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Completely recyclable biopolymers with linear and cyclic topologies via ring-opening polymerization of γ-butyrolactone

Nature Chemistry volume 8, pages 42–49 (2016)Cite this article

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Abstract

Ring-opening polymerization (ROP) is a powerful synthetic methodology for the chemical synthesis of technologically important biodegradable aliphatic polyesters from cyclic esters or lactones. However, the bioderived five-membered γ-butyrolactone (γ-BL) is commonly referred as ‘non-polymerizable’ because of its low strain energy. The chemical synthesis of poly(γ-butyrolactone) (PγBL) through the ROP process has been realized only under ultrahigh pressure (20,000 atm, 160 °C) and only produces oligomers. Here we report that the ROP of γ-BL can, with a suitable catalyst, proceed smoothly to high conversions (90%) under ambient pressure to produce PγBL materials with a number-average molecular weight up to 30 kg mol–1 and with controlled linear and/or cyclic topologies. Remarkably, both linear and cyclic PγBLs can be recycled back into the monomer in quantitative yield by simply heating the bulk materials at 220 °C (linear polymer) or 300 °C (cyclic polymer) for one hour, which thereby demonstrates the complete recyclability of PγBL.

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Figure 1: Proposed mechanism and employed catalysts for the ROP of γ-BL.
Figure 2: MALDI-TOF mass spectra of PγBLs.
Figure 3: PγBLs with different topologies.
Figure 4: Thermodynamics of the γ-BL polymerization.
Figure 5: PγBL topology, thermal stability, intrinsic viscosity and dynamic mechanical behaviour.
Figure 6: Thermal recyclability of linear and cyclic PγBL.

References

  1. Hillmyer, M. A. & Tolman, W. B. Aliphatic polyester block polymers: renewable, degradable, and sustainable. Acc. Chem. Res. 47, 2390–2396 (2014).

    Article  CAS  PubMed  Google Scholar 

  2. Jérôme, C. & Lecomte, P. Recent developments in ring-opening polymerization of lactones. Adv. Polym. Sci. 245, 173–217 (2012).

    Google Scholar 

  3. Albertsson, A.-C. & Varma, I. K. Aliphatic polyesters: synthesis, properties and applications. Adv. Polym. Sci. 157, 1–40 (2002).

    Article  CAS  Google Scholar 

  4. Rieth, L. R., Moore, D. R., Lobkovsky, E. B. & Coates, G. W. Single-site β-diiminate zinc catalysts for the ring-opening polymerization of β-butyrolactone and β-valerolactone to poly(3-hydroxyalkanoates). J. Am. Chem. Soc. 124, 15239–15248 (2002).

    Article  CAS  PubMed  Google Scholar 

  5. Bomgardner, M. M. Biobased polymers. Chem. Eng. News 92, 10–14 (2014).

    Google Scholar 

  6. Bozell, J. J. & Petersen, G. R. 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).

    Article  CAS  Google Scholar 

  7. Allcock, H. R., Lampe, F. W. & Mark, J. E. Contemporary Polymer Chemistry 3rd edn (Pearson, 2003).

    Google Scholar 

  8. Odian, G . Principles of Polymerization 3rd edn (Wiley-Interscience, 1991).

    Google Scholar 

  9. Sawada, H. Thermodynamics of Polymerization (Marcel Dekker, 1976).

    Google Scholar 

  10. Houk, K. H., Jabbari, A., Hall, H. K. Jr & Alemán, C. Why δ-valerolactone polymerizes and γ-butyrolactone does not. J. Org. Chem. 73, 2674–2678 (2008).

    Article  CAS  PubMed  Google Scholar 

  11. Nobes, G. A. R., Kazlauska, R. J. & Marchessault, R. H. Lipase-catalyzed ring-opening polymerization of lactones: a novel route to poly(hydroxyalkanoate)s. Macromolecules 29, 4829–4833 (1996).

    Article  CAS  Google Scholar 

  12. Moore, T., Adhikari, R. & Gunatillake, P. Chemosynthesis of bioresorbable poly(γ-butyrolactone) by ring-opening polymerisation: a review. Biomaterials 26, 3771–3782 (2005).

    Article  CAS  PubMed  Google Scholar 

  13. Martin, D. P. & Williams, S. F. Medical applications of poly-4-hydroxybutyrate: a strong flexible absorbable biomaterial. Biochem. Eng. J. 16, 97–105 (2003).

    Article  CAS  Google Scholar 

  14. Korte, F. & Glet, W. Hochdruckreaktionen. II. Die polymerisation von γ-butyrolacton und δ-valerolactam bei hohen drücken. J. Polym. Sci. Polym. Lett. 4, 685–689 (1966).

    Article  CAS  Google Scholar 

  15. Yamashita, K., Yamamoto, K. & Kadokawa, J.-I. Acid-catalyzed ring-opening polymerization of γ-butyrolactone under high-pressure conditions. Chem. Lett. 43, 213–215 (2014).

    Article  CAS  Google Scholar 

  16. Oishi, A., Taguchi, Y. & Fujita, K. Production method of poly(γ-butyrolactone) using metal complex catalyst. Japanese Patent JP2003252968 (2003).

  17. Oishi, A., Taguchi, Y., Fujita, K., Ikeda, Y. & Masuda, T. Production of poly-γ-butyrolactone. Japanese Patent JP2000281767 (2000).

  18. Duda, A. & Kowalski, A. in Handbook of Ring-Opening Polymerization (eds Dubois, P., Coulembier, O. & Raquez, J.-M.) Ch. 1, 1–51 (Wiley-VCH, 2009).

    Google Scholar 

  19. Alemán, C., Betran, O., Casanovas, J., Houk, K. H. & Hall, H. K. Jr. Thermodynamic control of the polymerizability of five-, six-, and seven-membered lactones. J. Org. Chem. 74, 6237–6244 (2009).

    Article  PubMed  CAS  Google Scholar 

  20. Saiyasombat, W. et al. Ring strain and polymerizability of cyclic esters. Polymer 39, 5581–5585 (1998).

    Article  CAS  Google Scholar 

  21. Duda, A. & Penczek, S. Oligomerization and copolymerization of γ-butyrolactone—a monomer known as unable to homopolymerize, 1. Macromol. Chem. Phys. 197, 1273–1283 (1996).

    Article  CAS  Google Scholar 

  22. Tada, K., Numata, Y., Saegusa, T. & Furukawa, J. Copolymerization of γ-buyrolactone and β-propiolactone. Makromol. Chem. 77, 220–228 (1964).

    Article  CAS  Google Scholar 

  23. Zhou, J., Schmidt, A. M. & Ritter, H. Bicomponent transparent polyester networks with shape memory effect. Macromolecules 43, 939–942 (2010).

    Article  CAS  Google Scholar 

  24. Hong, M. & Chen, E. Y.-X. Coordination ring-opening copolymerization of naturally renewable α-methylene-γ-butyrolactone into unsaturated polyesters. Macromolecules 47, 3614–3624 (2014).

    Article  CAS  Google Scholar 

  25. Chen, E. Y.-X. Coordination polymerization of polar vinyl monomers by single-site metal catalysts. Chem. Rev. 109, 5157–5214 (2009).

    Article  CAS  PubMed  Google Scholar 

  26. O'Keefe, B. J., Hillmyer, M. A. & Tolman, W. B. R. Polymerization of lactide and related cyclic esters by discrete metal complexes. J. Chem. Soc. Dalton Trans. 2215–2224 (2001).

  27. Yasuda, H. Organo transition metal initiated living polymerizations. Prog. Polym. Sci. 25, 573–626 (2000).

    Article  CAS  Google Scholar 

  28. Mecerreyes, D., Jérôme, R. & Dubois, P. Novel macromolecular architectures based on aliphatic polyesters: relevance of the ‘coordination–insertion’ ring-opening polymerization. Adv. Polym. Sci. 147, 1–59 (1999).

    Article  CAS  Google Scholar 

  29. Yasuda, H. & Ihara, E. Rare earth metal-initiated living polymerizations of polar and nonpolar monomers. Adv. Polym. Sci. 133, 53–101 (1997).

    Article  CAS  Google Scholar 

  30. Kuran, W. Coordination polymerization of heterocyclic and heterounsaturated monomers. Prog. Polym. Sci. 23, 919–992 (1998).

    Article  CAS  Google Scholar 

  31. Stevels, W. M., Ankoné, M. J. K., Dijkstra, P. J. & Feijen, J. Kinetics and mechanism of ε-caprolactone polymerization using yttrium alkoxides as initiators. Macromolecules 29, 8296–8303 (1996).

    Article  CAS  Google Scholar 

  32. Dudnik, A. S., Weidner, V. L., Motta, A., Delferro, M. & Marks, T. J. Atom-efficient regioselective 1,2-dearomatization of functionalized pyridines by an earth-abundant organolanthanide catalyst. Nature Chem. 6, 1100–1107 (2014).

    Article  CAS  Google Scholar 

  33. Brown, H. A. & Waymouth, R. M. Zwitterionic ring-opening polymerization for the synthesis of high molecular weight cyclic polymers. Acc. Chem. Res. 46, 2585–2596 (2013).

    Article  CAS  PubMed  Google Scholar 

  34. Endo, K. Synthesis and properties of cyclic polymers. Adv. Polym. Sci. 217, 121–183 (2008).

    CAS  Google Scholar 

  35. Semlyen, J. A. Cyclic Polymers 2nd edn (Kluwer Academic, 2000).

    Google Scholar 

  36. Bielawski, C. W., Benitez, D. & Grubbs, R. H. An ‘endless’ route to cyclic polymers. Science 297, 2041–2044 (2002).

    Article  CAS  PubMed  Google Scholar 

  37. Kricheldorf, H. R. Cyclic polymers: synthetic strategies and physical properties. J. Polym. Sci. A 48, 251–284 (2010).

    Article  CAS  Google Scholar 

  38. Guo, L. & Zhang, D. Cyclic poly(α-peptoid)s and their block copolymers from N-heterocyclic carbene-mediated ring-opening polymerizations of N-substituted N-carboxylanhydrides. J. Am. Chem. Soc. 131, 18072–18074 (2009).

    Article  CAS  PubMed  Google Scholar 

  39. Culkin, D. A. et al. Zwitterionic polymerization of lactide to cyclic poly(lactide) by using N-heterocyclic carbene organocatalysts. Angew. Chem. Int. Ed. 46, 2627–2630 (2007).

    Article  CAS  Google Scholar 

  40. Amgoune, A., Thomas, C. M., Roisnel, T. & Carpentier, J.-F. Ring-opening polymerization of lactide with group 3 metal complexes supported by dianionic alkoxy-amino-bisphenolate ligands: combining high activity, productivity, and selectivity. Chem. Eur. J. 12, 169–179 (2006).

    Article  CAS  Google Scholar 

  41. Ma, H. & Okuda, J. Kinetics and mechanism of L-lactide polymerization by rare earth metal silylamido complexes: effect of alcohol addition. Macromolecules 38, 2665–2673 (2005).

    Article  CAS  Google Scholar 

  42. Boyle, T. J. & Ottley, L. A. M. Advances in structurally characterized lanthanide alkoxide, aryloxide, and silyloxide compounds. Chem. Rev. 108, 1896–1917 (2008).

    Article  CAS  PubMed  Google Scholar 

  43. Wang, Y., Zhao, W., Liu, X., Cui, D. & Chen, E. Y.-X. Ligand-free magnesium catalyst system: immortal polymerization of L-lactide with high catalyst efficiency and structure of active intermediates. Macromolecules 45, 6957–6965 (2012).

    Article  CAS  Google Scholar 

  44. Thomas, C. & Bibal, B. Hydrogen-bonding organocatalysts for ring-opening polymerization. Green Chem. 16, 1687–1699 (2014).

    Article  CAS  Google Scholar 

  45. Kiesewetter, M. K., Shin, E. J., Hedrick, J. L. & Waymouth, R. M. Organocatalysis: opportunities and challenges for polymer synthesis. Macromolecules 43, 2093–2107 (2010).

    Article  CAS  Google Scholar 

  46. Kamber, N. E. et al. Organocatalytic ring-opening polymerization. Chem. Rev. 107, 5813–5840 (2007).

    Article  CAS  PubMed  Google Scholar 

  47. Carpentier, J.-F. Rare-earth complexes supported by tripodal tetradentate bis(phenolate) ligands: a privileged class of catalysts for ring-opening polymerization of cyclic esters. Organometallics 34, 4175–4189 (2015).

    Article  CAS  Google Scholar 

  48. Altenbuchner, P. T. et al. Versatile 2-methoxyethylaminobis(phenolate)yttrium catalysts: catalytic precision polymerization of polar monomers via rare earth metal-mediated group transfer polymerization. Macromolecules 47, 7742–7749 (2014).

    Article  CAS  Google Scholar 

  49. Amgoune, A., Thomas, C. M., Ilinca, S., Roisnel, T. & Carpentier, J.-F. Highly active, productive, and syndiospecific yttrium initiators for the polymerization of racemic β-butyrolactone. Angew. Chem. Int. Ed. 45, 2782–2784 (2006).

    Article  CAS  Google Scholar 

  50. Cai, C.-X., Amgoune, A., Lehmann, C. W. & Carpentier, J.-F. Stereoselective ring-opening polymerization of racemic lactide using alkoxy-amino-bi(phenolate) group 3 metal complexes. Chem. Commun. 2004, 330–331 (2004).

    Article  CAS  Google Scholar 

  51. Kaitz, J. A., Diesendruck, C. E. & Moore, J. S. End group characterization of poly(phthalaldehyde): surprising discovery of a reversible, cationic macrocyclization mechanism. J. Am. Chem. Soc. 135, 12755–12761 (2013).

    Article  CAS  PubMed  Google Scholar 

  52. Roovers, J. in Cyclic Polymers 2nd edn (ed. Semlyen, J. A.) 347–384 (Kluwer Academic, 2000).

    Google Scholar 

  53. Drumright, R. E., Gruber, P. R. & Henton, D. E. Polylactic acid technology. Adv. Mater. 12, 1841–1846 (2000).

    Article  CAS  Google Scholar 

  54. McNeill, I. C. & Leiper, H. A. Degradation studies of some polyesters and polycarbonates 2. Polylactide: degradation under isothermal conditions, thermal degradation mechanism and photolysis of the polymer. Polym. Degrad. Stab. 11, 309–326 (1985).

    Article  CAS  Google Scholar 

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Acknowledgements

This work was supported by the National Science Foundation (NSF-1300267).

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  1. Department of Chemistry, Colorado State University, Fort Collins, 80523-1872, Colorado, USA

    Miao Hong & Eugene Y.-X. Chen

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  1. Miao Hong
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Contributions

M.H. and E.Y.-X.C. conceived the idea and designed the experiments. M.H. performed the experiments. M.H. and E.Y.C. co-wrote the manuscript and participated in data analyses and discussions. E.Y.-X.C. directed the project.

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Correspondence to Eugene Y.-X. Chen.

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Hong, M., Chen, EX. Completely recyclable biopolymers with linear and cyclic topologies via ring-opening polymerization of γ-butyrolactone. Nature Chem 8, 42–49 (2016). https://doi.org/10.1038/nchem.2391

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