WO2014009176A1 - Procédé de biodégradation anaérobie complète de mélanges polymères - Google Patents

Procédé de biodégradation anaérobie complète de mélanges polymères Download PDF

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WO2014009176A1
WO2014009176A1 PCT/EP2013/063647 EP2013063647W WO2014009176A1 WO 2014009176 A1 WO2014009176 A1 WO 2014009176A1 EP 2013063647 W EP2013063647 W EP 2013063647W WO 2014009176 A1 WO2014009176 A1 WO 2014009176A1
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hydroxybutyrate
poly
components
mol
biogas
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PCT/EP2013/063647
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German (de)
English (en)
Inventor
Carsten SINKEL
Robert Loos
Karlheinz JOCHEM
Kai Oliver SIEGENTHALER
Xin Yang
Ulf KÜPER
Mathias ZIMMERMANN
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Basf Se
Basf Schweiz Ag
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Publication of WO2014009176A1 publication Critical patent/WO2014009176A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones

Definitions

  • the present invention relates to a process for the complete anaerobic degradation of polymer mixtures comprising:
  • polyhydroxyalkanoate selected from the group consisting of poly-4-hydroxybutyrate, poly-3-hydroxybutyrate, poly (3-hydroxybutyrate-co-3-hydroxyvalerate), poly (3-hydroxybutyrate-co-3-) hydroxyhexanoates) and poly (3-hydroxybutyrate-co-4-hydroxybutyrate); and b) 5 to 75% by weight of an aliphatic-aromatic polyester containing:
  • WO-A 92/09654 describes linear aliphatic-aromatic polyesters which are biodegradable. Crosslinked, biodegradable polyesters are described in WO-A
  • polyesters described in WO-A 92/09654 and WO-A 96/15173 do not have an anaerobic degradation rate in mixtures with polyhydroxyalkanoates, which is significantly greater than the polyhydroxyalkanoate content.
  • the inventive mixtures whose polymer component b has a lower terephthalic acid content have an increased anaerobic degradation rate, which clearly exceeds the calculated value of the polyhydroxyalkanoate content. This is surprising and indicates that the polymer mixtures according to the invention have a synergy with respect to anaerobic degradation.
  • polyesters described at the outset which have a narrowly defined terephthalic acid content and a narrowly defined content of a polyfunctional component iv, it was possible, surprisingly, to prepare mechanically loadable films having a high anaerobic degradation rate.
  • Polyhydroxyalkanoates are primarily poly-4-hydroxybutyrates and poly-3-hydroxybutyrates or poly-3-hydroxybutyrate-co-4-hydroxybutyrates and copolyesters of the abovementioned polyhydroxybutyrates with 3-hydroxyvalerate, 3-hydroxyhexanoate and / or 3-hydroxyoctanoate.
  • Poly-3-hydroxybutyrates are sold, for example, by PHB Industrial under the brand name Biocycle® and by Tianan under the name Enmat®.
  • Poly-3-hydroxybutyrate-co-4-hydroxybutyrates are known in particular from Metabolix. They are sold under the trade name Mirel®.
  • Poly-3-hydroxybutyrate-co-3-hydroxyhexanoates are known, for example, from Kaneka.
  • Poly-3-hydroxybutyrate-co-3-hydroxyhexanoates generally have a 3-hydroxyhexanoate content of 1 to 20 and preferably from 3 to 15 mol%, based on the butyrate fraction.
  • the synergy in anaerobic degradation is found in all of the aforementioned polyhydroxyalkanoates. It is particularly pronounced for the copolymers: poly-3-hydroxybutyrate-co-3-hydroxyvalerate and especially for poly-3-hydroxybutyrate-co-4-hydroxybutyrate and poly-3-hydroxybutyrate-co-3-hydroxyhexanoate.
  • the abovementioned copolymers are particularly preferred for the novel polymer blends.
  • the polyhydroxyalkanoates generally have a molecular weight Mw of from 100,000 to 1,000,000, and preferably from 300,000 to 600,000.
  • the polyhydroxyalkanoates are preferably prepared by fermentation, as described, for example, in WO-A 2008010296 or WO-A 1999064498.
  • the synthesis of the polyester component b) is generally carried out in a two-stage reaction cascade (see WO09 / 127555 and WO09 / 127556).
  • the dicarboxylic acid derivatives as in the synthesis examples, are reacted together with the diol (for example 1,4-butanediol) in the presence of a transesterification catalyst to give a prepolyester.
  • the melt of the prepolyester thus obtained is usually condensed at an internal temperature of 200 to 250 ° C within 3 to 6 hours at reduced pressure while distilling off released diol to the desired viscosity.
  • the catalysts used are usually zinc, aluminum and in particular titanium catalysts.
  • Titanium catalysts such as tetra (isopropyl) orthotitanate and in particular tetrabutyl orthotitanate (TBOT) have the advantage over the tin, antimony, cobalt and lead catalysts frequently used in the literature, such as, for example, tin dioctanoate, that residual amounts of catalyst or secondary product of the catalyst remaining in the product are less toxic. This fact is particularly important in the case of biodegradable polyesters, since they enter the environment directly, for example as composting bags or mulch films.
  • TBOT tetrabutyl orthotitanate
  • the polyesters according to the invention are optionally subsequently chain-extended according to the processes described in WO 96/15173 and EP-A 488 617.
  • the prepolyester is reacted, for example, with chain extenders vib), such as with diisocyanates or with epoxy-containing polymethacrylates, in a chain extension reaction to give a polyester having a viscosity of 60 to 450 ml / g, preferably 80 to 250 ml / g.
  • the polyester component b) is prepared by the continuous process described in WO2009127556.
  • the abovementioned ranges of viscosity numbers merely serve as indications for preferred process variants, but are not intended to be limiting for the present application subject.
  • the polyesters according to the invention can also be prepared in a batch process.
  • the aliphatic and the aromatic dicarboxylic acid derivative, the diol and a branching agent iva are mixed in any metering order and condensed to form a prepolyester.
  • a polyester having the desired viscosity number can be prepared.
  • polybutylene terephthalate succinates, azelates, brassates and, in particular, adipates and sebacates having an acid number, measured in accordance with DIN EN 12634, of less than 1.0 mg KOH / g and a viscosity number greater than 130 ml / g can be obtained by the abovementioned processes and a MVR according to ISO 1133 of less than 6 cm 3/10 min (190 ° C, 2.16 kg weight).
  • polyester according to the invention with higher MVR can be interesting to ISO 1133 of up to 30 cm 3/10 min (190 ° C, 2.16 kg weight).
  • the polyesters generally have an MVR according to ISO 1133 1-30 cm 3/10 min and preferably 2 to 20 cm 3/10 min (190 ° C, 2, 16 kg weight).
  • Sebacic acid, azelaic acid and brassylic acid (i) are derived from renewable resources, in particular from vegetable oils such as e.g. Castor oil accessible.
  • the terephthalic acid ii is used in 5 to 35 mol% and preferably 10 to 25 mol% based on the diacid components i and ii.
  • Terephthalic acid and the aliphatic dicarboxylic acid can be used either as the free acid or in the form of ester-forming derivatives.
  • Particularly suitable ester-forming derivatives are the di-C 1 - to C 6 -alkyl esters, such as dimethyl, diethyl, di-n-propyl, diisopropyl, di-n-butyl, diisobutyl, di-t-butyl, Di-n-pentyl, di-iso-pentyl or di-n-hexyl esters to name.
  • Anhydrides of dicarboxylic acids can also be used.
  • the dicarboxylic acids or their ester-forming derivatives can be used individually or as a mixture.
  • 09/024294 discloses a biotechnological process for the production of 1,4-butanediol from different carbohydrates with microorganisms from the class of Pasteurellaceae. Succinic acid is also accessible by biotechnological methods.
  • the diol (component iii) is added to the acids (components i and ii) in a ratio of diol to diacids of from 1.0 to 2.5: 1 and preferably from 1.3 to 2.2: 1 used. Excess diol are withdrawn during the polymerization, so that sets an approximately equimolar ratio at the end of the polymerization. By approximately equimolar is meant a diol / diacid ratio of 0.98 to 1: 1.
  • the said polyesters may have hydroxyl and / or carboxyl end groups in any ratio.
  • the abovementioned partially aromatic polyesters can also be end-group-modified.
  • OH end groups by Reaction with phthalic acid, phthalic anhydride, trimellitic acid, trimellitic anhydride, pyromellitic acid or pyromellitic anhydride are acid-modified.
  • a branching agent iva and optionally additionally a chain extender ivb selected from the group consisting of: a polyfunctional isocyanate, isocyanurate, oxazoline, epoxide, carboxylic anhydride, an at least trifunctional alcohol or an at least trifunctional carboxylic acid are used.
  • Suitable chain extenders ivb are polyfunctional and in particular difunctional isocyanates, isocyanurates, oxazolines, carboxylic anhydride or epoxides.
  • the crosslinkers iva) are generally obtainable in a concentration of 0 to 2% by weight, preferably 0.07 to 1% by weight and more preferably 0.1 to 0.5% by weight, based on the polymer the components i to iii used.
  • the chain extenders ivb) are generally used in a concentration of 0 to 2 wt .-%, preferably 0.1 to 1 wt .-% and particularly preferably 0.35 to 1 wt .-% based on the total weight of the components i used to iii.
  • Chain extenders as well as alcohols or carboxylic acid derivatives having at least three functional groups can also be regarded as branching agents.
  • Especially preferred compounds have three to six functional groups. Examples include: tartaric acid, citric acid, malic acid; Trimethylolpropane, trimethylolethane; pentaerythritol; Polyether triols and glycerol, trimesic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid and pyromellitic dianhydride.
  • Preference is given to polyols such as trimethylolpropane, pentaerythritol and in particular glycerol.
  • biodegradable polyesters with a structural viscosity can be built up.
  • the rheological behavior of the melts improves;
  • the biodegradable polyesters are easier to process, for example, better by melt consolidation to remove films.
  • Suitable bifunctional chain extenders are the following compounds: Under an aromatic diisocyanate ivb are mainly toluylene-2,4-diisocyanate, toluylene-2,6-diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4 , 4'-diphenylmethane diisocyanate, naphthylene-1, 5-diisocyanate or xylylene diisocyanate understood. Of these, 2,2'-, 2,4'- and 4,4'-diphenylmethanediisocyanate are particularly preferred. In general, the latter diisocyanates are used as a mixture.
  • the diisocyanates may also contain uretdione groups, for example for capping the isocyanate groups.
  • an aliphatic diisocyanate is primarily linear or branched alkylene diisocyanates or cycloalkylene diisocyanates having 2 to 20 carbon atoms, preferably 3 to 12 carbon atoms, for example 1, 6-hexamethylene diisocyanate, isophorone diisocyanate or methylene bis (4-isocyanatocyclohexane ), Understood.
  • Particularly preferred aliphatic diisocyanates are isophorone diisocyanate and in particular 1,6-hexamethylene diisocyanate.
  • the polyesters of the invention generally have a number average molecular weight (Mn) in the range of 5000 to 100,000, in particular in the range of 10,000 to 60,000 g / mol, preferably in the range of 15,000 to 38,000 g / mol, a weight-average molecular weight (Mw) of 30,000 to 300,000, preferably 35,000 to 200,000 g / mol and a Mw / Mn ratio of 1 to 6, preferably 2 to 4.
  • the viscosity number is between 30 and 450, preferably from 50 to 400 ml / g and particularly preferably from 80 to 250 ml / g (measured in o-dichlorobenzene / phenol (weight ratio 50/50)).
  • the melting point is in the range of 30 to 100, preferably in the range of 35 to 80 ° C.
  • the aliphatic dicarboxylic acid is preferably adipic acid and / or sebacic acid.
  • Component iii), the diol, is preferably 1,4-butanediol.
  • Komponete iv) the branching agent iva, is preferably glycerol.
  • novel polymer blends contain from 25 to 95% by weight, preferably from 30 to 90% by weight and particularly preferably from 35 to 85% by weight, of polyhydroxyalkanoate (a) and accordingly from 5 to 75% by weight, preferably from 10 to 70 Wt .-% and particularly preferably 15 to 65 wt .-% polyester component b.
  • an organic filler c is selected from the group consisting of: native or plasticized starch, natural fibers, wood flour, crushed cork, ground bark, nut shells, ground press cakes (vegetable oil refinery), dried production residues from fermentation or distillation of beverages such as beer, brewed sodas (eg bionade), wine or sake and / or an inorganic filler selected from the group consisting of: chalk, graphite , Gypsum, carbon black, iron oxide, calcium chloride, dolomite, kaolin, silica (quartz), sodium carbonate, titanium dioxide, silicate, wollastonite, mica, montmorillonite, talc, glass fibers and mineral fibers.
  • native or plasticized starch natural fibers, wood flour, crushed cork, ground bark, nut shells, ground press cakes (vegetable oil refinery), dried production residues from fermentation or distillation of beverages such as beer, brewed sodas (eg bionade), wine or sake and / or an inorganic filler selected from the
  • Starch and amylose may be native, ie non-thermoplasticized or thermoplasticized with plasticizers such as glycerol or sorbitol (EP-A 539 541, EP-A 575 349, EP 652 910).
  • Thermoplastified starch is particularly preferred because it itself is likewise degraded anaerobically and films which, in addition to starch, contain the polymer components a and b, provide good mechanical properties.
  • mixtures of starch and polymer component b (without polymer component a) show no synergy with respect to anaerobic degradability.
  • thermoplasticized starch is added to the polymer blends containing the components a and b, usually in a ratio of 0 to 50, preferably 5 to 50 and particularly preferably 10 to 35 wt .-%. Sheets produced from this have excellent tear resistance and at the same time complete anaerobic degradation. They are particularly suitable for the production of very thin, tear-resistant films.
  • natural fibers are, for example, cellulose fibers, hemp fibers, sisal, kenaf, jute, flax, abaca, coconut fiber or even regenerated cellulose fibers (rayon) such.
  • B. Cordenkamaschinen understood.
  • mineral fillers such as chalk, graphite, gypsum, Leitruß, iron oxide, calcium chloride, dolomite, kaolin, silica (quartz), sodium carbonate, titanium dioxide, silicate, wollastonite, mica, montmorillonite or talc
  • the mechanical properties of the films such as Significantly improve tear propagation resistance.
  • the mineral fillers are used in a concentration of 1 to 50, preferably 4 to 30 and particularly preferably 8 to 25% by weight, based on the polymer components i to iv.
  • the anaerobically degradable polyester mixtures a, b may further contain polymers such as polylactic acid, polycaprolactone, aliphatic polyesters, polyglycolic acid and polypropylene propylene carbonate in an amount of 0 to 30% by weight, preferably 5 to 20% by weight.
  • polymers such as polylactic acid, polycaprolactone, aliphatic polyesters, polyglycolic acid and polypropylene propylene carbonate in an amount of 0 to 30% by weight, preferably 5 to 20% by weight.
  • Aliphatic polyesters include polyesters of aliphatic C 2 -C 12 alkanediols and C 4 -C 36 aliphatic alkanedicarboxylic acids such as polybutylene succinate (PBS), polybutylene adipate (PBA), polybutylene succinate adipate (PBSA), polybutylene succein sebacate (PBSSe), polybutylene sebacate adipate (PBSeA), polybutylene sebacate (PBSe) or corresponding polyesteramides understood.
  • PBS polybutylene succinate
  • PBSA polybutylene succinate adipate
  • PBSSe polybutylene succein sebacate
  • PBSeA polybutylene sebacate adipate
  • PBSe polybutylene sebacate
  • the aliphatic polyesters are marketed by Showa Highpolymers under the name Bionolle® and by Mitsubishi under the name GSPIa®. Newer developments are in the WO
  • the biodegradable polyester mixtures may contain further ingredients known to the person skilled in the art but not essential to the invention.
  • plastics technology such as stabilizers; nucleating agents; Neutralizing agents; Lubricants and release agents such as stearates (in particular calcium stearate) or erucic acid amide or behenamide; Plasticizers such as citric acid esters (especially acetyl tributyl citrate), glyceric acid esters such as triacetylglycerol or ethylene glycol derivatives, surfactants such as polysorbates, palmitates or laurates; Waxes such as beeswax or beeswax esters; Antistatic, UV absorber; UV stabilizers; Antifog agents or dyes.
  • the additives are used in concentrations of 0 to 5 wt .-%, in particular 0.1 to 2 wt .-% based on the polyesters of the invention.
  • Plasticizers may be present in 0.1 to 10% by weight in the polyesters of the invention.
  • biodegradable polyester mixtures according to the invention from the individual components can be carried out by known processes (EP 792 309 and US Pat. No. 5,883,199).
  • all mixing partners can be mixed and reacted at elevated temperatures, for example from 120 ° C. to 250 ° C., in mixing apparatuses known in the art, for example kneaders or extruders, in one process step.
  • the polymer blends may in turn contain from 0.05 to 2% by weight of a compatibilizer.
  • Preferred compatibilizers are carboxylic acid anhydrides such as maleic anhydride and in particular the previously described epoxide group-containing copolymers based on styrene, acrylic ester and / or methacrylic acid ester.
  • the epoxy groups bearing units are preferably glycidyl (meth) acrylates.
  • the epoxy-containing copolymers of the above type are sold for example by BASF Resins BV under the trademark Joncryl ® ADR.
  • As tolerability keitsvermittler particularly suitable Joncryl ® ADR, for example, the 4368th
  • Component iv, the aforementioned fillers or the other auxiliaries mentioned above are preferably added by previously prepared masterbatches of the auxiliaries in polymer component a or b.
  • polymers or polymer mixtures can undergo a degradation process in two fundamentally different ways.
  • the polymeric structure of a macromolecule can be resolved solely under the influence of abiotic factors (physico-chemical parameters, such as: UV radiation, temperature, pH, moisture, influence of oxygen radicals), which ultimately leads to a transfer of the polymer in Oligomers, monomers or from the degradation resulting reaction products leads.
  • abiotic factors phyto-chemical parameters, such as: UV radiation, temperature, pH, moisture, influence of oxygen radicals
  • the biodegradation of polymers is primarily due to the biochemical interaction of microorganisms (bacteria rien, archaea, fungi) with the polymer.
  • the breakage of the chemical bonds in the polymer is achieved by specific interactions with the enzymes of the microorganisms.
  • the interplay of different microorganisms and their enzymes eventually leads to mineralization of the polymer.
  • the polymer is not only recycled into monomers or oligomers, but rather is converted enzymatically into the microbial metabolic end products water, carbon dioxide and methane (under anaerobic conditions).
  • Abiotic and biological degradation often occur in parallel - but it is crucial that the mineralization is at the end of biodegradation.
  • the biological degradation of macromolecules per se is a very diverse process that results in different rates of degradation in terms of habitat and the abiotic parameters prevailing there.
  • a correspondingly high compatibility between polymer and enzyme is necessary for efficient biodegradation. Consequently, a high degradation rate can be achieved if the conditions prevailing in the habitat are optimal for the microorganisms involved and a specific interaction between the polymer chain and the enzyme is ensured.
  • Decisive factors here are the temperature, the pH value, the presence or absence of oxygen and the availability of nutrients, minerals and trace elements.
  • the respective habitat will dominate different consortia with a very variable number of microorganisms (total cell count: cells per volume, biodiversity: number of microbial species in the habitat) and lead to the described different rates of degradation.
  • the efficiency of the respective process is related to how much biogas (volume CO2 and CH4) can be obtained from the amount of substrate (carbon source) and how high the quality of the biogas produced is (proportion CH4).
  • the methane formation potential of a substrate can thus be determined by measuring the methane formed in a defined time unit and compared quantitatively with other substrates.
  • a simple volume determination of the biogas formed is often carried out, in which the CO2 is washed out in advance by means of sodium hydroxide solution.
  • the volume of methane formed can be determined directly.
  • the total volume of the biogas can be determined first and the quantitative analysis of the biogas composition is subsequently followed by gas chromatography. Considering later technical application and better comparability, anaerobic degradation is usually taken into account for a maximum of 2 months in all test procedures.
  • Plastics Determination of complete anaerobic degradability Plastic materials in an aqueous medium - Method by analysis of the released biogas in the VDI guideline
  • the present method is also intended to include test methods other than the
  • anaerobic degradability used in the application thus refers primarily to VDI 4630.
  • the present invention accordingly relates in particular to a process for the complete anaerobic degradation of polymer mixtures of the composition:
  • a polyhydroxyalkanoate selected from the group consisting of poly-4-hydroxybutyrates, poly-3-hydroxybutyrates, poly (3-hydroxybutyrates-co-3-hydroxyvalerates) , Poly (3-hydoxybutyrate-co-3-hydroxyhexanoate and poly (3-hydroxybutyrate-co-4-hydroxybutyrate) and
  • an aliphatic-aromatic polyester comprising: i) from 65 to 95 mol%, based on the components i to ii, of one or more C5-C36 dicarboxylic acid derivatives or C5- C36-dicarboxylic acids; ii) from 35 to 5 mol%, based on the components i to ii, of a terephthalic acid derivative or a terephthalic acid; iii) from 98 to 100 mol%, based on components i to ii, of a C 2 -C 8 -alkylenediol or C 2 -C 6 -oxyalkylenediol; iv) from 0 to 2% by weight, based on the components i to iii, of at least one polyfunctional compound containing at least two isocyanate, isocyanurate, oxazoline or epoxide groups or at
  • anaerobic degradation can be determined by means of one of the methods according to VDI 4630 or ISO 15985.
  • the method according to VDI 4630 is particularly preferred as mentioned above.
  • the inoculum used in the VDI 4630 was an LUFA sludge.
  • the content of dry matter was 3.7% of the fresh substance, with the ash 1, 8% of the fresh substance (49.5% of the dry matter) and the organic substance (loss on ignition) 1, 9% of the fresh substance (50.5% of Dry matter); the pH was about 7.4 to 7.8.
  • the complete anaerobic degradation of polymer blends with a high content of polymer component a greater than 70% and in particular greater than 90%, is determined as follows. It is assumed that the proportion of the polymer component a is degraded to 100%. The experimentally determined amount of biogas is deducted from the amount of biogas formed and the excess attributed to the degradation of the polymer component b. From this value, it is possible to check, based on the above tabulated values, whether component b has degraded to greater than 90%.
  • polymer blends containing 80 wt .-% or more polymer component b are not completely degraded according to the above criteria.
  • the polymer component b as a pure substance is not degraded at all anaerobically.
  • biodegradable polyester mixtures are suitable for the production of films and film tapes for nets and fabrics, tubular films, chill-roll Films with and without orientation in a further process step, with and without metallization or SiOx coating suitable.
  • layer thicknesses of the films of 5 to 45 ⁇ m and in particular of 10 to 30 ⁇ m are advantageous.
  • the films containing the polymer components a) and b) are suitable for tubular films and stretch films.
  • Possible applications here are bottom folding bags, side seam bags, carrying bags with handle holes, shrink labels or shirt carrier bags, inliners, heavy bags, freezer bags, composting bags, agricultural films (mulch films), film bags for food packaging, removable sealing film - transparent or opaque - weldable sealing film - transparent or opaque -, sausage casing, salad foil, plastic wrap (stretch film) for fruit and vegetables, meat and fish, stretch wrap for wrapping pallets, foil for nets, packaging foils for snacks, chocolate and muesli bars, peelable lid foils for dairy packs (yoghurt, cream, etc.) ), Fruits and vegetables, semi-hard packaging for smoked sausage and cheese.
  • the films mentioned are predestined for packaging meat, poultry, meat products, processed meat, sausages, smoked sausages, seafood, fish, crabmeat, cheese, cheese products, desserts, patties, etc. , With meat, fish, poultry, tomato stuffing, pastes and spreads; Bread, cakes, other baked goods; Fruit, fruit juices, vegetables, tomato paste, salads; Pet food; pharmaceutical products; Coffee, coffee-based products; Milk or cocoa powder, coffee whitener, baby food; dried foods; Jams and jellies; Spreads, chocolate cream; Ready meals. For more information, see reference in "Food Processing Handbook," James G. Brennan, Wiley-VCH, 2005.
  • the films also have very good adhesion properties, making them ideal for paper coating, such as paper cups and paper plates A combination of these methods or a coating by spraying, knife coating or dipping is conceivable.
  • biogood which includes biowaste, green waste, expired and inedible food, trays, stalks, etc. of so-called domestic waste, as well as waste, residues in the cultivation of food and in the production of food, disposed of in landfills.
  • methane a harmful greenhouse gas
  • composting facilities, and biogas plants in particular is the best solution of total eco-balance.
  • the biogood has often been collected using paper bags or newsprint that are easily soaked, collected, or collected Hygienic and breathable packaging such as garbage bags or packaging for food are used, but are not degraded in biogas plants under the prevailing anaerobic conditions there.
  • packaging for food and waste bags for organic waste
  • the following process is an extremely interesting alternative:
  • a method of disposing of biogas in a biogas plant comprising, in a first step, the biogas in a package containing polymer blends of the composition: a) from 25 to 95% by weight of a polyhydroxyalkanoate selected from the group consisting of poly-4-hydroxybutyrate, Poly-3-hydroxybutyrate, poly (3-hydroxybutyrate-co-3-hydroxyvalerate), poly (3-hydroxybutyrate-co-3-hydroxyhexanoate and poly (3-hydroxybutyrate-co-4-hydroxybutyrate) and b) 5 to 75 wt % of an aliphatic polyester containing:
  • the molecular weights Mn and Mw of the partially aromatic polyesters were determined in accordance with DIN 55672-1. Eluent hexafluoroisopropanol (HFIP) + 0.05% by weight of trifluoroacetic acid Ka salt; The calibration was carried out with narrowly distributed polymethyl methacrylate standards. The determination of the viscosity numbers was carried out according to DIN 53728 Part 3, January 3, 1985, capillary viscometry. A micro Ubbelohde viscometer, type M-II, was used. The solvent used was the mixture: phenol / o-dichlorobenzene in a weight ratio of 50/50. Modulus of elasticity and elongation at break were determined by means of a tensile test according to ISO 527-3: 2003.
  • the tear strength was determined by an Elmendorf test according to
  • the test machine used is a Zwick 1 120 equipped with a spherical punch with a diameter of 2.5 mm.
  • the sample a circular piece of film to be measured, was clamped perpendicular to the test die and passed through it at a constant test speed of 50 mm / min. Through the plane defined by the jig. During the test, both the force as well as the elongation recorded, thus determining the puncture work.
  • the anaerobic degradation rates of the biodegradable polyester blends and the blends prepared for comparison were determined as follows:
  • the contents of the fermenter were inoculum derived from measurements of biogas yields in a batch process and prepared under defined conditions (according to VDI 4630). Deviating from the chosen specifications (VDI 4630), however, the material had an increased dry matter content (TS) of approx. 4.5% (w / v) and an increased proportion of organic dry substance (oTS) of approx. 50% (w / w ).
  • TS dry matter content
  • oTS organic dry substance
  • the fermenters were initially filled with 4.5 l of conditioned seed material, 30 g of the corresponding test substance were added (corresponds to a ratio of oTS inoculum to oTS test substance of 3.375: 1 (v / w)), the fermenter sealed gas-tight and the gas phase of the Fermenter substituted with nitrogen.
  • the resulting biogas was collected in a gas collection bag, which was connected to the gas compartment of the fermenter via gastight hose connections.
  • the volume measurement of the biogas formed was discontinuous, the determination of the gas composition was carried out by IR measurement (CFU, CO2, O2) and by means of electrochemical sensors (H2S) in the gas chromatograph.
  • Polymer component a (polyhydroxyalkanoate)
  • Polyester B1 (comparative)
  • the polyester B1 thus obtained has a viscosity number of 84 ml / g and a
  • biogas production is significantly above the theoretically expected value (50% PHB in the mixture corresponds to a maximum of 503 L / kg biogas) : + 28%, 4: + 65%, 5: + 45%).
  • This synergistic effect is surprising.
  • the biodegradability of the polymer mixture, which was used in the experiments V1, V2 and V6, is significantly lower in the considered time interval.

Abstract

Procédé de dégradation anaérobie complète de mélanges polymères ayant la composition suivante : a) 25 à 95 % en poids d'un polyhydroxyalcanoate choisi dans le groupe constitué par les poly-4-hydroxybutyrates, les poly-3-hydroxybutyrates, les poly(3-hydroxybutyrates-co-3-hydroxyvalérates), les poly(3-hydroxybutyrates-co-3-hydroxyhexanoates et les poly(3-hydroxybutyrates-co-4-hydroxybutyrates) et b) 5 à 75 % en poids d'un polyester aliphatique-aromatique contenant i) 65 à 95 % en moles, rapporté aux constituants i à ii, d'un ou de plusieurs dérivés d'acide dicarboxylique C5-C36 ou d'acides dicarboxyliques C5-C36 ; ii) 35 à 5 % en moles, rapporté aux constituants i à ii, d'un dérivé de l'acide téréphtalique ou d'un acide téréphtalique ; iii) 98 à 100 % en moles, rapporté aux constituants i à ii, d'un alkylène diol C2-C8 ou d'un oxyalkylène diol C2-C6 ; iv) 0 à 2 % en poids, rapporté aux constituants i à iii, d'au moins un composé polyfonctionnel contenant au moins deux groupes isocyanate, isocyanurate, oxazoline ou époxyde, ou au moins trois groupes alcool ou acide carboxylique.
PCT/EP2013/063647 2012-07-10 2013-06-28 Procédé de biodégradation anaérobie complète de mélanges polymères WO2014009176A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024087609A1 (fr) * 2022-10-28 2024-05-02 北京蓝晶微生物科技有限公司 Composition de polyhydroxyalcanoate contenant de l'acide polybasique et corps moulé en polyhydroxyalcanoate

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0488617A2 (fr) 1990-11-26 1992-06-03 Showa Highpolymer Co., Ltd. Une méthode pour la préparation de polyester saturé
WO1992009654A2 (fr) 1990-11-30 1992-06-11 Eastman Kodak Company Melanges de copolyesters aliphatiques aromatiques et d'esters/de polymeres de cellulose
EP0539541A1 (fr) 1991-05-03 1993-05-05 Novamont Spa Compositions polymeres biodegradables a base d'amidon et de polymeres thermoplastiques.
EP0575349A1 (fr) 1991-02-20 1993-12-29 NOVAMONT S.p.A. Compositions polymeres biodegradables a base d'amidon et de polymeres thermoplastiques
US5281691A (en) 1992-06-19 1994-01-25 Eastman Kodak Company Poly(3-hydroxyalkanoates)
EP0652910A1 (fr) 1992-08-03 1995-05-17 NOVAMONT S.p.A. Composition polymere biodegradable
WO1996015173A1 (fr) 1994-11-15 1996-05-23 Basf Aktiengesellschaft Polymeres biodegradables, leur procede de production et leur utilisation pour la fabrication de corps moules biodegradables
US5883199A (en) 1997-04-03 1999-03-16 University Of Massachusetts Polyactic acid-based blends
WO1999064498A1 (fr) 1998-06-09 1999-12-16 Metabolix, Inc. Procedes et appareil de production de suspensions de polymeres amorphes
US20040225269A1 (en) 2003-05-08 2004-11-11 The Procter & Gamble Company Molded or extruded articles comprising polyhydroxyalkanoate copolymer and an environmentally degradable thermoplastic polymer
WO2008010296A1 (fr) 2006-07-21 2008-01-24 Kaneka Corporation Micro-organisme doté d'un gène remplacé et procédé de production de polyester à l'aide dudit micro-organisme
WO2009024294A1 (fr) 2007-08-17 2009-02-26 Basf Se Mannheimia succini producens ddl producteur d'acide succinique microbien
WO2009127556A1 (fr) 2008-04-15 2009-10-22 Basf Se Procédé de production en continu de polyesters biodégradables
WO2009127555A1 (fr) 2008-04-15 2009-10-22 Basf Se Procédé de fabrication en continu de polyesters biodégradables
WO2010034711A1 (fr) 2008-09-29 2010-04-01 Basf Se Polyesters aliphatiques

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0488617A2 (fr) 1990-11-26 1992-06-03 Showa Highpolymer Co., Ltd. Une méthode pour la préparation de polyester saturé
WO1992009654A2 (fr) 1990-11-30 1992-06-11 Eastman Kodak Company Melanges de copolyesters aliphatiques aromatiques et d'esters/de polymeres de cellulose
EP0575349A1 (fr) 1991-02-20 1993-12-29 NOVAMONT S.p.A. Compositions polymeres biodegradables a base d'amidon et de polymeres thermoplastiques
EP0539541A1 (fr) 1991-05-03 1993-05-05 Novamont Spa Compositions polymeres biodegradables a base d'amidon et de polymeres thermoplastiques.
US5281691A (en) 1992-06-19 1994-01-25 Eastman Kodak Company Poly(3-hydroxyalkanoates)
EP0652910A1 (fr) 1992-08-03 1995-05-17 NOVAMONT S.p.A. Composition polymere biodegradable
WO1996015173A1 (fr) 1994-11-15 1996-05-23 Basf Aktiengesellschaft Polymeres biodegradables, leur procede de production et leur utilisation pour la fabrication de corps moules biodegradables
EP0792309A1 (fr) 1994-11-15 1997-09-03 Basf Aktiengesellschaft Polymeres biodegradables, leur procede de production et leur utilisation pour la fabrication de corps moules biodegradables
US5883199A (en) 1997-04-03 1999-03-16 University Of Massachusetts Polyactic acid-based blends
WO1999064498A1 (fr) 1998-06-09 1999-12-16 Metabolix, Inc. Procedes et appareil de production de suspensions de polymeres amorphes
US20040225269A1 (en) 2003-05-08 2004-11-11 The Procter & Gamble Company Molded or extruded articles comprising polyhydroxyalkanoate copolymer and an environmentally degradable thermoplastic polymer
WO2008010296A1 (fr) 2006-07-21 2008-01-24 Kaneka Corporation Micro-organisme doté d'un gène remplacé et procédé de production de polyester à l'aide dudit micro-organisme
WO2009024294A1 (fr) 2007-08-17 2009-02-26 Basf Se Mannheimia succini producens ddl producteur d'acide succinique microbien
WO2009127556A1 (fr) 2008-04-15 2009-10-22 Basf Se Procédé de production en continu de polyesters biodégradables
WO2009127555A1 (fr) 2008-04-15 2009-10-22 Basf Se Procédé de fabrication en continu de polyesters biodégradables
WO2010034711A1 (fr) 2008-09-29 2010-04-01 Basf Se Polyesters aliphatiques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JAMES G. BRENNAN: "Food Processing Handbook", 2005, WILEY- VCH

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024087609A1 (fr) * 2022-10-28 2024-05-02 北京蓝晶微生物科技有限公司 Composition de polyhydroxyalcanoate contenant de l'acide polybasique et corps moulé en polyhydroxyalcanoate

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