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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0058—Biocides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
• • 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
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
  • C08L69/005—Polyester-carbonates

Definitions

• the present invention relates to thermoplastic molding compositions stabilized against hydrolytic and microbial degradation from biodegradable polymers, a process for the production of concentrates based on thermoplastic biodegradable polymers, a process for the production of hydrolysis-stabilized and antimicrobial or microbistatic thermoplastic, biodegradable molding compositions and the use of Molding compositions stabilized according to the invention as biodegradable materials for the production of semi-finished products, films, injection molded parts, mono- and multifilaments. Fibers. Nonwovens and fabrics as well as the moldings or semi-finished products, foils, injection molded parts, mono- and multifilaments, fibers, nonwovens and fabrics themselves.
• Biodegradable plastics are known (see for example EP-A 561 224,
• biodegradable materials are generally accessible to a hydrolytic degradation mechanism that not only in the presence of microorganisms living in the soil, water and compost, but also at a slow to moderate speed in the presence of moisture during the storage of the granules and during their use manufactured products expires.
• the object of the present invention is to control this premature degradation and loss of material properties and, in particular, to slow it down, without adversely affecting the desired biodegradation of the finished parts after use.
• Another object is to increase the storage stability and extend the usability, in particular under moist climate conditions, of the semi-finished products and finished parts produced from the molding compositions according to the invention. It has now been found that the addition of additives and stabilizers to biodegradable polymers delays the start of biological and hydrolytic degradation in such a way that long-term applications, for example in construction or landscaping, are possible with these materials.
• the invention relates to thermoplastic, biodegradable molding compositions containing biodegradable polymers and at least one stabilizer selected from the group AI) and A2)
• AI 0 to 50 wt .-%, preferably 0.001 to 30 wt .-% and particularly preferred
• stabilizers selected from at least one from the group of hydrolysis stabilizers, such as, for example, aliphatic or aromatic monomeric, oligomeric or polymeric carbodimides, such as, for example, urethanized carbodiimides.
• aromatic or aliphatic isocyanates such as 2,6-diisopropylphenyl isocyanate, for example 2,6-diisopropyl
• A2) 0 to 50% by weight, preferably 0.001 to 30% by weight and particularly preferably 0.01 to 5% by weight, based on the total mixture, of a stabilizer selected from at least one from the group of microbial protection agents, for example thiurams , Thiophthalimides, sulfamides, urea derivatives, triazole derivatives, triazoline derivatives, benzimidazole derivatives, benzimidazolylcarbamic acid derivatives, arylsulfones, sulfenylsulfamides, phenols and phenolates, thiobenzothiazole derivatives, amino alcohols, isothiazoline
• a stabilizer selected from at least one from the group of microbial protection agents, for example thiurams , Thiophthalimides, sulfamides, urea derivatives, triazole derivatives, triazoline derivatives, benzimidazole derivatives, benzimidazolylcarbamic acid derivatives,
• fillers and reinforcing materials preferably natural mineral, synthetic inorganic or natural organic based on renewable raw materials or synthetic organic, metallic or a mixture of several of these components.
• the invention also relates to additive concentrates based on the biodegradable polymers themselves.
• Previous concentrates based, for example, on polyethylene or polyesters do not meet the requirement for complete biodegradation.
• the melting ranges of conventional concentrates, for example based on aromatic polyesters, and the biodegradable, mostly aliphatic or only partially aromatic, plastics are very different, so that homogeneous incorporation of the known concentrates into biodegradable polymers is made more difficult.
• the concentrates based on the biodegradable plastics have the advantage of good material compatibility and the associated homogeneous distribution of the additives in the respective matrix.
• the concentrates generally contain up to 40% by weight, preferably 1 to 30 wt .-%, in particular 5 to 20 wt .-% stabilizer based on the total mixture.
• suitable biodegradable polymers are aliphatic polyesters or copolyesters, aromatic polyesters or copolyesters, aromatic-aliphatic copolyesters, polycarbonates, polyester carbonates, aliphatic or partially aromatic polyester urethanes, polyester amides, polyether amides, polyether ester amides, cellulose ethers, cellulose ether esters, thermoplastic starch, starch derivatives or co- polymeric or a mixture of these components.
• the following polymers are preferably suitable:
• A) aliphatic bifunctional alcohols preferably linear C2 to C 0 di-alcohols such as ethanediol, butanediol, hexanediol or particularly preferably butanediol and / or optionally cycloaliphatic bifunctional alcohols, preferably having 5 or 6 carbon atoms in the cycloaliphatic ring, such as for example Cyclohexanedimethanol, and / or partially or completely instead of the diols, monomeric or oligomeric polymers based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights of up to 8000, preferably up to 4000, and / or optionally small amounts of branched bifunctional alcohols, preferably C ⁇ - C1-4 alkyldiols, such as neopentylglycol, and additionally, if appropriate, small amounts of higher-functional alcohols, such as 1,2,
• 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, or a mixture and / or a copolymer A and B, the aromatic acids making up no more than 50% by weight, based on all acids;
• C) aliphatic bifunctional alcohols preferably linear C 2 - to C ] 0 -di alcohols such as ethanediol, butanediol, hexanediol, particularly preferably butanediol and / or optionally cycloaliphatic bifunctional alcohols, preferably with a C5 or Cg cycloaliphatic ring, such as for example cyclohexanedimethanol, and / or partially or completely monomeric instead of diols or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof having molecular weights up to 4000, preferably to 1000, and / or optionally small amounts of branched bifunctional alcohols, preferably C3-C 12 - alkyl diols such as Neopentlyglykol, and additionally optionally small amounts of higher-functional alcohols, preferably, C 3 -C 1 2
• aromatic acids making up no more than 50% by weight, based on all acids
• Amines and / or amino alcohols with preferably 2 to 12 carbon atoms in the alkyl chain e.g. Ethylenediamine or aminoethanol and / or optionally further modified amines or alcohols such as, for example, ethylenediaminohansulfonic acid, as the free acid or as a salt,
• ester content C) and / or D) is at least 75% by weight, based on the sum of C), D) and E).
• 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 C2 to C 10 dialcohols, such as, for example, ethanediol, butanediol, hexanediol, particularly preferably butanediol, and / or optionally cycloaliphatic bifunctional alcohols, preferably having 5 to 8 carbon atoms, 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 of the copolymers thereof with molecular weights of up to 10,000, preferably up to 8,000, particularly preferably up to 5,000, and / or optionally small amounts of branched bifunctional alcohols, preferably C3-Ci 2 -alkyldiols, such as neopentyl glycol and additionally, if appropriate, small amounts of higher-functional alcohol
• K) 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, or a mixture and / or a copolymer of I) and K), the aromatic acids not making up more than 50% by weight, based on all acids,
• an amide component from acid- and amine-functionalized building blocks preferably with 4 to 20 C atoms in the cycloaliphatic chain, preferably ⁇ -laurolactam, ⁇ -caprolactam, particularly preferably ⁇ -caprolactam,
• the ester portion I) and / or K) being at least 30% by weight, based on the sum of I), K), L) and M), preferably the weight portion of the ester structures is 30 to 70% by weight, the proportion of the amide structures is 70 to 30% by weight.
• the polyether ester amides are composed in particular of the following monomers: Oligomeric polyols consisting of polyethylene glycols, polypropylene glycols, randomly or block-like polyglycols from mixtures of ethylene oxide or propylene oxide, or polytetrahydrofurans with molecular weights (weight average) between 100 and 10,000 and
• monomeric diols preferably C2-Ci2-alkyldiols, in particular C-C6-alkyldiols, for example ethylene glycol, 1,4-butanediol, 1,3-propanediol, 1,6-hexanediol,
• Dicarboxylic acids preferably C 2 -Ci 2 -, particularly preferably C2-C 6 -alkyldicarboxylic acids, for example oxalic acid, succinic acid, adipic acid, also in the form of their respective esters (methyl, ethyl, etc.)
• Amino alcohols with 2 to 12 carbon atoms in the alkyl chain for example ethanolamine, propanolamine
• cyclic lactams with 5 to 12, preferably 6 to 11, carbon atoms, such as ⁇ -caprolactam or laurolactam etc.
• ⁇ -aminocarboxylic acids with 6 to 12 carbon atoms in the alkyl chain such as aminocaproic acid etc.
• both hydroxyl- or acid-terminated polyesters with molecular weights between 300 and 10,000 can be used as the ester-forming component.
• the proportion of ether and ester fractions in the polymer is generally 5 to 85% by weight, based on the total polymer.
• the polyether ester amides according to the invention generally have a medium one
• M vv determined according to gel chromatography in cresol against standard polystyrene from 10,000 to 300,000, preferably from 15,000 to 150,000, in particular from 15,000 to 100,000.
• All acids can also be used in the form of derivatives such as acid chlorides or esters, both as monomeric and as oligomeric esters.
• the biodegradable polyesteramides according to the invention can be synthesized 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 of 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 possible to accelerate the polycondensation.
• the polycondensation to polyester amides can be Turn of lysine, lysine derivatives or other amidic branching products such as aminoethylaminoethanol can be influenced, which both accelerate the condensation and lead to branched products (see for example DE-A 38 31 709).
• 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 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 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 glycerol, tetrafunctional 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 is possible with these polymers. This does not hinder the biodegradation of these materials.
• the biodegradable / compostable polyester urethanes, polyesters, polyester carbonates and polyester amides generally have a molecular weight of at least
• a particularly preferred polycarbodiimide is the aromatic polycarbodiimide which is substituted with isopropyl groups in the o-position to the carbodiimide groups, ie in the 2,6- or 2,4,6-position on the benzene nucleus.
• the polycarbodiimides contained preferably have an average molecular weight of 1500 to 15,000, but in particular of 9,000 to 12,000.
• it is possible to add small amounts of aromatic and / or aliphatic (poly) carbodiimides To increase the thermo-oxidative resistance in such a way that the end group contents of the biodegradable plastics are reduced and the biodegradable plastic is hydrolytically stable.
• the carbodiimides can be prepared by processes known per se (for example DE-AS 25 37 685, DE-AS 11 56 401, DE-AS 24 19 968, FR 1 180 307).
• Fillers and reinforcing materials suitable according to the invention can be minerals, such as, for example, kaolin, chalk, gypsum, mica, lime or talc, or natural substances, such as, for example, starch or modified starch, cellulose or cellulose derivatives or cellulose products, wood flour or natural fibers such as, for example, hemp, flax, sisal, Rape or ramie.
• Iron powder iron oxides, iron alloys (for example ferrotitanium, ferromolybdenum, ferro-manganese), tungsten, tungsten carbide, ferrotungsten, molybdenum, manganese, cobalt, copper, zinc, tin or bismuth or combinations thereof can also be used as metallic fillers.
• the biodegradable / fully compostable polyester urethanes, polyesters, polyester carbonates and polyester amides according to the invention can be equipped with conventional additives.
• Modifiers and / or processing aids such as nucleating agents, plasticizers, mold release agents, flame retardants, impact modifiers, stabilizers, for example for thermostability, oxidation stability, UV and light stability, can give color
• Agents e.g. pigments
• additives customary in the field of thermoplastic are used, whereby care must be taken to ensure that the full compostability is not impaired or that the remaining substances, for example mineral auxiliaries, are harmless in the compost.
• the additives are generally added in an amount of up to 15% by weight, based on the total mixture.
• the molding compositions according to the invention are biodegradable, preferably completely biodegradable. Molding compositions which can be classified as completely degradable according to DIN 54 900 are particularly preferred.
• polyester urethanes The biodegradable / fully compostable polyester urethanes according to the invention.
• Polyesters, polyester carbonates and polyester amides can also be mixed with other blend partners, for example thermoplastic starch, it being important to ensure that the complete compostability is not impaired or the remaining substances, for example mineral auxiliaries, are harmless in the compost.
• Polyethylene modified polyethylenes such as, for example, maleic anhydride-modified LDPE, a fluorine thermoplastic such as, for example, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkoxy-vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, ethylene-chloro-trifluorethylene , Polyvinylidene fluoride, polyvinyl fluoride, perfluoroalkoxyalkane, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer, amorphous perfluoropolymers, polyvinyl chloride, polyvinylidene chloride, a polypropylene, a polyvinyl alcohol, a polyvinyl acetate, a partially hydrolyze
• Polyester or copolyester an aromatic polyester or copolyester, an aromatic-aliphatic copolyester, a polycarbonate, a polyester carbonate, a partially aromatic polyurethane, an aliphatic polyurethane, a polyester urethane, a polyamide, a polyester amide, a polyether amide, a polyether ester amide, a cellulose loose ether, a cellulose ether ester, a starch derivative or a copolymer or a
• the blend partners can up to a content of 99 wt .-%. preferably up to 70% by weight, based on the total amount of the molding composition.
• the invention further relates to a process for the preparation of the molding compositions according to the invention, characterized in that the individual components and, if appropriate, further additives (customary additives) are mixed in a known manner and at elevated temperatures, preferably from 150 to 300 ° C., in conventional units such as Internal kneaders, extruders and twin-screw extruders are melt-compounded and melt-extruded.
• the invention further relates to a process for the preparation of the molding compositions according to claims 1 to 15, wherein the biodegradable polymer is mixed and mixed with a concentrate of biodegradable polymer and at least one stabilizer AI) or A2) and optionally component B) and additives melt compounded and melt extruded at elevated temperature.
• extruders that can be used are: a fully intermeshing, closely intermeshing twin-screw extruder, a single-screw extruder for high-performance extrusion, which works on the principle
• Stator / rotor (eg Staromix ® from Reifen Reifenberger) works, a three-screw extruder, a continuous / discontinuous KO kneader, a continuous dispersion kneader with a slow-running rotor-stator combination (eg KEX, Drais, Mannheim).
• the invention further relates to the use of the molding compositions according to the invention for the production of semifinished products, films, in particular hygiene films, garbage bags, roofing underlays and films as a component of clothing, injection moldings, in particular plant pots, planting chambers, plant binders, multifilaments. Monofilaments, fibers, in particular cut fibers, fibers for coating heat-sealable filter papers, nonwovens and fabrics, in particular geotextiles, protective work clothing. Automotive interior trim as well as the articles themselves.
• polyesteramide e.g. BAK® 1095 from Bayer AG
• aromatic polycarbodiimide e.g. Stabaxol® P100 from Rhein Chemie Rheinau GmbH
• BAK® 1095 is a polyester amide of adipic acid, butanediol and caprolactam with an ester / amide weight ratio of 70/30, statistically copolycondensed with a relative solution viscosity of 2.78 measured on a 1% by weight solution in meta-cresol at 20 ° C.
• BAK® 2195 is a polyester amide from 32.3% by weight adipic acid, 1 1.7% by weight 1,4-butanediol, 15.0% by weight diethy englycol, 41% by weight AH salt, statistically copolycondensed, with a relative solution viscosity of 2.8, measured on a 1 wt .-% solution in m-cresol at 20 ° C.
• BAK® 2195 is injection molded as a mixture with a concentrate prepared according to Example 1 to test rods (80 * 10 * 4 mm). The rods are stored at 60 ° C in water, which is mixed with 0.02% by weight sodium azide as a biocide to keep them sterile. The results are shown in Table 2.

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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)
• Life Sciences & Earth Sciences (AREA)
• Biodiversity & Conservation Biology (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Polyurethanes Or Polyureas (AREA)
• Artificial Filaments (AREA)

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• 1997
  • 1997-12-09 DE DE19754418A patent/DE19754418A1/de not_active Withdrawn
• 1998
  • 1998-11-28 WO PCT/EP1998/007690 patent/WO1999029768A1/de not_active Application Discontinuation
  • 1998-11-28 CN CN98811939A patent/CN1281482A/zh active Pending
  • 1998-11-28 AU AU18763/99A patent/AU1876399A/en not_active Abandoned
  • 1998-11-28 CA CA002313192A patent/CA2313192A1/en not_active Abandoned
  • 1998-11-28 KR KR1020007006220A patent/KR20010032889A/ko not_active Application Discontinuation
  • 1998-11-28 EP EP98963527A patent/EP1037943A1/de not_active Withdrawn
  • 1998-11-28 JP JP2000524352A patent/JP2001525473A/ja active Pending
  • 1998-12-08 ZA ZA9811205A patent/ZA9811205B/xx unknown
• 2000
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