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and in addition optionally minor amounts of higher functional acids with 2 to 10 C atoms, or M) an amide fraction formed from acid-functionalised and amine-functionalised building blocks with 4 to 20 C atoms in the cycloaliphatic chain, or a mixture of L) and M) as amide fraction, wherein the ester fraction I) and/or K) is 30 to 70 wt.% and the fraction of the amide structures is 70 to 30 wt.%. referred to the sum of I), K), L) and M).

5. Moulding composition according to claim 4, wherein the biodegradable polymer is selected from the following groups aliphatic or partially aromatic polyesters containing A) ethanediol, butanediol, hexanediol and/or 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 of up to 1000 and/or optionally minor amounts of branched bifunctional C3-C12 alkyl diols and in addition optionally minor amounts of higher functional alcohols selected from 1,2,3-propanetriol or trimethylol-propane as well as succinic acid or adipic acid and/or optionally aromatic bifunctional acids selected from terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and in addition optionally minor amounts of higher functional acids or B) acid-functionalised and alcohol-functionalised building blocks selected from hydroxybutyric acid, hydroxyvaleric acid, lactic acid, .epsilon.
-caprolactone, dilactide, or mixtures thereof, or a mixture and/or a copolymer formed from A and B, wherein the proportion of the aromatic acids is not more than 50 wt.%
referred to all acids;

aliphatic or partially aromatic polyester urethanes containing C) aliphatic bifunctional alcohols, selected from ethanediol, butanediol, hexanediol and/or 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 1000, and/or optionally minor amounts of branched C3-C12 alkyl diols and in addition optionally minor amounts of C3-C12 alkyldiols as well as aliphatic bifunctional acids, selected from succinic acid and adipic acid and/or optionally aromatic bifunctional acids selected from terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and in addition optionally minor amounts of higher functional acids or D) acid-functionalised and alcohol-functionalised building blocks, selected from hydroxybutyric acid, hydroxyvaleric acid, lactic acid, .epsilon.
-caprolactone, dilactide, or mixtures thereof or a mixture and/or a copolymer of C and D, wherein the proportion of the aromatic acids is not more than 50 wt.%
referred to all acids;

E) of the reaction product of C and/or D with aliphatic and/or cycloaliphatic bifunctional and in addition optionally higher functional isocyanates, selected from tetramethylene diisocyanate, hexamethylene diisocyanate and/or isophorone diisocyanate, optionally in addition with linear and/or branched and/or cycloaliphatic bifunctional and/or higher functional alcohols, selected from ethanediol, hexanediol, butanediol and/or cyclohexanedi-methanol, and/or optionally in addition with linear and/or branched and/or cycloaliphatic bifunctional and/or higher functional amines and/or aminoalcohols selected from ethylenediamine or amino ethanol and/or optionally ethylenediaminoethanesulfonic acid, as free acid or as a salt, wherein the proportion of the ester C) and/or D) is at least 75 wt.% referred to the sum of C), D) and E);

aliphatic or aliphatic-aromatic polyester carbonates containing F) cycloaliphatic bifunctional alcohols, selected from ethanediol, butanediol, hexanediol and cyclohexanedimethanol, or mixtures thereof 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 of up to 1000 and/or optionally minor amounts of branched C2-C12 alkyldicarboxylic acids and in addition optionally minor amounts of higher functional alcohols selected from 1,2,3-propanetriol and trimethylolpropane as well as aliphatic bifunctional acids selected from succinic acid, adipic acid and/or optionally aromatic bifunctional acids selected from terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and in addition optionally minor amounts of higher functional acids or G) acid-functionalised and alcohol-functionalised building blocks, selected from hydroxybutyric acid, hydroxyvaleric acid, lactic acid, E
-caprolactone, dilactide, or mixtures thereof or a mixture and/or a copolymer of F and G, wherein the proportion of the aromatic acids is not more than 50 wt.%
referred to all acids, H) a carbonate fraction that is obtained from bisphenol A and carbonate donors, or a carbonate fraction that is obtained from aliphatic carbonic acid esters or their derivatives or aliphatic carboxylic acids or their derivatives and carbonate donors, wherein the ester fraction F) and/or G) is at least 70 wt.%, referred to the sum of F), G) and H;

aliphatic or partially aromatic polyester amides containing I) aliphatic bifunctional alcohols, selected from ethanol, butanediol, hexanediol and/or 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 of up to 1000 and/or optionally minor amounts of branched C3-C13 alkyl diols and in addition optionally minor amounts of higher functional C3-C12 alkylpolyols as well as of aliphatic bifunctional acids, selected from succinic acid and adipic acid and/or optionally aromatic bifunctional acids selected from terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid and in addition optionally minor amounts of higher functional acids or K) acid-functionalised and alcohol-functionalised building blocks, selected from hydroxybutyric acid, hydroxyvaleric acid, lactic acid, .epsilon.
-caprolactone, dilactide, or mixtures thereof or a mixture and/or a copolymer formed of I) and K), wherein the proportion of the aromatic acids is not more than 50 wt.%
referred to all acids, L) an amide fraction of amines, selected from hexamethylenediamine and/or isophorone diamine and adipic acid and/or optionally minor amounts of branched bifunctional and/or optionally aromatic bifunctional acids selected from terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid and in addition optionally minor amounts of higher functional acids with 2 to 10 C atoms, or M) an amide fraction formed from acid-functionalised and amine-functionalised building blocks, selected from .omega.-laurinlactam and .epsilon.-caprolactam, or mixtures thereof.

6. Moulding compositions according to one or more of the preceding claims whose metallic or mineral filler has a density > 4 g/cm3.

7. Moulding compositions according to claim 6, whose filler is iron, tungsten, molybdenum or an alloy of the latter and further metals, or is a mineral of natural or synthetic origin containing the latter.

8. Moulding compositions according to one or more of the preceding claims with a density of >2 g/cm3.

9. Moulding compositions according to claim 8 with a density of 2 to 16 g/cm3.

14. Moulding compositions according to one or more of the preceding claims, wherein the polymer is a polyester amide.

11. Use of the moulding compositions according to one or more of the preceding claims for producing moulded bodies, sheets, fibres and extrudates.

12. Use of the moulding compositions according to one or more of the preceding claims for producing constituents of ballistic projectiles, angling weights, angling hooks and constituents thereof, sound insulating materials, thermally conducting components for electronic equipment, structural components and housing constituents for electromagnetic shielding of electrical equipment, electrically conducting moulded parts of arbitrary shape, as well as magnetic moulded parts of free shape and design.

13. Moulded bodies, sheets, fibres and extrudates which can be obtained from moulding compositions according to one or more of the preceding claims.