[ { "id": "pla", "label": "Aliphatic polyester · FOCUS", "family": "Aliphatic polyester", "focus": true, "name": "PLA, lactide copolymers & blends", "tagline": "Polylactide from fermentation-derived lactic acid, including stereocomplex PLA and PLA blends.", "scope": "L/D-lactide, stereocomplex PLA (scPLA), PLA/PBAT, PLA/PHA and PLA/PBS blends, nucleation, heat resistance and impact modification.", "what": [ "Polylactide (PLA) is an aliphatic polyester made from lactic acid. Auras et al. describe it as derived from renewable resources and biodegradable, and review it as a packaging material.", "PLA is also being developed for durable products. Nagarajan et al. describe the main obstacle as PLA's high strength but low toughness, together with limited heat resistance." ], "chemistry": [ "Lactic acid is chiral, so PLA can be built from L- and D-lactyl units. Blending poly(L-lactide) and poly(D-lactide) gives a stereocomplex; Tsuji reports that stereocomplexation improves mechanical properties, heat resistance and hydrolysis resistance.", "High-molar-mass PLA is usually made by ring-opening polymerisation (ROP) of lactide, the cyclic dimer of lactic acid (see Chemistry)." ], "production": [ "Fermentation gives lactic acid, which is converted to lactide and polymerised by ROP. Tin(II) 2-ethylhexanoate (Sn(Oct)₂) is the classic catalyst; Kowalski et al. show that polymerisation proceeds by monomer insertion into a tin–alkoxide bond formed with an alcohol co-initiator." ], "properties": [ "Jiang et al. report neat PLA as strong and stiff but brittle, and blend it with flexible PBAT to raise elongation and toughness at the cost of strength and modulus.", "Auras et al. report lower melting and glass transition temperatures for PLA than for PET and PS, and gas permeability lower than PS but higher than PET." ], "eol": { "bio_based_origin": "Made from renewable resources (Auras et al.). The bio-based share of a specific grade must be measured or declared separately.", "biodegradability": "Environment-dependent. Haider et al. report that PLA is basically non-degradable in seawater; McKeown and Jones report a slow biodegradation rate in the natural environment.", "compostability": "McKeown and Jones describe industrial composting of PLA as giving water and carbon dioxide. Home compostability is not assumed.", "recyclability": "Chemical recycling routes back to monomers and platform chemicals are reviewed by McKeown and Jones." }, "key_players": [], "applications": [ "packaging films and containers", "durable parts (research focus)" ], "challenges": [ "Brittleness and low toughness for durable use; balancing toughness against stiffness and heat resistance.", "Slow crystallisation, which limits heat resistance unless nucleated or annealed.", "Hydrolytic sensitivity during melt processing and in humid service." ], "challenge_links": [ "heat", "toughness", "processing", "moisture", "eol" ], "structures": [ "lactic-acid", "l-lactide", "pla-ru", "sn-oct2" ], "refs": [ "auras2004", "tsuji2005", "kowalski2000", "dechycabaret2004", "jiang2006", "nagarajan2016", "saeidlou2012", "lim2008", "mckeown2020", "haider2019", "noda2004", "garlotta2001", "farah2016", "raquez2013" ], "support": [ { "ref": "auras2004", "quote": "By being truly biodegradable, derived from renewable resources" }, { "ref": "auras2004", "quote": "PLA also has lower melting and glass transition temperatures than PET and PS." }, { "ref": "tsuji2005", "quote": "Stereocomplexation enhances the mechanical properties, the thermal‐resistance, and the hydrolysis‐resistance of PLA‐based materials." }, { "ref": "kowalski2000", "quote": "polymerization proceeds by simple monomer insertion into the" }, { "ref": "nagarajan2016", "quote": "a biobased and biodegradable polymer as polylactic acid (PLA) with its high strength but low toughness" }, { "ref": "jiang2006", "quote": "elongation and toughness were dramatically increased" }, { "ref": "haider2019", "quote": "poly(lactic acid) is basically non‐degradable in seawater" }, { "ref": "mckeown2020", "quote": "in the natural environment, PLA has a slow biodegradation rate" } ] }, { "id": "pha", "label": "Microbial polyester · FOCUS", "family": "Microbial polyester", "focus": true, "name": "PHA family & copolymers", "tagline": "Polyhydroxyalkanoates made inside bacterial cells, from PHB to copolymers such as PHBV and PHBHHx.", "scope": "PHB, PHBV, P3HB4HB, PHBHHx (PHBH), mcl-PHA and blends; fermentation feedstocks including sugars, oils, wastes, CO₂ and methane.", "what": [ "Polyhydroxyalkanoates (PHAs) are polyesters produced by many bacteria. Chen reviews their use as bioplastics, fine chemicals and biomaterials and describes an industrial value chain from fermentation to materials.", "Bugnicourt et al. report that most commercial PHAs come from pure cultures on renewable feedstocks such as glucose, while research is moving to waste streams as growth media." ], "chemistry": [ "The basic member is poly(3-hydroxybutyrate) (PHB). Copolymers add other hydroxyalkanoate units. Noda et al. report that medium-chain-length side groups lower crystallinity and melting temperature, which eases processing and adds ductility." ], "production": [ "Cells polymerise (R)-3-hydroxyacyl-CoA monomers and store the polymer as intracellular granules; the polymer is then extracted and compounded (see Chemistry for the PhaA/PhaB/PhaC pathway)." ], "properties": [ "Noda et al. describe PHA thermal decomposition as starting at relatively low temperature, so a lower melting point widens the processing window." ], "eol": { "bio_based_origin": "Produced by bacterial fermentation of renewable or waste feedstocks (Bugnicourt et al.).", "biodegradability": "Bugnicourt et al. report high biodegradability in different environments, not only in composting plants. Results remain specific to grade, thickness and environment.", "compostability": "Not assessed here for specific grades; check certification against EN 13432 or ISO 17088.", "recyclability": "Not assessed here." }, "key_players": [], "applications": [ "packaging", "moulded goods", "paper coatings", "non-woven fabrics", "films" ], "challenges": [ "Narrow processing window between melting and thermal degradation for PHB-rich grades.", "Cost and feedstock variability of fermentation and extraction.", "Slow crystallisation and ageing of PHB." ], "challenge_links": [ "processing", "toughness", "feedstock", "cost", "scale" ], "structures": [ "r-3hb", "phb-ru", "3hv", "4hb", "3hhx" ], "refs": [ "chen2009", "sudesh2000", "bugnicourt2014", "noda2004", "laycock2017" ], "support": [ { "ref": "chen2009", "quote": "PHA applications as bioplastics, fine chemicals, implant biomaterials, medicines and biofuels" }, { "ref": "bugnicourt2014", "quote": "Most commercially available PHAs are obtained with pure microbial cultures grown on renewable feedstocks" }, { "ref": "bugnicourt2014", "quote": "high biodegradability in different environments, not just in composting plants" }, { "ref": "noda2004", "quote": "effectively lowers the crystallinity and the melt temperature" }, { "ref": "noda2004", "quote": "the thermal decomposition temperature of PHAs is then relatively low" } ] }, { "id": "pef", "label": "Furanic polyester · FOCUS", "family": "Furanic polyester", "focus": true, "name": "PEF and furan polyesters", "tagline": "Poly(ethylene furanoate) from 2,5-furandicarboxylic acid and ethylene glycol, and its furanoate relatives.", "scope": "FDCA/FDME + MEG; PEF copolymers and blends; also PBF, PTF and PPF.", "what": [ "Poly(ethylene furanoate) (PEF) is the furan analogue of PET. Burgess et al. describe it as a fully biosourced alternative to PET with greatly improved barrier properties.", "Nakajima et al. classify PEF as a new bio-based polymer, as opposed to upgraded biodegradable polyesters (PLA, PHA) and drop-in analogues (bio-PET)." ], "chemistry": [ "Burgess et al. attribute PEF's lower gas permeability to suppressed furan ring-flipping, which slows diffusion, rather than to lower gas solubility." ], "production": [ "Eerhart et al. model PEF production in three units - fructose from corn starch, conversion of fructose into furanics, and oxidation to FDCA followed by polymerisation with ethylene glycol." ], "properties": [ "Burgess et al. report greatly improved barrier and attractive thermal and mechanical properties relative to PET. Specific values belong in the property table only with a quote and DOI." ], "eol": { "bio_based_origin": "Can be fully bio-based when both FDCA and ethylene glycol are bio-based (Burgess et al.). Grade-specific content must be measured.", "biodegradability": "Not assessed here.", "compostability": "Not assessed here.", "recyclability": "Not assessed here; compatibility with PET recycling streams is an open question for the tracker." }, "key_players": [], "applications": [ "bottles and films (barrier packaging", "research and pilot)" ], "challenges": [ "Scale-up of FDCA and polymer production; cost against PET.", "Climate footprint depends on feedstock and system boundary (Eerhart et al. model cradle-to-grave cases)." ], "challenge_links": [ "barrier", "scale", "cost", "lca", "eol" ], "structures": [ "hmf", "fdca", "fdme", "eg", "pef-ru", "pdo", "tpa" ], "refs": [ "burgess2014", "sousa2015", "papageorgiou2014", "eerhart2012", "vanputten2013", "nakajima2017", "gandini2016" ], "support": [ { "ref": "burgess2014", "quote": "can provide a fully biosourced alternative to PET with greatly improved barrier properties and attractive thermal and mechanical properties" }, { "ref": "burgess2014", "quote": "the drastic permeability reduction results from a decrease in diffusion coefficient caused by a hindrance in furan ring-flipping" }, { "ref": "nakajima2017", "quote": "new biobased polymers such as poly(ethylene 2,5-furandicarboxylate) (PEF)" }, { "ref": "eerhart2012", "quote": "the oxidation to the monomer 2,5-furandicarboxylic acid (FDCA) and polymerization with ethylene glycol (EG) into PEF" } ] }, { "id": "bio-polyesters", "label": "Aliphatic/semi-aromatic polyesters", "family": "Aliphatic and semi-aromatic polyesters", "focus": false, "name": "Other bio-based polyesters", "tagline": "Bio-based PBS/PBSA, bio-content PBAT, isosorbide polyesters and chemically recyclable lactone polymers.", "scope": "bio-PBS/PBSA, bio-content PBAT, isosorbide polyesters (PEIT), poly(alkylene furanoate) relatives, chemically recyclable lactones (for example from α-methylene-γ-butyrolactone).", "what": [ "Poly(butylene succinate) (PBS) and its copolymers are biodegradable polyesters made from succinic acid and butanediol (Xu and Guo). Either monomer can come from fossil or bio-based routes, so the bio-based share is grade-specific.", "PBAT is made by polycondensation of butanediol, adipic acid and terephthalic acid (Jian et al.). It is biodegradable; bio-based content depends on which monomers are bio-sourced." ], "chemistry": [ "Hong and Chen showed polymers from γ-butyrolactone that can be depolymerised back to monomer, a design principle for chemically recyclable polyesters." ], "production": [ "Step-growth polycondensation of diacids and diols (see Chemistry)." ], "properties": [ "Xu and Guo report a wide thermoplastic processing window for PBS, suitable for extrusion, injection moulding, thermoforming and film blowing." ], "eol": { "bio_based_origin": "Grade-specific; depends on the origin of each monomer.", "biodegradability": "PBS and PBAT are described as biodegradable (Xu and Guo; Jian et al.). Environment matters (Haider et al.).", "compostability": "Not assessed here for specific grades.", "recyclability": "Lactone-based designs aim at chemical recycling to monomer (Hong and Chen; Coates and Getzler)." }, "key_players": [], "applications": [ "films", "injection-moulded and thermoformed parts" ], "challenges": [ "Separating bio-based content claims from biodegradability claims.", "Cost and scale of bio-succinic acid and bio-butanediol." ], "challenge_links": [ "claims", "cost", "eol" ], "structures": [ "succinic", "bdo", "adipic", "isosorbide", "mbl", "pbs-ru" ], "refs": [ "xu2010", "jian2020", "fenouillot2010", "hong2016", "coates2020", "robert2016", "haider2019" ], "support": [ { "ref": "xu2010", "quote": "production of the monomers succinic acid and butanediol" }, { "ref": "xu2010", "quote": "PBS has a wide temperature window for thermoplastic processing" }, { "ref": "jian2020", "quote": "PBAT has been commercialized by polycondensation reaction of butanediol (BDO), adipic acid (AA) and terephthalic acid (PTA)" } ] }, { "id": "polyamides", "label": "Polyamides", "family": "Polyamides", "focus": false, "name": "Bio-based polyamides", "tagline": "PA11 from castor oil, PA 5.X from bio-cadaverine, and long-chain polyamides from plant-oil diacids.", "scope": "PA11 (castor), PA 5.X (cadaverine), PA410, PA610, PA1010, new bio-diamines and diacids.", "what": [ "Winnacker and Rieger review bio-based polyamides and note that some, such as PA-11 (Rilsan), have been established for decades while many others remain at research stage.", "1,5-Diaminopentane (cadaverine) can be produced biotechnologically as a polyamide building block (Kind and Wittmann)." ], "chemistry": [ "Polyamides form by polycondensation of diamines with diacids, or of amino acids. Bio-based building blocks can add side groups, functionality or stereochemistry (Winnacker and Rieger)." ], "production": [ "Castor-derived 11-aminoundecanoic acid gives PA11; sebacic acid from castor is a diacid for PA610 and PA1010." ], "properties": [ "Hydrogen bonding between amide groups controls crystallinity and moisture uptake; values belong in the property table only with a quote and DOI." ], "eol": { "bio_based_origin": "Grade-specific; PA11 is built from a castor-derived monomer.", "biodegradability": "Not assessed here.", "compostability": "Not assessed here.", "recyclability": "Not assessed here." }, "key_players": [], "applications": [ "engineering parts (as cited in reviews)" ], "challenges": [ "Moisture uptake and dimensional stability.", "Feedstock concentration (castor) and cost." ], "challenge_links": [ "moisture", "feedstock", "cost" ], "structures": [ "aua", "ricinoleic", "sebacic", "cadaverine", "dmda", "pa11-ru" ], "refs": [ "winnacker2016", "kind2011", "nakajima2017" ], "support": [ { "ref": "winnacker2016", "quote": "While some biopolyamides are known for decades and well established (e.g., PA‐11, Rilsan)" } ] }, { "id": "polycarbonates", "label": "Polycarbonates", "family": "Polycarbonates", "focus": false, "name": "Isosorbide & CO₂-based polycarbonates", "tagline": "Polycarbonates from the sugar-derived diol isosorbide, and from epoxide/CO₂ ring-opening copolymerisation.", "scope": "Isosorbide polycarbonate; epoxide/CO₂ ROCOP (PPC, poly(limonene carbonate)).", "what": [ "Isosorbide is a rigid bicyclic diol derived from sugars; Fenouillot et al. review polymers made from it and its isomers.", "Grignard et al. review routes that use CO₂ as a C1 feedstock for polymers." ], "chemistry": [ "Byrne et al. report alternating copolymerisation of limonene oxide and CO₂ with zinc catalysts to a regioregular polycarbonate with more than 99 % carbonate linkages." ], "production": [ "Melt transesterification for isosorbide polycarbonates; catalytic ROCOP for CO₂-based polycarbonates (see Chemistry)." ], "properties": [ "Not summarised here; see checked developments and the property table." ], "eol": { "bio_based_origin": "Isosorbide is sugar-derived. CO₂-derived carbon is neither fossil nor biogenic by default; report it separately.", "biodegradability": "Not assessed here.", "compostability": "Not assessed here.", "recyclability": "Not assessed here." }, "key_players": [], "applications": [ "not summarised here" ], "challenges": [ "Accounting for CO₂-derived content separately from bio-based content.", "Catalyst cost and selectivity in ROCOP." ], "challenge_links": [ "claims", "lca", "scale" ], "structures": [ "isosorbide", "po", "limonene" ], "refs": [ "fenouillot2010", "grignard2019", "byrne2004" ], "support": [ { "ref": "byrne2004", "quote": "The copolymer contains >99% carbonate linkages" } ] }, { "id": "polyurethanes", "label": "Urethanes", "family": "Urethanes", "focus": false, "name": "Bio-polyurethanes & NIPU", "tagline": "Bio-based polyols and isocyanates, and non-isocyanate polyurethanes from cyclic carbonates and amines.", "scope": "Bio-polyols (castor, other plant oils, lignin), bio-isocyanates (for example PDI), cyclic carbonate + amine NIPU.", "what": [ "Conventional polyurethanes are made from polyisocyanates and polyols. Rokicki et al. review non-isocyanate polyurethanes (NIPU), which avoid isocyanates, and identify poly(hydroxy-urethane)s from cyclic carbonates and amines as the most developed route." ], "chemistry": [ "Polyaddition of a polyol to an isocyanate gives urethane links. In NIPU, an amine opens a cyclic carbonate to give a hydroxyurethane (see Chemistry)." ], "production": [ "Bio-polyols from plant oils or lignin; bio-based diisocyanates such as pentamethylene diisocyanate; cyclic carbonates such as glycerol carbonate." ], "properties": [ "Not summarised here." ], "eol": { "bio_based_origin": "Grade-specific; usually only part of the formulation is bio-based.", "biodegradability": "Not assessed here.", "compostability": "Not assessed here.", "recyclability": "Not assessed here." }, "key_players": [], "applications": [ "foams", "coatings", "adhesives (as cited)" ], "challenges": [ "Residual fossil components (isocyanate, amine) in \"bio-based\" PU.", "Slower cure and lower molar mass in many NIPU systems." ], "challenge_links": [ "claims", "processing", "durability" ], "structures": [ "glycerol-carbonate", "pdi", "ricinoleic", "coniferyl" ], "refs": [ "rokicki2015", "upton2016" ], "support": [ { "ref": "rokicki2015", "quote": "poly(hydroxy‐urethane)s, based upon multicyclic carbonates and aliphatic amines" } ] }, { "id": "thermosets", "label": "Networks", "family": "Networks", "focus": false, "name": "Bio-based thermosets & vitrimers", "tagline": "Epoxies from vanillin and plant oils, itaconic and furan networks, cardanol resins and dynamic covalent networks.", "scope": "Vanillin/lignin epoxies, epoxidised plant oils, itaconic and furan Diels–Alder networks, cardanol benzoxazines, dynamic covalent networks.", "what": [ "Auvergne et al. review bio-based thermosetting epoxies; Fache et al. describe vanillin as a key intermediate for bio-based polymers.", "Fortman et al. note that covalent cross-links make thermosets robust but prevent recycling into similar-value goods, and review recyclable cross-linked designs." ], "chemistry": [ "Montarnal et al. reported networks that are stable like thermosets yet can be reshaped in the melt - the vitrimer concept based on exchangeable covalent bonds.", "Robert and Friebel review itaconic acid as an unsaturated building block for renewable polyesters." ], "production": [ "Curing of bio-based epoxy monomers with hardeners; free-radical curing of unsaturated polyesters; dynamic exchange chemistry for vitrimers." ], "properties": [ "Not summarised here." ], "eol": { "bio_based_origin": "Grade-specific; hardeners and catalysts are often fossil-based.", "biodegradability": "Not assessed here.", "compostability": "Not assessed here.", "recyclability": "Conventional thermosets cannot be remelted; vitrimers and other dynamic networks are designed to be reprocessed (Fortman et al.)." }, "key_players": [], "applications": [ "composites", "coatings", "adhesives (as cited)" ], "challenges": [ "Long-term stability of inherently dynamic networks (Fortman et al.).", "Fossil hardeners and residual fossil content." ], "challenge_links": [ "durability", "claims", "eol" ], "structures": [ "vanillin", "itaconic", "furfuryl-alcohol", "cardanol" ], "refs": [ "auvergne2014", "fache2015", "fortman2018", "montarnal2011", "robert2016" ], "support": [ { "ref": "fortman2018", "quote": "they also prevent recycling of these materials into similar-value goods" }, { "ref": "fortman2018", "quote": "long-term environmental stability of inherently dynamic polymers" }, { "ref": "montarnal2011", "quote": "A polymer shows thermoset-like stability while displaying melt processability like that of a thermopolymer." } ] }, { "id": "natural-polymers", "label": "Modified natural polymers", "family": "Modified natural polymers", "focus": false, "name": "Cellulose, lignin, starch, protein & chitosan polymers", "tagline": "Materials made by modifying polymers that nature already builds - shown by representative units only.", "scope": "Cellulose esters, thermoplastic starch, lignin-based polymers, protein plastics, chitosan.", "what": [ "Klemm et al. describe cellulose as a linear homopolymer of D-glucose units with broad capacity for chemical modification, including cellulose esters and ethers.", "Zhang et al. report that starch becomes thermoplastic with plasticisers, heat and shear; Verbeek and van den Berg describe how proteins are extruded into thermoplastics with plasticisers.", "Upton and Kasko review polymers made from lignin, monolignols and lignin-derived chemicals such as vanillin." ], "chemistry": [ "Structures on this site show a representative repeat or model unit (glucopyranose, glucosamine, coniferyl alcohol, lysine). Natural polymers are never drawn as invented full structures." ], "production": [ "Esterification or etherification of cellulose; plasticisation of starch and proteins in extrusion; functionalisation of lignin." ], "properties": [ "Zhang et al. report that most thermoplastic starch has a glass transition between about -75 and 10 °C and tensile strength typically below 6 MPa." ], "eol": { "bio_based_origin": "Bio-based backbone; additives and modifying reagents may not be.", "biodegradability": "Grade- and modification-specific; not assessed here.", "compostability": "Not assessed here.", "recyclability": "Not assessed here." }, "key_players": [], "applications": [ "films", "coatings", "moulded goods (as cited)" ], "challenges": [ "Moisture sensitivity of starch and protein materials.", "Low tensile strength of thermoplastic starch." ], "challenge_links": [ "moisture", "toughness", "feedstock" ], "structures": [ "beta-glucose", "alpha-glucose", "coniferyl", "glucosamine", "l-lysine" ], "refs": [ "klemm2005", "zhang2014", "verbeek2010", "upton2016", "rinaudo2006", "isikgor2015" ], "support": [ { "ref": "klemm2005", "quote": "Formed by the repeated connection of D ‐glucose building blocks" }, { "ref": "zhang2014", "quote": "Starch exhibits usable thermoplastic properties when plasticizers, elevated temperatures, and shear are present." }, { "ref": "zhang2014", "quote": "TPS has low tensile properties, typically below 6 MPa in tensile strength (TS)." }, { "ref": "verbeek2010", "quote": "To avoid degradation, the required chain mobility is achieved by plasticizers." } ] }, { "id": "scope-review", "label": "Watch · scope review", "family": "Scope review", "focus": false, "name": "Drop-ins, mass balance & biocomposites", "tagline": "Bio-PE/PP/PET/PA, mass-balance attributed products and biofilled fossil polymers - tracked, never counted as new bio-based polymers.", "scope": "Bio-PE/PP/PET/PA, ISCC PLUS mass balance, biofilled fossil polymers. Shown separately and labelled.", "what": [ "Drop-in polymers have the same chemical structure as their fossil counterparts. Siracusa and Blanco review bio-PE, bio-PP and bio-PET as bio-based polymers analogous to petroleum-derived ones.", "Mass-balance attribution assigns a bio-based share to products through chain-of-custody bookkeeping. The European Commission's policy framework states that this method is not considered suitable for confirming the actual share of bio-based content.", "A bio-based filler in a fossil polymer matrix is a composite, not a new bio-based polymer." ], "chemistry": [ "Drop-ins share structures with incumbents (for example ethylene glycol and terephthalic acid in PET), so chemistry gives no new performance - the change is in feedstock." ], "production": [ "Bio-ethanol to ethylene for bio-PE; bio-based ethylene glycol for partly bio-based PET; mass-balance allocation in shared crackers." ], "properties": [ "Same as the fossil counterpart for true drop-ins." ], "eol": { "bio_based_origin": "Measured (radiocarbon) or attributed (mass balance) - always record which.", "biodegradability": "Bio-based plastics are not necessarily biodegradable or compostable (European Commission).", "compostability": "Not assumed.", "recyclability": "Usually the same stream as the fossil counterpart." }, "key_players": [], "applications": [ "same as incumbents" ], "challenges": [ "Claim accounting - measured bio-based carbon versus mass-balance attribution.", "Feedstock sustainability and land use." ], "challenge_links": [ "claims", "feedstock", "lca" ], "structures": [ "eg", "tpa" ], "refs": [ "siracusa2020", "nakajima2017", "lambert2017" ], "support": [ { "ref": "siracusa2020", "quote": "bio-based polymers analogous to petroleum-derived ones" } ] } ]