Infinite polymer networks: control of porous morphology and novel chemical functionalisation strategies

Rights statement
Awarding institution
  • University of Strathclyde
Date of award
  • 2022
Thesis identifier
  • T16218
Person Identifier (Local)
  • 201789512
Qualification Level
Qualification Name
  • Infinite polymer networks are used as advanced materials in a wide range of applications, from separation science to polymer-supported technologies. Often, these materials are used in highly demanding applications where tight control over the polymer structure, porosity and chemical functionality is a prerequisite to success. The development of new and improved methods for controlling structure, porosity and chemical functionality will enable the preparation of the next generation of infinite polymer networks. The first major part of the research study focused on the control of polymer microsphere porosity by reversible-deactivation radical polymerisation under precipitation polymerisation conditions. Here, improved control over the uniformity of polymer primary chain lengths was expected to translate into improved control over pore network formation. It was found that reversible addition-fragmentation chain-transfer (RAFT) precipitation polymerisation had a significant controlling influence upon the size and functionality of porous polymer microspheres and upon porous morphology of hypercrosslinked polymers. Secondly, a novel Meldrum’s Acid-based polymer functionalisation route was devised and implemented. A polymerisable Meldrum’s Acid derivative was incorporated into precipitation polymerisations protocols to yield polymer microspheres decorated with Meldrum’s Acid residues. Thermal treatment of the polymer microspheres revealed highly-reactive ketene functional groups which were used as chemical handles in a range of polymer-analogous organic reactions. Finally, an investigation into stimuli-responsive polymer microspheres was conducted. Visible light-responsive donor-acceptor Stenhouse adducts (DASAs) were shown to exhibit a degree of reversible photo-switching when bound to polymer microspheres. The switch between open and closed DASA forms significantly impacted upon the physical properties of the polymer supports, most significantly as a change in the polymers’ hydrophilic/hydrophobic balance and mean particle diameters. This innovation opens a path to the development of light-responsive infinite polymer networks where the size, porosity and wettability of the network can be modulated by exposure to visible light.
Advisor / supervisor
  • Cormack, Peter
Resource Type
Embargo Note
  • This thesis is restricted to Strathclyde users only until 1st June 2027