Sequential Modification of ADMET Polyketone via Oxime Chemistry and Electrophilic Alkoxyetherification

Abstract

Post-polymerization modification is a facile and efficient method for the generation of diverse functional polymers. Herein, polymer-based molecular arrays were obtained by using sequential modification. First, periodic polyketone P0 was synthesized via acyclic diene metathesis (ADMET) polymerization of α,ω-diene M0. Oxime chemistry was employed in the functionalization of the ketone moieties of P0 using three commercially available alkoxyamine hydrochlorides. Finally, electrophilic alkoxyetherification, a four-component reaction, was employed in the modification of alkene groups on polymer main chains using N-bromosuccinimide (NBS), tetrahydrofuran, and fluorinated carboxylic acid. Complete conversion of reactive sites was observed in both steps, and the two modification reactions exhibited excellent compatibility. The thermal properties of the polymers as thermal stability, and glass transition and melting behaviours were investigated by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC).