Sustainable Polyester Elastomers from Lactones: Synthesis, Properties, and Enzymatic Hydrolyzability

Guilhem X. De Hoe, Michael T. Zumstein, Brandon J. Tiegs, Jacob P. Brutman, Kristopher McNeill, Michael Sander, Geoffrey W. Coates, Marc A. Hillmyer

Research output: Contribution to journalArticlepeer-review

40 Scopus citations

Abstract

Chemically cross-linked elastomers are an important class of polymeric materials with excellent temperature and solvent resistance. However, nearly all elastomers are petroleum-derived and persist in the environment or in landfills long after they are discarded; this work strives to address these issues by demonstrating the synthesis of renewable, enzymatically hydrolyzable, and mechanically competitive polyester elastomers. The elastomers described were synthesized using a novel bis(β-lactone) cross-linker and star-shaped, hydroxyl-terminated poly(γ-methyl-ϵ-caprolactone). Using model compounds, we determined that the bis(β-lactone) cross-linker undergoes acyl bond cleavage to afford β-hydroxyesters at the junctions. The mechanical properties of the cross-linked materials were tunable and competitive with a commodity rubber band. Furthermore, the elastomers demonstrated high thermal stability and a low glass transition (-50 °C), indicating a wide range of use temperatures. The polyester networks were also subjected to enzymatic hydrolysis experiments to investigate the potential for these materials to biodegrade in natural environments. We found that they readily hydrolyzed at neutral pH and environmentally relevant temperatures (2-40 °C); complete hydrolysis was achieved in all cases at temperature-dependent rates. The results presented in this work exemplify the development of high performance yet sustainable alternatives to conventional elastomers.

Original languageEnglish (US)
Pages (from-to)963-973
Number of pages11
JournalJournal of the American Chemical Society
Volume140
Issue number3
DOIs
StatePublished - Jan 24 2018

Bibliographical note

Funding Information:
We acknowledge our principal funding source for this work, the Center for Sustainable Polymers at the University of Minnesota, which is a National Science Foundation supported Center for Chemical Innovation (CHE-1413862). We would also like to acknowledge the Institute of Biogeochemistry and Pollutant Dynamics (IBP) at ETH Zurich, as the enzymatic hydrolysis studies were made possible through use of IBP equipment. We thank Prof. Mark Lever and Prof. Martin Schroth for their help in obtaining equipment used for the lowtemperature hydrolysis experiments, as well as Dr. Angelika Neitzel, Dr. Thomas Vidil, and Dr. Gordon Getzinger for helpful discussions. We also thank Dr. Deborah Schneiderman for her help with shear rheology and Dr. David Giles for advice on dynamic mechanical thermal analysis.

Funding Information:
We acknowledge our principal funding source for this work, the Center for Sustainable Polymers at the University of Minnesota, which is a National Science Foundation supported Center for Chemical Innovation (CHE-1413862). We would also like to acknowledge the Institute of Biogeochemistry and Pollutant Dynamics (IBP) at ETH Zurich, as the enzymatic hydrolysis studies were made possible through use of IBP equipment. We thank Prof. Mark Lever and Prof. Martin Schroth for their help in obtaining equipment used for the low-temperature hydrolysis experiments, as well as Dr. Angelika Neitzel, Dr. Thomas Vidil, and Dr. Gordon Getzinger for helpful discussions. We also thank Dr. Deborah Schneiderman for her help with shear rheology and Dr. David Giles for advice on dynamic mechanical thermal analysis.

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