Multiblock copolymers, composed of different combinations and number of blocks, offer appreciable opportunities for new advanced materials. However, exploring this parameter space using traditional block copolymer synthetic techniques, such as living polymerization of sequential blocks, is time-consuming and requires stringent conditions. Using thiol addition across norbornene chemistry, we demonstrate a simple synthetic approach to multiblock copolymers that produces either random or alternating architectures, depending on the choice of reactants. Past reports have highlighted the challenges associated with using thiol-ene chemistry for polymer-polymer conjugation; however, using norbornene as the "ene" yielded multiblock copolymers at least four or five blocks. Preparation of new multiblock copolymers containing two or three block chemistries highlights the versatility of this new approach. These materials were thermally stable and showed microphase separation according to characterization by DSC, SAXS, and AFM. This chemical platform offers a facile and efficient route to exploring the many possibilities of multiblock copolymers.
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