Topology and molecular weight distribution control in polymers

The composition and structural architecture of polymers plays an important role in determining their materials performance in various applications. Therefore, synthesis of a well-defined polymer is highly desirable to not only control structure-property relationships but even provide design strategies for desired material performance. The implementation of ‘living’ radical polymerization (LRP) allows the preparation of functional polymers in a highly controlled manner and with the potential to be made on industrial scales. In addition to control over chain dimensions and architecture, LRP further accommodates the incorporation of diverse chemical functionality to build more complex polymer structures using chemical approaches such as ‘click’ chemistry and dynamic covalent chemistry. In this thesis, we focused on controlling polymer conformation (e.g. cyclic structures) in solution, including their design and characterization. We then applied dynamic covalent chemistry to post-modify these well-defined polymer to obtain insights into the kinetics that control single-chain folding, crosslinking and applications towards polymer healing materials.

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