A circular polyester platform based on simple gem-disubstituted valerolactones | Nature Chemistry

2022-11-08 04:41:20 By : Ms. annie wang

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Nature Chemistry (2022 )Cite this article High Purity Thulium

A circular polyester platform based on simple gem-disubstituted valerolactones | Nature Chemistry

Geminal disubstitution of cyclic monomers is an effective strategy to enhance the chemical recyclability of their polymers, but it is utilized for that purpose alone and often at the expense of performance properties. Here we present synergistic use of gem-α,α-disubstitution of available at-scale, bio-based δ-valerolactones to yield gem-dialkyl-substituted valerolactones (\({\rm{VL}}^{{\rm{R}}_{2}}\) ), which generate polymers that solve not only the poor chemical recyclability but also the low melting temperature and mechanical performance of the parent poly(δ-valerolactone); the gem-disubstituted polyesters (\({\rm{PVL}}^{{\rm{R}}_{2}}\) ) therefore not only exhibit complete chemical recyclability but also thermal, mechanical and transport properties that rival or exceed those of polyethylene. Through a fundamental structure–property study that reveals intriguing impacts of the alkyl chain length on materials performance of \({\rm{PVL}}^{{\rm{R}}_{2}}\) , this work establishes a simple circular, high-performance polyester platform based on \({\rm{VL}}^{{\rm{R}}_{2}}\) and highlights the importance of synergistic utilization of gem-disubstitution for enhancing both chemical recyclability and materials performance of sustainable polyesters.

This is a preview of subscription content, access via your institution

Get full journal access for 1 year

All prices are NET prices. VAT will be added later in the checkout. Tax calculation will be finalised during checkout.

Get time limited or full article access on ReadCube.

All prices are NET prices.

All of the data necessary to support the conclusions of this paper are provided in the paper and its Supplementary Information.

Shi, C. et al. Design principles for intrinsically circular polymers with tunable properties. Chem 7, 2896–2912 (2021).

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

Article  PubMed  CAS  Google Scholar 

Geyer, R., Jambeck, J. R. & Law, K. L. Production, use, and fate of all plastics ever made. Sci. Adv. 3, e1700782 (2017).

Article  PubMed  PubMed Central  Google Scholar 

The New Plastics Economy: Rethinking the Future of Plastics (World Economic forum, Ellen MacArthur Foundation, McKinsey and Company, 2016); www.ellenmacarthurfoundation.org/publications/the-new-plasticseconomy-rethinking-the-future-of-plastics

Borrelle, S. B. et al. Predicted growth in plastic waste exceeds efforts to mitigate plastic pollution. Science 369, 1515–1518 (2020).

Article  PubMed  CAS  Google Scholar 

Coates, G. W. & Getzler, Y. D. Y. L. Chemical recycling to monomer for an ideal, circular polymer economy. Nat. Rev. Mater. 5, 501–516 (2020).

Worch, J. C. & Dove, A. P. 100th anniversary of macromolecular science viewpoint: toward catalytic chemical recycling of waste (and future) plastics. ACS Macro Lett. 9, 1494–1506 (2020).

Article  PubMed  CAS  Google Scholar 

Kumar, A. et al. Hydrogenative depolymerization of nylons. J. Am. Chem. Soc. 142, 14267–14275 (2020).

Article  PubMed  CAS  PubMed Central  Google Scholar 

Zhang, F. et al. Polyethylene upcycling to long-chain alkylaromaticsby tandem hydrogenolysis/aromatization. Science 370, 437–441 (2020).

Article  PubMed  CAS  Google Scholar 

Jehanno, C., Pérez-Madrigal, M. M., Demarteau, J., Sardon, H. & Dove, A. P. Organocatalysis for depolymerisation. Polym. Chem. 10, 172–186 (2019).

Fagnani, D. E. et al. 100th anniversary of macromolecular science viewpoint: redefining sustainable polymers. ACS Macro Lett. 10, 41–53 (2020).

Lau, W. W. Y. et al. Evaluating scenarios toward zero plastic pollution. Science 369, 1455–1461 (2020).

Article  PubMed  CAS  Google Scholar 

Lu, X.-B., Liu, Y. & Zhou, H. Learning nature: recyclable monomers and polymers. Chem. Eur. J. 24, 11255–11266 (2018).

Article  PubMed  CAS  Google Scholar 

Rahimi, A. & García, J. M. Chemical recycling of waste plastics for new materials production. Nat. Rev. Chem. 1, 0046 (2017).

Kaitz, J. A., Lee, O. P. & Moore, J. S. Depolymerizable polymers: preparation, applications, and future outlook. MRS Commun. 5, 191–204 (2015).

Hong, M. & Chen, E. Y. X. Chemically recyclable polymers: a circular economy approach to sustainability. Green Chem. 19, 3692–3706 (2017).

Hong, M. & Chen, E. Y. X. Future directions for sustainable polymers. Trends Chem. 1, 148–151 (2019).

Tang, X. & Chen, E. Y. X. Toward infinitely recyclable plastics derived from renewable cyclic esters. Chem 5, 284–312 (2019).

Zhang, X., Fevre, M., Jones, G. O. & Waymouth, R. M. Catalysis as an enabling science for sustainable polymers. Chem. Rev. 118, 839–885 (2018).

Article  PubMed  CAS  Google Scholar 

Schneiderman, D. K. & Hillmyer, M. A. 50th anniversary perspective: there is a great future in sustainable polymers. Macromolecules 50, 3733–3749 (2017).

Nishida, H. et al. Poly(tetramethyl glycolide) from renewable carbon, a racemization-free and controlled depolymerizable polyester. Macromolecules 44, 12–13 (2011).

Fahnhorst, G. W., Hoe, G. X. D., Hillmyer, M. A. & Hoye, T. R. 4-Carboalkoxylated polyvalerolactones from malic acid: tough and degradable polyesters. Macromolecules 53, 3194–3201 (2020).

Article  PubMed  CAS  PubMed Central  Google Scholar 

Fahnhorst, G. W. & Hoye, T. R. A. Carbomethoxylated polyvalerolactone from malic acid: synthesis and divergent chemical recycling. ACS Macro Lett. 7, 143–147 (2018).

Article  PubMed  CAS  Google Scholar 

Cederholm, L., Olsén, P., Hakkarainen, M. & Odelius, K. Turning natural δ-lactones to thermodynamically stable polymers with triggered recyclability. Polym. Chem. 11, 4883–4894 (2020).

MacDonald, J. P. & Shaver, M. P. An aromatic/aliphatic polyester prepared via ring-opening polymerisation and its remarkably selective and cyclable depolymerisation to monomer. Polym. Chem. 7, 553–559 (2016).

Hong, M. & Chen, E. Y.-X. Completely recyclable biopolymers with linear and cyclic topologies via ring-opening polymerization of γ-butyrolactone. Nat. Chem. 8, 42–49 (2016).

Article  PubMed  CAS  Google Scholar 

Hong, M. & Chen, E. Y.-X. Towards truly sustainable polymers: a metal-free recyclable polyester from biorenewable non-strained γ-butyrolactone. Angew. Chem. Int. Ed. 55, 4188–4193 (2016).

Zhu, J.-B., Watson, E. M., Tang, J. & Chen, E. Y.-X. A synthetic polymer system with repeatable chemical recyclability. Science 360, 398–403 (2018).

Article  PubMed  CAS  Google Scholar 

Zhu, J. B. & Chen, E. Y.-X. Catalyst-sidearm-induced stereoselectivity switching in polymerization of a racemic lactone for stereocomplexed crystalline polymer with a circular life cycle. Angew. Chem. Int. Ed. 58, 1178–1182 (2019).

Cywar, R. M., Zhu, J.-B. & Chen, E. Y.-X. Selective or living organopolymerization of a six-five bicyclic lactone to produce fully recyclable polyesters. Polym. Chem. 10, 3097–3106 (2019).

Sangroniz, A. et al. Packaging materials with desired mechanical and barrier properties and full chemical recyclability. Nat. Commun. 10, 3559 (2019).

Article  PubMed  PubMed Central  Google Scholar 

Xiong, W. et al. Geminal dimethyl substitution enables controlled polymerization of penicillamine-derived β-thiolactones and reversed depolymerization. Chem 6, 1831–1843 (2020).

Shi, C. et al. Hybrid monomer design for unifying conflicting polymerizability, recyclability, and performance properties. Chem 7, 670–685 (2021).

Shi, C. et al. High-performance pan-tactic polythioesters with intrinsic crystallinity and chemical recyclability. Sci. Adv. 6, eabc0495 (2020).

Article  PubMed  CAS  PubMed Central  Google Scholar 

Yuan, J. et al. 4-Hydroxyproline-derived sustainable polythioesters: controlled ring-opening polymerization, complete recyclability, and facile functionalization. J. Am. Chem. Soc. 141, 4928–4935 (2019).

Article  PubMed  CAS  Google Scholar 

Yu, Y., Fang, L.-M., Liu, Y. & Lu, X.-B. Chemical synthesis of CO2-based polymers with enhanced thermal stability and unexpected recyclability from biosourced monomers. ACS Catal. 11, 8349–8357 (2021).

Liu, Y., Zhou, H., Guo, J.-Z., Ren, W.-M. & Lu, X.-B. Completely recyclable monomers and polycarbonate: approach to sustainable polymers. Angew. Chem. Int. Ed. 56, 4862–4866 (2017).

Ellis, W. C. 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).

Saxon, D. J., Gormong, E. A., Shah, V. M. & Reineke, T. M. Rapid synthesis of chemically recyclable polycarbonates from renewable feedstocks. ACS Macro Lett. 10, 98–103 (2021).

Article  PubMed  CAS  Google Scholar 

Abell, B. A., Snyderl, R. L. & Coates, G. W. Chemically recyclable thermoplastics from reversible-deactivation polymerization of cyclic acetals. Science 373, 783–789 (2021).

Schneiderman, D. K. et al. Chemically recyclable biobased polyurethanes. ACS Macro Lett. 5, 515–518 (2016).

Article  PubMed  CAS  Google Scholar 

Lloyd, E. M. et al. Fully recyclable metastable polymers and composites. Chem. Mater. 31, 398–406 (2019).

Diesendruck, C. E. et al. Mechanically triggered heterolytic unzipping of a low-ceiling-temperature polymer. Nat. Chem. 6, 623–628 (2014).

Article  PubMed  CAS  Google Scholar 

Beromi, M. M. et al. Iron-catalysed synthesis and chemical recycling of telechelic 1,3-enchained oligocyclobutanes. Nat. Chem. 13, 156–162 (2021).

Article  PubMed Central  Google Scholar 

Sathe, D. et al. Olefin metathesis-based chemically recyclable polymers enabled by fused-ring monomers. Nat. Chem. 13, 743–750 (2021).

Article  PubMed  CAS  Google Scholar 

Chen, H., Shi, Z., Hsu, T.-G. & Wang, J. Overcoming the low driving force in forming depolymerizable polymers through monomer isomerization. Angew. Chem. Int. Ed. 60, 25493–25498 (2021).

Jung, M. E. & Piizzi, G. Gem-disubstituent effect: theoretical basis and synthetic applications. Chem. Rev. 105, 1735–1766 (2005).

Article  PubMed  CAS  Google Scholar 

Bachrach, S. M. The Gem-dimethyl effect revisited. J. Org. Chem. 73, 2466–2468 (2008).

Article  PubMed  CAS  Google Scholar 

Zhou, J., Sathe, D. & Wang, J. Understanding the structure–polymerization thermodynamics relationships of fused-ring cyclooctenes for developing chemically recyclable polymers. J. Am. Chem. Soc. 144, 928–934 (2022).

Article  PubMed  CAS  Google Scholar 

Save, M., Schappacher, M. & Soum, A. Controlled ring-opening polymerization of lactones and lactides initiated by lanthanum isopropoxide, 1 general aspects and kinetics. Macromol. Chem. Phys. 203, 889–899 (2002).

Larrañaga, A. & Lizundia, E. A review on the thermomechanical properties and biodegradation behaviour of polyesters. Eur. Polym. J. 121, 109296 (2019).

Rabnawaz, M., Wyman, I., Auras, R. & Cheng, S. A roadmap towards green packaging: the current status and future outlook for polyesters in the packaging industry. Green Chem. 19, 4737–4753 (2017).

Reinišová, L. & Hermanová, S. Poly(trimethylene carbonate-co-valerolactone) copolymers are materials with tailorable properties: from soft to thermoplastic elastomers. RSC Adv. 10, 44111–44120 (2020).

Article  PubMed  PubMed Central  Google Scholar 

Schneiderman, D. K. & Hillmyer, M. A. Aliphatic polyester block polymer design. Macromolecules 49, 2419–2428 (2016).

Olsén, P., Odelius, K. & Albertsson, A.-C. Thermodynamic presynthetic considerations for ring-opening polymerization. Biomacromolecules 17, 699–709 (2016).

Article  PubMed  PubMed Central  Google Scholar 

Tang, X. et al. Biodegradable polyhydroxyalkanoates by stereoselective copolymerization of racemic diolides: stereocontrol mechanism and polyolefin-like properties. Angew. Chem. Int. Ed. 59, 7881–7890 (2020).

Tang, X., Westlie, A. H., Watson, E. M. & Chen, E. Y.-X. Stereosequenced crystalline polyhydroxyalkanoates from diastereomeric monomer mixtures. Science 366, 754–758 (2019).

Article  PubMed  CAS  Google Scholar 

Häußler, M., Eck, M., Rothauer, D. & Mecking, S. Closed-loop recycling of polyethylene-like materials. Nature 590, 423–427 (2021).

Munnuri, S. et al. Catalyst-controlled diastereoselective synthesis of cyclic amines via C–H functionalization. J. Am. Chem. Soc. 139, 18288–18294 (2017).

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

Wang, Y. & Xu, T. Topology-controlled ring-opening polymerization of o-carboxyanhydride. Macromolecules 53, 8829–8836 (2020).

The work performed at Dalian University of Technology was supported by the National Natural Science Foundation of China (grant no. 21774017) and the Fundamental Research Funds for the Central Universities (grant no. DUT20LK35). The work performed at Colorado State University was supported by RePLACE (Redesigning Polymers to Leverage A Circular Economy) funded by the Office of Science of the US Department of Energy via award no. DE-SC0022290.

State Key Laboratory of Fine Chemicals, Department of Chemistry, School of Chemical Engineering, Dalian University of Technology, Dalian, China

Xin-Lei Li, Jing-Yang Jiang & Tie-Qi Xu

Department of Chemistry, Colorado State University, Fort Collins, CO, USA

Ryan W. Clarke & Eugene Y.-X. Chen

You can also search for this author in PubMed  Google Scholar

You can also search for this author in PubMed  Google Scholar

You can also search for this author in PubMed  Google Scholar

You can also search for this author in PubMed  Google Scholar

You can also search for this author in PubMed  Google Scholar

X.-L.L., T.-Q. X. and E.Y.-X.C. conceived the idea and designed the experiments. X.-L.L., R.W.C. and J.-Y.J. performed the experiments, and analysed and processed the data. All authors co-wrote the manuscript and participated in data analyses and discussions.

Correspondence to Tie-Qi Xu or Eugene Y.-X. Chen.

T.X. and X.L. are named inventors on a Chinese patent application submitted by Dalian University of Technology that covers the polyester based on α,α-disubstituted valerolactones as well as the their preparation method and degradation. E.Y.-X.C. is a named inventor on a US patent application submitted by Colorado State University Research Foundation, which covers chemically circular semi-crystalline polyesters. The other authors declare no competing interests.

Nature Chemistry thanks Joshua Worch and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Li, XL., Clarke, R.W., Jiang, JY. et al. A circular polyester platform based on simple gem-disubstituted valerolactones. Nat. Chem. (2022). https://doi.org/10.1038/s41557-022-01077-x

DOI: https://doi.org/10.1038/s41557-022-01077-x

Anyone you share the following link with will be able to read this content:

Sorry, a shareable link is not currently available for this article.

Provided by the Springer Nature SharedIt content-sharing initiative

Nature Chemistry (Nat. Chem.) ISSN 1755-4349 (online) ISSN 1755-4330 (print)

A circular polyester platform based on simple gem-disubstituted valerolactones | Nature Chemistry

Lanthanum Cerium Alloy Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.