Opening and Closing Rings

New Polymers from Sustainable Feedstock

Biodegradable aliphatic polyesters built from sustainable feedstocks are one of the most promising solutions to address the pollution and oil-dependence challenges of modern plastics, but remain limited in monomer scope and thus the accessible polymer properties. DOX monomers (1,3-dioxolan-4-ones) provide facile access to a range of novel monomers from renewable α-hydroxy acids and can be polymerized to give structurally divergent aliphatic polyesters with high retention of stereochemistry. Reaction kinetics, structure/property relationships, copolymers of traditional cyclic esters, and direct recycling of waste paraformaldehyde showcase the scope of this new reaction in polymer chemistry.

DOX

Cairns, S. A.; Schultheissa, A.; Shaver, M. P. “A broad scope of aliphatic polyesters prepared by elimination of small molecules from sustainable 1,3-dioxolan-4-ones” Polym. Chem. 2017, 8, 557

Olefin-Metathesis on Polymers

Olefin-metathesis offers a versatile methodology for introducing new functionality and generating new structures. We use olefin cross-metathesis in both pre- and post- polymerisation modification of biodegradable lactones to introduce an array of functional groups to tune the thermal properties of the polymers. We also use ring-closing metathesis as an efficient method to control the conformation of cyclopolymers. Further modification of the aforementioned rings can generate novel biometric polymeric materials.

Mo, Fern TOC

Sinclair, F.; Chen, L.; Greenland, B. W.; Shaver, M. P. “Installing Multiple Functional Groups on Biodegradable Polyesters via Post-Polymerization Olefin Cross-Metathesis” Macromolecules 2016, 49, 6826

Aromatic-Aliphatic Polyesters

Aromatic polymers, such as polystyrene are versatile in their scope of applications due to their chemical and physical properties. Our research focuses on synthesising biodegradable, aromatic containing polyesters through new monomer design. Exploitation of the monomer-polymer equilibrium can tune the rate and extent of enzymatic and catalytic degradation to provide an insight into less energy consuming methods of recycling and reusing plastics.

Vishal TOC

Lizundia, E.; Makwana, V.; Larrañaga, A.; Vilas, J.; Shaver, M. P. “Thermal, structural and degradation properties of an aromatic–aliphatic polyester built through ring-opening polymerisation” Polym. Chem. 2017, 8-3530