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Sustainable polymers from renewable resources

Nature volume 540, pages 354362 (15 December 2016) | Download Citation

Abstract

Renewable resources are used increasingly in the production of polymers. In particular, monomers such as carbon dioxide, terpenes, vegetable oils and carbohydrates can be used as feedstocks for the manufacture of a variety of sustainable materials and products, including elastomers, plastics, hydrogels, flexible electronics, resins, engineering polymers and composites. Efficient catalysis is required to produce monomers, to facilitate selective polymerizations and to enable recycling or upcycling of waste materials. There are opportunities to use such sustainable polymers in both high-value areas and in basic applications such as packaging. Life-cycle assessment can be used to quantify the environmental benefits of sustainable polymers.

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References

  1. 1.

    Natural resources: curse or blessing? J. Econ. Lit. 49, 366–420 (2011).

  2. 2.

    et al. Plastic waste inputs from land into the ocean. Science 347, 768–771 (2015).

  3. 3.

    , , , & Bioplastics science from a policy vantage point. New Biotechnol. 30, 635–646 (2013).

  4. 4.

    , & Present and future development in plastics from biomass. Biofuel. Bioprod. Bior. 4, 25–40 (2010).

  5. 5.

    in Environmental Impact of Polymers (eds Hamaide, T., Deterre, R., & Feller, J.-F.) Ch. 6, 91–107 (John Wiley, 2014).

  6. 6.

    , , & Preparation of thermoplastic polyurethanes using in situ generated poly(propylene carbonate)-diols. Polym. Chem. 3, 1215–1220 (2012). This paper demonstrates the use of polycarbonate polyols produced using carbon dioxide as a monomer to make polyurethanes.

  7. 7.

    , , & Life cycle assessment of CO2 capture and utilization: a tutorial review. Chem. Soc. Rev. 43, 7982–7994 (2014).

  8. 8.

    et al. Worldwide innovations in the development of carbon capture technologies and the utilization of CO2. Energy Environ. Sci. 5, 7281–7305 (2012).

  9. 9.

    , , , & Mechanistic aspects of the copolymerization of CO2 with epoxides using a thermally stable single-site cobalt(III) catalyst. J. Am. Chem. Soc. 131, 11509–11518 (2009).

  10. 10.

    et al. Copolymerization of CO2 and meso epoxides using enantioselective β-diiminate catalysts: a route to highly isotactic polycarbonates. Chem. Sci. 5, 4004–4011 (2014).

  11. 11.

    , , , & Adding value to power station captured CO2: tolerant Zn and Mg homogeneous catalysts for polycarbonate polyol production. ACS Catal. 5, 1581–1588 (2015). This paper highlights the use of carbon dioxide captured from a power station in the United Kingdom in the production of polycarbonate polyols.

  12. 12.

    , , , & Bio-based polycarbonate from limonene oxide and CO2 with high molecular weight, excellent thermal resistance, hardness and transparency. Green Chem. 18, 760–770 (2016). This paper demonstrates the production and scale-up of fully bio-based polylimonene carbonate, prepared through the copolymerization of carbon dioxide with epoxide, and evaluates its properties.

  13. 13.

    , & Copolymerization of carbon dioxide and epoxide. J. Polym. Sci. B 7, 287–292 (1969).

  14. 14.

    et al. Ring-opening copolymerization (ROCOP): synthesis and properties of polyesters and polycarbonates. Chem. Commun. 51, 6459–6479 (2015).

  15. 15.

    Making plastics from carbon dioxide: salen metal complexes as catalysts for the production of polycarbonates from epoxides and CO2. Chem. Rev. 107, 2388–2410 (2007).

  16. 16.

    , & CO2 copolymers from epoxides: catalyst activity, product selectivity, and stereochemistry control. Acc. Chem. Res. 45, 1721–1735 (2012).

  17. 17.

    , , & Recent advances in CO2/epoxide copolymerization — new strategies and cooperative mechanisms. Coordin. Chem. Rev. 255, 1460–1479 (2011).

  18. 18.

    & Discrete metal-based catalysts for the copolymerization of CO2 and epoxides: discovery, reactivity, optimization, and mechanism. Angew. Chem. Int. Edn Engl. 43, 6618–6639 (2004).

  19. 19.

    , & Optically active polycarbonates: asymmetric alternating copolymerization of cyclohexene oxide and carbon dioxide. J. Am. Chem. Soc. 121, 11008–11009 (1999).

  20. 20.

    & One-pot synthesis of a triblock copolymer from propylene oxide/carbon dioxide and lactide: intermediacy of polyol initiators. Angew. Chem. Int. Edn Engl. 52, 10602–10606 (2013).

  21. 21.

    , & Pre-rate-determining selectivity in the terpolymerization of epoxides, cyclic anhydrides, and CO2: a one-step route to diblock copolymers. Angew. Chem. Int. Edn Engl. 47, 6041–6044 (2008).

  22. 22.

    , , & Copolymerization and terpolymerization of carbon dioxide/propylene oxide/phthalic anhydride using a (salen)Co(III) complex tethering four quaternary ammonium salts. Beilstein J. Org. Chem. 10, 1787–1795 (2014).

  23. 23.

    , & Selective polymerization catalysis: controlling the metal chain end group to prepare block copolyesters. J. Am. Chem. Soc. 137, 12179–12182 (2015).

  24. 24.

    Poly(propylene carbonate), old copolymers of propylene oxide and carbon dioxide with new interests: catalysis and material properties. Pol. Rev. 48, 192–219 (2008).

  25. 25.

    & Life cycle assessment of polyols for polyurethane production using CO2 as feedstock: insights from an industrial case study. Green Chem. 16, 3272–3280 (2014). This paper presents a life-cycle assessment that compares the production of polyols for polyurethane manufacture from petrochemical sources or through partial substitution with carbon dioxide.

  26. 26.

    , , & Alternating copolymerization of limonene oxide and carbon dioxide. J. Am. Chem. Soc. 126, 11404–11405 (2004).

  27. 27.

    , , & Renewable polycarbonates and polyesters from 1,4-cyclohexadiene. Green Chem. 17, 300–306 (2015).

  28. 28.

    , & Synthesis and characterization of fully-biobased α,ω-dihydroxyl poly(limonene carbonate)s and their initial evaluation in coating applications. Eur. Polym. J. 67, 449–458 (2015).

  29. 29.

    et al. Stereocomplexed poly(limonene carbonate): a unique example of the cocrystallization of amorphous enantiomeric polymers. Angew. Chem. Int. Edn Engl. 54, 1215–1218 (2015). This paper demonstrates the production of polylimonene carbonate stereocomplexes through efficient catalysis.

  30. 30.

    , , & Cellulose: fascinating biopolymer and sustainable raw material. Angew. Chem. Int. Edn Engl. 44, 3358–3393 (2005).

  31. 31.

    et al. Synthesis of ethylene glycol and terephthalic acid from biomass for producing PET. Green Chem. 18, 342–359 (2016).

  32. 32.

    & Dehydration of ethanol to ethylene. Ind. Eng. Chem. Res. 52, 9505–9514 (2013).

  33. 33.

    Twenty years of PET bottle to bottle recycling — an overview. Resour. Conserv. Recycling 55, 865–875 (2011).

  34. 34.

    et al. Organocatalytic depolymerization of poly(ethylene terephthalate). J. Polym. Sci. A 49, 1273–1281 (2011).

  35. 35.

    et al. Techno-economic Feasibility of Large-scale Production of Bio-based Polymers in Europe. Technical Report EUR 22103 EN (European Communities, 2005).

  36. 36.

    & Recent progress in sustainable polymers obtained from cyclic terpenes: synthesis, properties, and application potential. ChemSusChem 8, 2455–2471 (2015).

  37. 37.

    & From monomers to polymers from renewable resources: recent advances. Prog. Polym. Sci. 48, 1–39 (2015).

  38. 38.

    The irruption of polymers from renewable resources on the scene of macromolecular science and technology. Green Chem. 13, 1061–1083 (2011).

  39. 39.

    , , , & Limonene: a versatile chemical of the bioeconomy. Chem. Commun. 50, 15288–15296 (2014).

  40. 40.

    , & Progress in renewable polymers from natural terpenes, terpenoids, and rosin. Macromol. Rapid Commun. 34, 8–37 (2013).

  41. 41.

    et al. Sustainable cycloolefin polymer from pine tree oil for optoelectronics material: living cationic polymerization of β-pinene and catalytic hydrogenation of high-molecular-weight hydrogenated poly(β-pinene). Polym. Chem. 5, 3222–3230 (2014).

  42. 42.

    & Alternating copolymers of limonene with methyl methacrylate: kinetics and mechanism. J. Macromol. Sci. A 40, 593–603 (2003).

  43. 43.

    et al. A high-performance recycling solution for polystyrene achieved by the synthesis of renewable poly(thioether) networks derived from D-limonene. Adv. Mater. 26, 1552–1558 (2014).

  44. 44.

    , , , & Design of renewable hydrogel release systems from fiberboard mill wastewater. Biomacromolecules 11, 1406–1411 (2010).

  45. 45.

    , , & Thermoplastic elastomers derived from menthide and tulipalin A. Biomacromolecules 13, 3833–3840 (2012). This paper describes how a monomer derived from wild mint (Mentha arvesis) can be copolymerized with one from a tulip (Tulipa gesneriana) to produce fully bio-based block copolyester thermoplastic elastomers.

  46. 46.

    , & Sustainable thermoplastic elastomers from terpene-derived monomers. ACS Macro Lett. 3, 717–720 (2014).

  47. 47.

    , & Long-chain aliphatic polymers to bridge the gap between semicrystalline polyolefins and traditional polycondensates. Chem. Rev. 116, 4597–4641 (2016).

  48. 48.

    et al. Chemical and technical aspects of the synthesis of chlorohydrins from glycerol. Ind. Eng. Chem. Res. 53, 8939–8962 (2014).

  49. 49.

    , , & Efficient selective and atom economic catalytic conversion of glycerol to lactic acid. Nature Commun. 5, 5084 (2014).

  50. 50.

    , , & Structure–properties relationship of fatty acid-based thermoplastics as synthetic polymer mimics. Polym. Chem. 4, 5472–5517 (2013).

  51. 51.

    Plenish high oleic soybean oil. The first biotech soybean product with consumer nutrition benefits. Agro Food Ind. High-Tech 24, 10–11 (2013).

  52. 52.

    , & Plant oil renewable resources as green alternatives in polymer science. Chem. Soc. Rev. 36, 1788–1802 (2007).

  53. 53.

    , & Catalytic isomerizing ω-functionalization of fatty acids. ACS Catal. 5, 5951–5972 (2015).

  54. 54.

    , , & Long-chain aliphatic polyesters from plant oils for injection molding, film extrusion and electrospinning. Green Chem. 16, 2008–2014 (2014). This paper reveals how plant oils can be converted by means of highly selective catalysis to produce polyesters with properties that mimic polyethylene.

  55. 55.

    , , , & Unsymmetrical α,ω-difunctionalized long-chain compounds via full molecular incorporation of fatty acids. ACS Catal. 5, 4519–4529 (2015).

  56. 56.

    et al. Polymers from fatty acids: poly(ω-hydroxyl tetradecanoic acid) synthesis and physico–mechanical studies. Biomacromolecules 12, 3291–3298 (2011).

  57. 57.

    , & Enzyme-catalysis breathes new life into polyester condensation polymerizations. Trends Biotechnol. 28, 435–443 (2010).

  58. 58.

    & Large-ring lactones from plant oils. Green Chem. 15, 2361–2364 (2013).

  59. 59.

    , , , & Mimicking (linear) low-density polyethylenes using modified polymacrolactones. Macromolecules 48, 4779–4792 (2015).

  60. 60.

    , , & Ring-opening metathesis polymerization of a naturally derived macrocyclic glycolipid. Macromolecules 46, 3293–3300 (2013).

  61. 61.

    et al. Synthetic polyester from algae oil. Angew. Chem. Int. Edn Engl. 53, 6800–6804 (2014).

  62. 62.

    , , & Self-healing and thermoreversible rubber from supramolecular assembly. Nature 451, 977–980 (2008).

  63. 63.

    , , & Silica-like malleable materials from permanent organic networks. Science 334, 965–968 (2011).

  64. 64.

    , & Self-healable polymer networks based on the cross-linking of epoxidised soybean oil by an aqueous citric acid solution. Green Chem. 15, 3360–3366 (2013).

  65. 65.

    & Plastics derived from biological sources: present and future: a technical and environmental review. Chem. Rev. 112, 2082–2099 (2012). This review provides a techno–environmental assessment of bio-based polymers and monomers.

  66. 66.

    , , & Synthetic polymers from sugar-based monomers. Chem. Rev. 116, 1600–1636 (2016).

  67. 67.

    & Technology development for the production of biobased products from biorefinery carbohydrates—the US Department of Energy's “Top 10” revisited. Green Chem. 12, 539–554 (2010).

  68. 68.

    , & An overview of polylactides as packaging materials. Macromol. Biosci. 4, 835–864 (2004).

  69. 69.

    , , & From lactic acid to poly(lactic acid) (PLA): characterization and analysis of PLA and its precursors. Biomacromolecules 12, 523–532 (2011).

  70. 70.

    , & Recent advances in lactic acid production by microbial fermentation processes. Biotechnol. Adv. 31, 877–902 (2013).

  71. 71.

    , , , & Shape-selective zeolite catalysis for bioplastics production. Science 349, 78–80 (2015).

  72. 72.

    , , , & Lactic acid as a platform chemical in the biobased economy: the role of chemocatalysis. Energy Environ. Sci. 6, 1415–1442 (2013).

  73. 73.

    , , & Stereocomplex formation between enantiomeric poly(lactides). Macromolecules 20, 904–906 (1987).

  74. 74.

    , & Comparing life cycle energy and GHG emissions of bio-based PET, recycled PET, PLA, and man-made cellulosics. Biofuel. Bioprod. Bior. 6, 625–639 (2012).

  75. 75.

    & Life cycle assessment of the manufacture of lactide and PLA biopolymers from sugarcane in Thailand. Int. J. Life Cycle Assess. 15, 970–984 (2010).

  76. 76.

    Corbion. Corbion Purac successfully develops PLA resin from second generation feedstocks. Corbion (2015).

  77. 77.

    & Poly(hydroxyalkanoates) — a fifth class of physiologically important organic biopolymers. Angew. Chem. Int. Edn Engl. 32, 477–502 (1993).

  78. 78.

    , & Replacing fossil based PET with biobased PEF; process analysis, energy and GHG balance. Energy Environ. Sci. 5, 6407–6422 (2012). This paper describes a life-cycle assessment that compares the outputs associated with petrochemical-derived PET and biomass-derived PEF.

  79. 79.

    et al. Chain mobility, thermal, and mechanical properties of poly(ethylene furanoate) compared to poly(ethylene terephthalate). Macromolecules 47, 1383–1391 (2014).

  80. 80.

    , , & in Biobased Monomers, Polymers, and Materials Vol. 1105 ACS Symposium Series Ch. 1, 1–13 (American Chemical Society, 2012).

  81. 81.

    et al. Alternative monomers based on lignocellulose and their use for polymer production. Chem. Rev. 116, 1540–1599 (2015).

  82. 82.

    , & Alternating copolymerization of epoxides and cyclic anhydrides: an improved route to aliphatic polyesters. J. Am. Chem. Soc. 129, 11330–11331 (2007).

  83. 83.

    , & Poly(propylene succinate): a new polymer stereocomplex. J. Am. Chem. Soc. 136, 15897–15900 (2014).

  84. 84.

    & Completely recyclable biopolymers with linear and cyclic topologies via ring-opening polymerization of γ-butyrolactone. Nature Chem. 8, 42–49 (2016).

  85. 85.

    , & Polymer synthesis: to react the impossible ring. Nature Chem. 8, 3–4 (2016).

  86. 86.

    , , , & Scalable production of mechanically tunable block polymers from sugar. Proc. Natl Acad. Sci. USA 111, 8357–8362 (2014).

  87. 87.

    et al. Creating hierarchical structures in renewable composites by attaching bacterial cellulose onto sisal fibers. Adv. Mater. 20, 3122–3126 (2008).

  88. 88.

    , & Supra-molecular ecobionanocomposites based on polylactide and cellulosic nanowhiskers: synthesis and properties. Biomacromolecules 13, 2013–2019 (2012).

  89. 89.

    et al. From interfacial ring-opening polymerization to melt processing of cellulose nanowhisker-filled polylactide-based nanocomposites. Biomacromolecules 12, 2456–2465 (2011).

  90. 90.

    , , , & Biodegradable polymers from renewable sources: rheological characterization of hemicellulose-based hydrogels. Biomacromolecules 6, 684–690 (2005).

  91. 91.

    et al. High-performance green flexible electronics based on biodegradable cellulose nanofibril paper. Nature Commun. 6, 7170 (2015).

  92. 92.

    , & Anionic ring-opening polymerization of methyl 4,6-O-benzylidene-2,3-O-carbonyl-α-D-glucopyranoside: a first example of anionic ring-opening polymerization of five-membered cyclic carbonate without elimination of CO2. Macromolecules 38, 3562–3563 (2005).

  93. 93.

    et al. Polycarbonates derived from glucose via an organocatalytic approach. J. Am. Chem. Soc. 135, 6826–6829 (2013).

  94. 94.

    & Strategies for the conversion of lignin to high-value polymeric materials: review and perspective. Chem. Rev. 116, 2275–2306 (2015).

  95. 95.

    , , & Formic-acid-induced depolymerization of oxidized lignin to aromatics. Nature 515, 249–252 (2014).

  96. 96.

    & A route for lignin and bio-oil conversion: dehydroxylation of phenols into arenes by catalytic tandem reactions. Angew. Chem. Int. Edn Engl. 52, 11499–11503 (2013).

  97. 97.

    , & Biorenewable polyethylene terephthalate mimics derived from lignin and acetic acid. Green Chem. 12, 1704–1706 (2010).

  98. 98.

    et al. Structure property relationships of biobased n-alkyl bisferulate epoxy resins. Green Chem. (2016).

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Acknowledgements

The UK Engineering and Physical Sciences Research Council (EP/K035274/1, EP/M013839/1, EP/L017393/1 and EP/K014070/1) and the China Scholarship Council Imperial Scholarship (Y.Z.) are acknowledged for funding.

Author information

Author notes

    • Yunqing Zhu
    •  & Charles Romain

    These authors contributed equally to this work.

Affiliations

  1. Chemistry Research Laboratory, Department of Chemistry, University of Oxford, Oxford OX1 3TA, UK.

    • Yunqing Zhu
    •  & Charlotte K. Williams
  2. Department of Chemistry, Imperial College London, London SW7 2AZ, UK.

    • Charles Romain

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Competing interests

C.K.W. is a director and founder of Econic Technologies.

Corresponding author

Correspondence to Charlotte K. Williams.

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