Synthesis of functional polymers via click polymerisation and multicomponent reactions

This work presented herein is aiming to investigate the preparation and post-polymerisation modification of functional polymers with click reactions and multicomponent reactions. Three click reactions, the para-fluoro thiol click reaction (PFTR), the thiol-bromo click reaction and the Sulphur (VI) fluoride exchange (SuFEx) click reaction have been studied in the preparation of step-growth polymers. As a result, novel fluorinated poly (aryl thioether)s via simultaneous PFTR and thiol-bromo click reaction, telechelic polyoxazolines and amphiphilic multiblock polyoxazoline have been synthesized and reported for the first time, whilst corresponding thermal properties, hydrophobicity, and the ability of self-assembly have been characterised. The study on step-growth polymerisation via SuFEx click reaction did not lead to the successful preparation of novel polymers, while the limitation has been investigated. However, SuFEx clickable polyoxazolines has been synthesized for the first time utilizing a sulfonyl fluoride group-containing initiator, which opens an avenue for future investigation. The Ugi-4-component reaction was employed as an example of multicomponent reaction, and corresponding step-growth polymerisation of sustainable monomers, as well as solid-phase supported synthesis of sequence defined peptoid structures have been investigated. Novel polypeptoids with up to 83.9% bio-sourced mass were prepared via Ugi-4-component polymerisation of bio-sourced diamines and dicarboxylic acids, while the thermal properties could be tuned to produce room temperature elastomers or crystallised polymers, and multigram scale synthesis was shown practicable. Sequence defined multifunctional peptoid oligomers were also synthesized and characterised with MALDI-ToF, while these peptoids could be interesting for studies on self-assembly and the effect of side-chain position on polymer properties