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WO2025215069A1 - Réutilisation de bioplastiques en polymérisation - Google Patents

Réutilisation de bioplastiques en polymérisation

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Publication number
WO2025215069A1
WO2025215069A1 PCT/EP2025/059688 EP2025059688W WO2025215069A1 WO 2025215069 A1 WO2025215069 A1 WO 2025215069A1 EP 2025059688 W EP2025059688 W EP 2025059688W WO 2025215069 A1 WO2025215069 A1 WO 2025215069A1
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WO
WIPO (PCT)
Prior art keywords
weight
polyester
biodegradable
solvent
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2025/059688
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English (en)
Inventor
Roberto Vallero
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novamont SpA
Original Assignee
Novamont SpA
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Filing date
Publication date
Application filed by Novamont SpA filed Critical Novamont SpA
Publication of WO2025215069A1 publication Critical patent/WO2025215069A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
    • C08J11/08—Recovery or working-up of waste materials of polymers without chemical reactions using selective solvents for polymer components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention relates to the chemical recycling of waste bioplastics, and in particular to the processing of biodegradable compositions comprising biopolymers for the selective recovery of polyesters suitable for reuse in polymerisation reactions. It also relates to a polymerisation process for obtaining biodegradable polyesters from polyesters selectively recovered from biodegradable plastics
  • biopolymers generally refers to biodegradable and/or bio-based polymers.
  • Biodegradable polymers are defined as polymers that are able to degrade once they have reached the end of their primary use and be organically recycled by nourishing microorganisms without generating an accumulation of waste in the environment.
  • Bio-based polymers are defined as those obtained from natural or renewable resources, that is from sources that, by their very nature, can be regenerated within the time scale of a human lifetime.
  • biodegradable bio-based polymers can be recycled in the recycling plants already used for their fossil-based counterparts, biodegradable polymers require specific alternative solutions depending on the characteristics of the polymers themselves.
  • the main technologies for the recycling of biopolymers currently include sorting, mechanical recycling, chemical recycling and depolymerisation by enzymes, which can be applied to postindustrial or post-consumer waste.
  • biodegradable items such as packaging films, bags and printed or thermoformed items for the food service industry may consist of one or more different biodegradable compositions, arranged for example in single or multiple layers, comprising different categories of biodegradable polymers, such as (aliphatic and/or aliphatic-aromatic) diacid-diol polyesters, polyhydroxy alkanoates, polymers of natural origin, together with fillers and/or other additives; such articles may also contain adhesives and inks.
  • biodegradable polymers such as (aliphatic and/or aliphatic-aromatic) diacid-diol polyesters, polyhydroxy alkanoates, polymers of natural origin, together with fillers and/or other additives; such articles may also contain adhesives and inks.
  • biodegradable polymers such as (aliphatic and/or aliphatic-aromatic) diacid-diol polyesters, polyhydroxy alkanoates, polymers of natural origin, together with fillers and/or other
  • EP 0 742 251 Bl allows PET to be recovered from polymer blends resulting from the recycling of plastics by first selectively separating the PVC and then the PET.
  • This process in addition to not allowing for the adequate removal of starch, involves multiple washes with different organic solvents.
  • this solvent selectively solubilises the biodegradable polyesters present (whether diacid-diol or hydroxyacid type), which can be separated from the waste bioplastic and reused in polymerisation reactions or in mechanical recycling, leaving a solid residue comprising starch and any insoluble additives such as fillers and/or other impurities.
  • the solvent can also be easily recovered and recycled in the process through simple evaporation. Polyesters can also be obtained in a further purified form for example by precipitation with environmentally-friendly polar non-solvents such as water or alcohols.
  • step 4) reusing the polyester obtained in step 3) in a polymerisation or thermoplastic conversion process, resulting in a biodegradable polymer composition.
  • the polymer composition fed to the process according to the invention contains one or more biodegradable polyesters and one or more further components chosen from a polymer of natural origin (preferably starch) and additives.
  • biodegradable polyesters are meant both polyhydroxy alkanoates and diacid-diol polyesters.
  • the latter are chosen from aliphatic polyesters, aromatic polyesters, aliphatic/aromatic polyesters or mixtures thereof.
  • the polyhydroxyalkanoates are preferably selected from the group consisting of the lactic acid polyesters, poly-s-caprolactone, polyhydroxybutyrate (PHB), polyhydroxybutyrate-valerate (PHBV), polyhydroxybutyrate-propanoate polyhydroxybutyrate -hexanoate (PHBH), polyhydroxybutyrate-decanoate, polyhydroxybutyrate-dodecanoate, polyhydroxybutyratehexadecanoate, polyhydro xybutyrate-octadecanoate, poly-3-hydroxybutyrate-4- hydroxybutyrate or mixtures thereof.
  • the polyhydroxyalkanoate in the starting composition comprises at least 70% by weight of one or more lactic acid polyesters.
  • said lactic acid polyesters are selected from the group consisting of poly L-lactic acid, poly D-lactic acid, poly D-L lactic acid stereo complex, copolymers comprising more than 50% in moles of said lactic acid polyesters or mixtures thereof.
  • lactic acid polyesters containing at least 95% by weight of repeating units derived from L-lactic or D-lactic acid or combinations thereof.
  • the lactic acid polyester comprises at least 95% by weight of units derived from L-lactic acid, ⁇ 5% by weight of repetitive units derived from D- lactic acid and has a melting temperature in the range 135-175°C.
  • Said diacid-diol polyester is chosen from aliphatic polyesters, aromatic polyesters, aliphatic/aromatic polyesters or mixtures thereof; preferably it is an aliphatic/aromatic polyester and/or an aliphatic polyester.
  • this preferably comprises: a) a dicarboxylic component comprising al) units derived from at least one aromatic dicarboxylic acid and a2) units derived from at least one saturated or unsaturated (preferably saturated) aliphatic dicarboxylic acid, b) a diol component comprising units derived from at least one saturated or unsaturated (preferably saturated) aliphatic diol.
  • aromatic dicarboxylic acids of component al) are preferably selected from aromatic dicarboxylic acids of the phthalic acid type, preferably terephthalic acid or isophthalic acid, more preferably terephthalic acid and heterocyclic aromatic dicarboxylic compounds, preferably 2,5-furandicarboxylic acid, 2,4-furandicarboxylic acid, 2,3 -furandicarboxylic acid, 3,4-furandicarboxylic acid, more preferably 2,5-furandicarboxylic acid, their esters, salts and mixtures thereof.
  • aromatic dicarboxylic acids of the phthalic acid type preferably terephthalic acid or isophthalic acid, more preferably terephthalic acid and heterocyclic aromatic dicarboxylic compounds, preferably 2,5-furandicarboxylic acid, 2,4-furandicarboxylic acid, 2,3 -furandicarboxylic acid, 3,4-furandicarboxylic acid, more preferably 2,5-fur
  • aromatic dicarboxylic acids comprise:
  • the aliphatic dicarboxylic acids of component a2) are preferably selected from saturated C2- C24, preferably C4-C13, more preferably C4-C11, dicarboxylic acids, their C1-C24, more preferably C1-C4, alkyl esters, their salts and mixtures thereof.
  • the saturated aliphatic dicarboxylic acids are selected from: succinic acid, 2-ethylsuccinic acid, glutaric acid, 2-methylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, brassylic acid and their Cl-24 alkyl esters.
  • the saturated aliphatic dicarboxylic acids comprise succinic acid, adipic acid, azelaic acid, sebacic acid or mixtures thereof.
  • any unsaturated aliphatic dicarboxylic acids in component a2) are preferably selected from itaconic acid, fumaric acid, maleic acid, 4-methylene-pimelic acid, 3,4-bis(methylene) nonandioic acid, 5-methylene-nonandioic acid, their C1-C24, preferably C1-C4, alkyl esters, their salts and mixtures thereof.
  • the unsaturated aliphatic dicarboxylic acids consist of itaconic acid or comprise mixtures comprising at least 50% in moles, preferably more than 60% in moles, more preferably more than 65% in moles of itaconic acid its C1-C24, preferably C1-C4, esters.
  • saturated aliphatic diols in component b) are preferably selected from 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11- undecanediol, 1,12-dodecanediol 1,13-tridecanediol, 1,4-cyclohexanedimethanol, neopentylglycol, 2-methyl- 1,3-propanediol, dianhydrosorbitol, dianhydromannitol, dianhydroiditol, cyclohexanediol, cyclohexaned
  • the diol component comprises at least 50% in moles of one or more diols chosen from 1,2- ethanediol, 1,3-propanediol, 1,4-butanediol. More preferably, the diol component comprises, or consists of, 1,4-butanediol.
  • any unsaturated aliphatic diols of component b are preferably selected from cis 2-buten-l,4-diol, trans 2-buten-l,4-diol, 2-butyn-l,4-diol, cis 2-penten-l,5-diol, trans 2- penten-l,5-diol, 2-pentyn-l,5-diol, cis 2-hexen-l,6-diol, trans 2-hexen-l,6-diol, 2-hexyn-l,6- diol, cis 3-hexen-l,6-diol, trans 3-hexen-l,6-diol, 3-hexen-l,6-diol, 3-hexyn-l,6-diol.
  • this preferably comprises: c) a dicarboxylic component comprising units derived from at least one saturated or unsaturated aliphatic dicarboxylic acid, d) a diol component comprising units derived from at least one saturated or unsaturated aliphatic diol.
  • the saturated aliphatic dicarboxylic acids in component c) are preferably present in amounts of 95 to 100% in moles with respect to the total dicarboxylic component; they are preferably chosen from saturated C2-C24, preferably C4-C13, more preferably C4-C11, dicarboxylic acids, their C1-C24, preferably C1-C4, alkyl esters, their salts and mixtures thereof.
  • the saturated aliphatic dicarboxylic acids are chosen from succinic acid, 2-ethylsuccinic acid, glutaric acid, 2-methylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, hexadecanedioic acid, octadecanedioic acid and Cl -24 alkyl esters thereof.
  • the dicarboxylic component comprises, or consists of, units derived from succinic acid.
  • Any unsaturated aliphatic dicarboxylic acids in component c) are present in an amount preferably from 0 to 5% in moles relative to the total dicarboxylic component; they are preferably chosen from itaconic acid, fumaric acid, maleic acid, 4-methyl-pimelic acid, 3,4-bis (methylene) nonandioic acid, 5-methylene-nonandioic acid, their C1-C24, preferably C1-C4, alkyl esters, their salts and mixtures thereof.
  • the unsaturated aliphatic dicarboxylic acids comprise itaconic acid or comprise mixtures comprising at least 50% in moles, preferably more than 60% in moles, more preferably more than 65% in moles, of itaconic acid and its C1-C24, preferably C1-C4, esters.
  • saturated aliphatic diols in component d) are preferably present in quantities of 95 to 100% in moles with respect to the total diol component; they are preferably chosen from 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5- pentanediol, 1,6-hexanediol, 1,7 -heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11 -undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,4-cyclohexanediol neopentylglycol, 2-methyl- 1,3-propanediol, dianhydrosorbitol, dianhydromann
  • the diol component comprises or consists of 1,4-butanediol.
  • the unsaturated aliphatic diols in component d) are preferably present in quantities of 0 to 5% in moles with respect to the total diol component; they are preferably selected from cis 2-buten-l,4-diol, trans 2-buten-l,4-diol, 2-butyn-l,4-diol, cis 2- penten-l,5-diol, trans 2-penten-l,5-diol, 2-pentyn-l,5-diol, cis 2-hexen-l,6-diol, trans 2-hexen- 1,6-diol, 2-hexyn-l,6-diol, cis 3-hexen-l,6-diol, trans 3-hexen-l,6-diol, 3-hexen-l,6-diol, 3-hexyn-l,6-diol.
  • the biodegradable composition fed to the process according to the present invention comprises one or more diacid-diol polyesters selected from the group consisting of: poly( 1,4-butylene succinate), poly( 1,4-butylene succinate-co-1,4- butylene adipate), poly(l,4-butylene succinate-co-l,4-butylene azelate), poly(l,4-butylene adipate-co- 1,4-butylene terephthalate), poly(l,4-butylene succinate-co-l,4-butylene terephthalate), poly( 1,4-butylene azelate-co- 1,4-butylene terephthalate), poly( 1,4-butylene brassylate-co- 1 ,4-butylene terephthalate), poly( 1 ,4-butylene sebacate-co- 1 ,4-butylene terephthalate), poly( 1 ,4-butylene
  • the aliphatic and/or aliphatic/aromatic polyesters (known as diacid-diol polyesters) of the biodegradable composition undergoing the process according to the present invention may further comprise repetitive units derived from at least one hydroxy acid in an amount of, for example, between 0 and 49%, preferably between 0 and 30% in moles, relative to the total moles of the dicarboxylic component.
  • hydroxy acids are glycolic acid, hydroxybutyric acid, hydroxycaproic acid, hydroxy valeric acid, 7-hydroxyheptanoic acid, 8- hydroxycaproic acid, 9-hydroxynonanoic acid, lactic acid or lactide.
  • Long molecules with two non-terminal functional groups may also be present, typically in quantities of no more than 10% in moles to the total moles of the dicarboxylic component.
  • Examples are dimer acids, ricinoleic acid and acids with epoxy functional groups, and also polyoxyethylenes with molecular weights between 200 and 10000.
  • Diamines, amino acids, and amino-alcohols may also be present in percentages of up to 30% in moles with respect to the total moles of the dicarboxylic component.
  • One or more polyfunctional molecules may also be present, typically in quantities of between 0.01 and 3% in moles to the total moles of the dicarboxylic component.
  • these molecules are glycerol, pentaerythritol, trimethylolpropane, citric acid, dipentaerythritol, monoanhydrosorbitol, monohydromannitol, acid triglycerides, polyglycerols, etc.
  • the biodegradable composition subjected to the process comprises at least one polyhydroxy alkanoate and at least one polyester from diacid- diol, in any proportion; for example, it comprises mixtures comprising from 1 to 99% by weight, preferably from 10% to 70% by weight, of polyhydroxyalkanoate, and from 99 to 1%, preferably from 30% to 60% by weight, of polyester from diacid-diol relative to the total weight of the mixture.
  • the biodegradable composition subjected to the process further comprises from 0 to 5% by weight, preferably from 0.01 to 0.45% by weight, relative to the total composition, of a cross-linking agent and/or chain extender having two or more functional groups, preferably chosen from peroxide groups, epoxy groups and isocyanate groups.
  • Examples of compounds having two or more functional groups containing isocyanate groups are p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4- diphenylmethane diisocyanate, l,3-phenylene-4-chloro diisocyanate, 1,5 -naphthalene diisocyanate, 4,4-diphenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 3-methyl-4,4'-diphenylmethane diisocyanate, diphenyl ester diisocyanate, 2,4-cyclohexane diisocyanate, 2,3 -cyclohexane diisocyanate l-methyl-2,4-cyclohexyl diisocyanate, 1-methyl- 2,6-cyclohexyl diisocyanate, bis-(cyclohexyl is
  • Examples of compounds having two or more functional groups carrying peroxide groups are benzoyl peroxide, lauroyl peroxide, isononanoyl peroxide, di-(t-butylperoxyisopropyl)benzene, t-butyl peroxide, dicumyl peroxide, alpha, alpha-di(t-butylperoxy)diisopropylbenzene, 2,5- dimethyl-2,5-di(t-butylperoxy)hexane, t-butyl cumyl peroxide, di-t-butyl peroxide, 2,5- dimethyl-2,5-di(t-butylperoxy)hex-3-yne, di(4-t-butylcyclohexyl)peroxydicarbonate, dicetyl peroxydicarbonate, dimiristyl peroxydicarbonate, 3,6,9-trimethyl-3,6,9-trimethyl-l,4,7- triperoxon
  • Examples of compounds with two or more functional groups carrying epoxy groups are polyepoxides from epoxidised oils and/or styrene-glycidyl ether-methyl methacrylate and/or glycidyl ether-methyl methacrylate.
  • the polymer composition subjected to the process according to the present invention also optionally includes one or more polymers of natural origin.
  • Said polymer of natural origin is advantageously selected from starch, chitin, chitosan, alginates, proteins such as gluten, zein, casein, collagen, gelatin, natural gums, cellulose (also in nanofibrils) and pectin.
  • Starch is preferred.
  • starch is used here to refer to all types of starch, that is: flour, native starch, hydrolysed starch, destructured starch, gelatinised starch, plasticised starch, thermoplastic starch, biofillers comprising complexed starch or mixtures of these.
  • starches such as potato, maize, tapioca and pea starch. Included in the definition are starches that can be easily deconstructed and have high initial molecular weights, such as potato or maize starch.
  • the starch may be present both as such and in a chemically modified form, such as in the form of starch esters with a degree of substitution between 0.2 and 2.5, hydroxypropyl starch, and starch modified with fatty chains.
  • the biodegradable composition typically also includes 1-40% by weight, relative to the weight of the starch, of one or more plasticisers chosen from water and polyols having 2 to 22 carbon atoms. As far as water is concerned, this may also be the water naturally present in starch.
  • plasticisers chosen from water and polyols having 2 to 22 carbon atoms.
  • this may also be the water naturally present in starch.
  • polyols polyols having 1 to 20 hydroxyl groups and/or containing 2 to 6 carbon atoms, their ethers, thioethers and organic and inorganic esters are preferred.
  • polyols examples include glycerol, diglycerol, poly glycerol, pentaerythritol, ethoxylated poly glycerol, ethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3- propanediol, 1,4-butanediol, neopentylglycol, sorbitol, sorbitol monoacetate, sorbitol diacetate, sorbitol monoethoxylate, sorbitol diethoxylate, and mixtures thereof. Examples of mixtures include between 2 and 90% by weight glycerol.
  • the polymer composition processed according to the present invention also optionally comprises one or more additional polymers other than the polyhydroxyalkanoates, diacid-diol polyesters and polymers of natural origin listed above.
  • These additional polymers are, for example, selected from the group consisting of vinyl polymers, aromatic diacid diol polyesters, polyamides, polyurethanes, polyureas, polycarbonates and mixtures thereof.
  • vinyl polymers include: polyethylene, polypropylene and their copolymers, polyvinyl alcohol and its copolymers such as butenediol/vinyl alcohol copolymer, polyvinyl acetate, polyethylene vinyl acetate and polyethylene vinyl alcohol, polystyrene, chlorinated vinyl polymers, poly acrylates.
  • Chlorinated vinyl polymers include polyvinyl chloride, polyvinylidene chloride, polyethylene chloride, poly(vinyl chloride - vinyl acetate), poly(vinyl chloride - ethylene), poly(vinyl chloride - propylene), poly(vinyl chloride - styrene), poly(vinyl chloride - isobutylene) as well as copolymers in which polyvinyl chloride accounts for more than 50% in moles. Such copolymers may be random, block or alternating.
  • polycarbonates that may be present are, for example, selected from the group consisting of polyalkylene carbonates, preferably polyethylene carbonates, polypropylene carbonates, polybutylene carbonates, mixtures thereof and both random and block copolymers.
  • polyethers examples are those selected from the group consisting of polyethylene glycols, polypropylene glycols, polybutylene glycols, their copolymers and mixtures thereof.
  • diacid diol polyesters other than those described above are concerned, these for example comprise a dicarboxylic component comprising, with respect to the total dicarboxylic component, 100% in moles of units derived from at least one aromatic dicarboxylic acid and a diol component comprising units derived from at least one saturated or unsaturated aliphatic diol.
  • said aromatic dicarboxylic acids and aliphatic diols are selected from those described above for the aliphatic-aromatic polyester of the composition according to the present invention.
  • the biodegradable composition according to the present invention optionally also contains one or more additives selected from the group consisting of fillers, plasticisers, UV stabilisers, lubricants, nucleating agents, surfactants, antistatic agents, pigments, flame retardant agents, compatibilising agents, lignin, organic acids, antioxidants, anti-mould agents, waxes, process aids. Inks and adhesives may also be present.
  • Said fillers are preferably selected from kaolin, wollastonite, barytes, clay, talc, calcium and magnesium carbonates, iron and lead carbonates, aluminium hydroxide, diatomaceous earth, aluminium sulfate, barium sulfate, silica, mica, titanium dioxide and mixtures thereof.
  • Such fillers such as talc, calcium carbonate or mixtures thereof, are typically present in the form of particles with an arithmetic mean diameter greater than 1 micron, measured along the major axis of the particle.
  • plasticisers in addition to the plasticisers preferably used for the preparation of de- structured starch described above, there may be one or more plasticisers selected from the group consisting of phthalates, such as, for example, diisononyl phthalate, trimellitates, such as, for example, trimellitic acid esters with C4-C20 mono-alcohols preferably selected from the group consisting of n-octanol and n-decanol, and aliphatic esters of mono- and dicarboxylic acids with linear or branched C2-C8 alkenes, for example neopentylglycol.
  • the selected plasticisers are preferably present up to 10% by weight, relative to the total weight of the composition.
  • the lubricants are for example zinc stearate, calcium stearate, aluminium stearate and acetyl stearate.
  • the composition according to the present invention comprises up to 1% by weight of lubricants, more preferably up to 0.5% by weight, relative to the total weight of the composition.
  • nucleating agents include saccharin sodium salt, calcium silicate, sodium benzoate, calcium titanate, boron nitride, isotactic polypropylene, low molecular weight PLA.
  • Process aids include, for example, slip agents.
  • slip agents are meant, for example, biodegradable fatty acid amides such as oleamide, erucamide, ethylene-bis-stearylamide, fatty acid esters such as glycerol oleates or glycerol stearates, saponified fatty acids such as stearates.
  • Pigments may also be present, for example titanium dioxide, clays, copper phthalocyanine, titanium dioxide, silicates, iron oxides and hydroxides, carbon black, and magnesium oxide.
  • compatibilising agents are di- and/or poly-functional compounds bearing isocyanate, peroxide, carbodiimide, isocyanurate, oxazoline, epoxy, anhydride or divinyl ether groups and mixtures thereof.
  • additives are preferably present in quantities of up to 10% by weight and more preferably up to 6% and even more preferably up to 2% by weight, relative to the total weight of the composition.
  • biodegradable polyester or biodegradable composition means a polyester or polymer composition that is biodegradable according to EN 13432.
  • the biodegradable composition subjected to process step 1) according to the present invention preferably originates from post-industrial waste (i.e. waste from industrial production, processing or manufacturing processes) and/or from post-consumer waste, for example from the plastics waste stream after appropriate sorting operations.
  • post-industrial waste i.e. waste from industrial production, processing or manufacturing processes
  • post-consumer waste for example from the plastics waste stream after appropriate sorting operations.
  • biodegradable compositions originating from, for example, flexible biodegradable items, such as packaging films, bags, and rigid items, such as moulded or thermoformed foodservice items, either from industrial waste or end-of-life, to be recycled.
  • flexible biodegradable articles are predominantly made of polymer compositions comprising starch
  • rigid biodegradable articles are predominantly made of polymer compositions comprising fillers.
  • the recycling process according to the invention is particularly advantageous when applied to waste polymer compositions from closed-loop collection chains (e.g. waste collection at the point of sale or consumption).
  • Said wastes are optionally subjected to one or more preliminary operations to remove organic or inorganic debris and residues, to obtain a homogeneous composition and enlarge the surface area to facilitate subsequent process step 1).
  • Said preliminary operations are advantageously selected from the group consisting of washing, screening, separation, comminution and conditioning.
  • Washing allows any residual non-plastic materials to be separated out and is carried out in one or more successive operations, for example in a tank or by means of a water jet on a belt.
  • Basic solutions can also be used, for example to remove adhesive labels from the waste.
  • Separation or sorting operations may be carried out for example manually, by density, by optical, magnetic or electrostatic systems, by dissolution or flotation.
  • Comminution operations include for example shredding or crushing, grinding, pelletising, and are intended to reduce the size of the waste material and bring it to a homogenous size, facilitating subsequent process step 1).
  • a size of less than 5 cm, less than 2 cm or less than 1 cm is preferred.
  • Conditioning may comprise drying or drying operations, for example in a flow of air.
  • the order of these preliminary operations depends on the origin and type of polymer composition fed to the process.
  • step 1) of the process there is fed a biodegradable composition, the polymer component of which consists of, or mainly comprises, one or more aliphatic and/or aliphatic/aromatic (preferably aliphatic/aromatic) diacid diol polyesters and starch.
  • a biodegradable composition the polymer component of which consists of, or mainly comprises, one or more aliphatic and/or aliphatic/aromatic (preferably aliphatic/aromatic) diacid diol polyesters and starch.
  • step 1) of the process there is fed a biodegradable composition consisting of, or mainly comprising, one or more aliphatic and/or aliphatic-aromatic diacid polyesters and one or more fillers.
  • step 1) of the process there is fed a biodegradable composition consisting of, or mainly comprising, one or more polyhydroxy alkanoates, one or more aliphatic and/or aliphatic-aromatic (preferably aliphatic/aromatic) diacid diol polyesters and starch.
  • a biodegradable composition consisting of, or mainly comprising, one or more polyhydroxy alkanoates, one or more aliphatic and/or aliphatic-aromatic (preferably aliphatic/aromatic) diacid diol polyesters and starch.
  • a biodegradable composition comprising, or mainly comprising, one or more polyhydroxyalkanoates, one or more diacid diol polyesters of the aliphatic and/or aliphatic-aromatic and one or more fillers and/or other additives is fed to step 1) of the process.
  • step 1) of the process according to the present invention the polymer composition described above is brought into contact with a first solvent comprising from 50% to 100% by weight of cyclopentanone, resulting in a liquid fraction comprising at least one polyester and a solid fraction comprising starch and/or additives and any insoluble impurities.
  • a first solvent comprising from 50% to 100% by weight of cyclopentanone
  • said first solvent essentially comprises cyclopentanone; preferably this comprises at least 60%, at least 70%, at least 80%, at least 90% by weight of cyclopentanone.
  • cyclopentanone is a by-product of the polymerisation of adipic acid
  • the process is particularly advantageous when the polymer composition fed thereto comprises aliphatic or aliphatic-aromatic polyesters whose aliphatic component comprises adipic acid.
  • the cyclopentanone can in fact be obtained directly from the waste products of the polymerisation process in step 4), with a net saving in terms of cost and the environmental sustainability of the recycling process.
  • said first solvent comprises at least 50% of cyclopentanone and up to 40% by weight, more preferably 10 to 25% by weight, of linear, cyclic or branched, saturated or unsaturated aliphatic alcohols.
  • the amount by weight of aliphatic alcohols with respect to cyclopentanone is preferably less than 1:1, more preferably less than 1:1.5, more preferably less than 1:2.
  • Saturated and unsaturated linear aliphatic alcohols with preferably a C2-C8, more preferably C2-C4 chain are preferred, C4 chain alcohols being most preferred.
  • C4 chain alcohols being most preferred.
  • aliphatic C2-C6, more preferably C2-C4, chain diols are preferred, C4 chain diols being most preferred.
  • Examples of preferred alcohols and diols are ethanol, propanol, propan-2-ol, 1 -butanol, butan- 2-ol, 3-buten-l-ol, 1 -pentanol, 3-pentanol, hexanol, 1,2-ethanediol, 1,2-propanediol, 1,3- propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, cyclohexanediol, dialkylene glycols, 2-buten-l,4-diol, 2-penten-l,5-diol, 2-hexen-l,6-diol, 3- hexen-l,6-diol and mixtures thereof.
  • said first solvent advantageously comprises up to 15%, preferably up to 10%, more preferably up to 7%, even more preferably up to 5% by weight of water.
  • the said first solvent comprises at least 0.5% by weight of water, more advantageously at least 1 % by weight of water, with respect to the weight of the solvent.
  • said first solvent includes i. 50-100% cyclopentanone by weight, ii. 0-40% by weight, preferably 5-30% by weight, even more preferably 10-25% by weight of alcohols, diols or their mixtures, and iii. 0-15% by weight, preferably 0.5%-10% by weight, of water.
  • said first solvent includes other components that are miscible with cyclopentanone.
  • examples are ketones or cyclic ethers such as tetrahydrofuran (THF).
  • said first solvent is a mixture comprising one or more saturated and/or unsaturated aliphatic C2-C4 alcohols, THF and water, in addition to cyclopentanone.
  • Said mixture has been found to be surprisingly selective in the solubilisation of diacid-diol polyesters, possibly in a mixture with hydroxy-acid polyesters, removing them from the biodegradable compositions comprising them even when non-biodegradable polymers such as polyolefins are present.
  • Said mixture may also advantageously be obtained as a byproduct of the polymerisation of diacid-diol polyesters comprising adipic acid and butanediol.
  • One example of a preferred mixture includes cyclopentanone (50-65% by weight), 3-buten-l- ol (15-25% by weight), 1-butanol (5-10% by weight), isopropanol (3-7% by weight), water (2- 5% by weight) and THF (1-5% by weight).
  • step 1) of the process according to the present invention said polymer composition is brought into contact with said first solvent in such quantities as to achieve a mass/volume ratio of preferably less than 25%, more preferably 2% to 20%, to facilitate solubilisation of the polyester present in the biodegradable composition.
  • Said step 1) is preferably carried out at a temperature between 50°C and the boiling temperature of the solution at the working pressure, which is preferably between atmospheric pressure and 2-3 bar.
  • step 1) will vary mainly according to the temperature and pressure conditions used and the manner of contact between the solvent and the polymer composition, for example from a few minutes under drastic conditions to 3 hours under milder conditions.
  • Step 1) is therefore preferably performed in equipment suitable for facilitating solubilisation of the polyester from the polymer composition.
  • reactors allowing effective mixing and adequate heat exchange surfaces will preferably be used.
  • a liquid fraction comprising at least one polyester and a solid fraction comprising starch and/or additives and any insoluble impurities are obtained in the form of a mixture or suspension.
  • Said solid fraction is separated from said liquid fraction in step 2) of the process, from which it constitutes a solid residue.
  • Said solid residue advantageously undergoes one or more washes with solvent, preferably under the conditions in step 1), which is then repeated one or more times.
  • the separation in step 2) is performed by any solid/liquid separation technique known to those skilled in the art, after possible cooling of the mixture according to the technique selected, for example at a temperature below 70°C or 50°C.
  • the separation operations in process step 2) are for example chosen from the group consisting of filtering, centrifuging or settling.
  • Filtering comprises for example microfiltering and ultrafiltering; centrifuging is preferred.
  • Said separation operations are preferably conducted using continuous or discontinuous vertical or horizontal axis machines (for example centrifuges, settlers).
  • the polyesters separated into the liquid fraction during step 2) of the process according to the invention are then obtained by simple removal of the solvent during step 3), or undergo optional purification steps.
  • step 4 They are subsequently reused, either alone or mixed with other monomers, in step 4) for the production of biodegradable plastics.
  • thermoplastic transformation processes to obtain biodegradable articles
  • polymerisation processes to produce a biodegradable polyester
  • the operations of removing solvent during step 3) are carried out using techniques known to those skilled in the art. For example, one or more operations chosen from adsorption, reverse osmosis, crystallisation, evaporation, distillation are performed. Multi-effect evaporators, potentially with mechanical or thermal recompression, and low residence time devices such as falling or scraped films, are particularly suitable.
  • the process according to the invention comprises an optional step of adding a second solvent (or non-solvent) in which said polyester is insoluble.
  • a second solvent or non-solvent
  • insoluble is meant a solubility of the polyester of less than 2% by weight/volume in said second solvent, measured by contacting the polyester with the solvent (with a solvent:polyester ratio of 1:10 by weight) at 25 °C for 24 hours in the presence of a soluble fraction having a Number Average Molecular Weight ⁇ 10000 g/mol, preferably ⁇ 5000 g/mol.
  • Said second solvent is preferably chosen from water, preferably C2-C4 saturated or unsaturated aliphatic alcohols, and mixtures thereof. It is advantageously used in a ratio of 1:2 to 10:1 by volume with respect to the first solvent if the second solvent is water or includes water; in a ratio of 1:1 to 10:1 by volume with respect to the first solvent if the second solvent is an aliphatic alcohol.
  • Said second solvent causes the polyester to precipitate out, and it is advantageously separated from the solvent mixture during step 3) through at least one solid/liquid separation operation, keeping any additives and/or impurities such as inks and adhesives in solution.
  • the thus purified polyester is more suitable for subsequent use in polymerisation.
  • the polyester is obtained in solid form at the end of step 3) and is dried (i.e. has a residual solvent content advantageously below 1% by weight).
  • the polyester After removal of the solvent or solvents present, the polyester is fed to step 4) for reuse in a polymerisation or thermoplastic transformation process.
  • the process according to the invention thus allows a biodegradable polyester or biodegradable polymer composition to be obtained again.
  • step 3 The polyester obtained in step 3) advantageously undergoes an optional depolymerisation step before being sent to step 4).
  • Said optional depolymerisation step can be carried out by solvolysis, for example by glycolysis or hydrolysis processes.
  • the reuse in polymerisation in process step 4) takes place by means of the process described in patent application WO 2022/013309 Al, in particular by means of hydrolysis, separation and repolymerisation steps.
  • the depolymerisation product optionally obtained comprises a mixture of the monomers of the polyesters present in the initial biodegradable composition, for example hydroxy acids, dicarboxylic acids and diols selected from those described above as components of the polyester in the initial biodegradable composition, and/or oligomers thereof.
  • Said monomers are advantageously selected from the group consisting of: adipic acid, azelaic acid, sebacic acid, succinic acid, terephthalic acid, furandicarboxylic acid, lactic acid, 3- hydroxybutyric acid, 3 -hydroxy valeric acid and 3 -hydroxyhexanoic acid, 1,2-ethanediol, 1,3- propanediol, 1,4-butanediol.
  • oligomer means each set of repeating units in the polymer chain (i.e. hydroxyacid units and/or diacid-diol units) having a molecular weight of less than 5000, preferably less than 2000.
  • step 4) mixtures of monomers and/or oligomers obtained downstream of one of the above-mentioned polyester depolymerisation processes are fed to said polymerisation reactions in an amount from 1% to 100% by weight, preferably from 2% to 50% by weight and more preferably from 5% to 30% by weight, relative to the weight of the mixture subjected to polymerisation, resulting in a biodegradable polyester.
  • a further object of the present invention is therefore a process for preparing a biodegradable polyester comprising feeding at least one biodegradable polyester selectively recovered from a polymer composition, and/or oligomers and/or monomers thereof, in particular a mixture of oligomers and/or monomers of the polyester obtained according to steps 1 to 3 of the process in claim 1 to a polymerisation reaction (esterification and/or polycondensation) in an amount from 1% to 100% by weight, preferably from 2% to 50% by weight and more preferably from 5% to 30% by weight, with respect to the weight of the mixture undergoing polymerisation.
  • a polymerisation reaction esteerification and/or polycondensation
  • the weight of the polymerised mixture is calculated without taking into account any solvent (for example water) present.
  • the amount of hydroxy acids or their oligomers in the polymerisation mixture is advantageously between 0% and 25% by weight, preferably between 2 and 15% by weight, relative to the total weight of the polymerisation mixture.
  • the amount of hydroxyacid or its oligomers that may be present in the polymerisation mixture is kept within the range indicated by one of the removal operations described for step 3), or by fractional extraction or precipitation.
  • the amount of monomers and/or oligomers is kept within the range indicated by adding further virgin or recycled monomers to the polymerisation mixture.
  • the polymerisation according to the invention is carried out according to any of the processes known in the state of the art. In particular, it may advantageously be carried out by polycondensation. Examples of synthesis processes that may advantageously be used for the preparation of polyesters are described in international patent application WO 2016/050963.
  • the polymerisation reaction according to the invention preferably comprises: (i) Preparation of an oligomer product through an esterification and/or transesterification reaction of a mixture comprising: a) a dicarboxylic component comprising: al) 0-80% in moles, relative to the total dicarboxylic component, of units derived from at least one aromatic dicarboxylic acid and/or its ester, salt or derivative, and a2) 20-100% in moles, with respect to the total dicarboxylic component, of units derived from at least one aliphatic dicarboxylic acid and/or its ester, salt or derivative, and b) a diol component, c) a hydroxy acid component in an amount of 0% to 25% by weight, preferably 2% to 15% by weight, of the total weight of said mixture,
  • step (iii) granulation of the polyester obtained from step (ii).
  • aromatic dicarboxylic acids, aliphatic dicarboxylic acids and diols are preferably selected from those described above as being components of the polyesters in the biodegradable starting composition.
  • the polymerisation reaction may be performed in the presence of a suitable catalyst.
  • suitable catalysts are organometallic tin compounds, for example stannoic acid derivatives, titanium compounds, for example ortho-butyl titanate, aluminium compounds, for example Al-triisopropyl, Antimony and Zinc and Zirconium compounds and mixtures thereof.
  • Said polymerisation is advantageously preceded by complete removal of water from the polymerisation mixture to avoid interference in the esterification step.
  • branching agents, compatibilising or stabilising agents such as those described above are advantageously added as components of the biodegradable starting composition.
  • the polymerisation product obtained is a biodegradable polyester and can in turn be subjected to reactive extrusion for the preparation of biodegradable polymer compositions.
  • the invention therefore also relates to the polymers obtained by the process described above.
  • the invention relates to a biodegradable polymer composition comprising said polymers and optionally further biodegradable polymers and additives known in the art, for example chosen from those described above for the biodegradable composition subjected to the depolymerisation process
  • Said biodegradable polymer composition obtained according to the invention can advantageously be used in, for example, blown film, cast extrusion, thermoforming and injection moulding processes, resulting in biodegradable articles with application in, for example, the packaging, foodservice or agro-textile sectors.
  • the invention thus relates to biodegradable articles comprising said biodegradable polymer composition.
  • Examples of articles comprising the composition according to the present invention are:
  • - stretch film also cling film for food, for baling in agriculture and for wrapping waste;
  • thermoforming such as containers, trays, plates, beverage dispensing capsules and printed circuit boards for electronics.
  • the solvent was a mixture comprising cyclopentanone (59% by weight), 3-buten-l-ol (20% by weight), 1-butanol (7% by weight), isopropanol (5% by weight), water (4% by weight) and THF (2% by weight).
  • step 1 the reactor was allowed to cool to 30°C and the resulting mixture was centrifuged at 1800 RCF until complete separation (approx. 30 seconds; step 2). The supernatant liquid fraction was removed and 150 g of a second solvent (or non-solvent) consisting of water was added, resulting in quantitative precipitation of the polyester.
  • a second solvent or non-solvent
  • the separated polyester then underwent a second solid/liquid separation operation by centrifuging at 1800 RCF for 30 minutes.
  • the residual solvent was removed by drying at 90°C for 24 hours (step 3).
  • the polyester thus obtained was then reused in polymerisation as a partial replacement for the virgin raw materials according to the procedure described below (step 4).
  • the reactor temperature was gradually raised to 230°C over a period of 120 minutes and then kept constant until at least 95% of theoretical conversion had been achieved.
  • the distillation column and water condenser were replaced with an air condenser connected to a mechanical pump, and 8g of polyester recovered from step 3 and 0.075g of tetra n-butyl titanate (corresponding to 120ppm by weight of Ti with respect to the theoretical amount of polyester obtainable) were added to the reactor, the temperature was raised to 240°C over the course of 30 minutes and at the same time the pressure was reduced to below 2 mbar.
  • the solvent was a mixture of cyclopentanone (91% by weight) and water (9% by weight).
  • step 1 the reactor was allowed to cool to 30°C and the resulting mixture was centrifuged at 1800 RCF until complete separation (approx. 30 minutes; step 2). The supernatant liquid fraction was removed and 150 g water was added, resulting in quantitative precipitation of the polyester.
  • the separated polyester then underwent a second solid/liquid separation operation by centrifuging at 1800 RCF for 30 minutes.
  • the residual solvent was removed by drying at 90°C for 24 hours (step 3).
  • the polyester thus obtained was suitable for direct reuse in polymerisation as a partial replacement for virgin raw materials.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
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Abstract

La présente invention concerne un procédé permettant de réutiliser une composition polymère contenant au moins un polyester biodégradable, un amidon et/ou des additifs, le procédé comprenant les étapes consistant à : (1) mettre en contact ladite composition polymère biodégradable avec un premier solvant comprenant de 50 à 100 % en poids de cyclopentanone, obtenir une fraction liquide comprenant au moins un polyester biodégradable et une fraction solide comprenant de l'amidon insoluble et/ou des additifs ; (2) séparer ladite fraction liquide comprenant au moins un polyester de ladite fraction solide ; (3) éliminer au moins partiellement ledit premier solvant de ladite fraction liquide ; (4) réutiliser le polyester obtenu à partir de ladite fraction liquide dans un procédé de polymérisation ou de transformation thermoplastique, ce qui permet d'obtenir une composition polymère biodégradable. L'invention concerne en outre les polyesters biodégradables obtenus au moyen dudit procédé de réutilisation, les compositions polymères biodégradables les contenant, et les articles biodégradables obtenus à partir de ceux-ci.
PCT/EP2025/059688 2024-04-09 2025-04-09 Réutilisation de bioplastiques en polymérisation Pending WO2025215069A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0118240A2 (fr) 1983-02-18 1984-09-12 Warner-Lambert Company Procédure pour moulage par injection d'amidon
EP0327505A2 (fr) 1988-02-03 1989-08-09 Warner-Lambert Company Matériau polymériques fabriqués à partir d'amidon déstructuré et d'au moins un matériau polymérique synthétique thermoplastique
EP0742251B1 (fr) 1995-05-08 2003-01-29 M&G POLIMERI ITALIA SPA Procédé de recyclage de mélanges de polymères contenant du polyéthylène téréphtalate
US7576173B2 (en) * 2004-09-13 2009-08-18 Metabolix Inc. Single solvent polymer extraction methods
GB2528494A (en) * 2014-07-24 2016-01-27 Worn Again Footwear And Accessories Ltd Recycling process
WO2016050963A1 (fr) 2014-10-03 2016-04-07 Novamont S.P.A. Procédé de production de polyesters aliphatiques-aromatiques
WO2022013309A1 (fr) 2020-07-15 2022-01-20 Novamont S.P.A. Réutilisation de bioplastiques en polymérisation

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0118240A2 (fr) 1983-02-18 1984-09-12 Warner-Lambert Company Procédure pour moulage par injection d'amidon
EP0327505A2 (fr) 1988-02-03 1989-08-09 Warner-Lambert Company Matériau polymériques fabriqués à partir d'amidon déstructuré et d'au moins un matériau polymérique synthétique thermoplastique
EP0742251B1 (fr) 1995-05-08 2003-01-29 M&G POLIMERI ITALIA SPA Procédé de recyclage de mélanges de polymères contenant du polyéthylène téréphtalate
US7576173B2 (en) * 2004-09-13 2009-08-18 Metabolix Inc. Single solvent polymer extraction methods
GB2528494A (en) * 2014-07-24 2016-01-27 Worn Again Footwear And Accessories Ltd Recycling process
WO2016050963A1 (fr) 2014-10-03 2016-04-07 Novamont S.P.A. Procédé de production de polyesters aliphatiques-aromatiques
WO2022013309A1 (fr) 2020-07-15 2022-01-20 Novamont S.P.A. Réutilisation de bioplastiques en polymérisation

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