A simple and divergent synthetic strategy of bottlebrush polymers (BBPs) is presented, consisting of postpolymerization modification of a macromonomer and grafting-through polymerization. Beginning with a single macromonomer, its direct modification could build a library of macromonomers with an identical chain length, thus guaranteeing the precision in the synthesis of BBPs. In this study, a newly designed norbornenyl-terminated poly(methyl acrylate) (NB-PMA) is proposed as a chemically robust template. Ti-mediated transesterification of NB-PMA successfully produces structurally diverse polyacrylates while maintaining the terminal norbornenyl group intact. All macromonomers obtained from transesterification possess a good grafting-through ring-opening metathesis polymerization reactivity, furnishing homo, random, and block BBPs in a controllable manner. Moreover, atomic force microscopy analysis supports the controlled side-chain length distribution in the resulting BBPs.
A new sequential post-polymerization modification route has been developed for the synthesis of multifunctional polymers from a simple aldehyde polymer. In the first modification step, a template polymer derived from the radical polymerization of 4-vinyl benzaldehyde undergoes Rh-catalyzed hydroacylation with alkenes to furnish a group of ketone polymers. In the second modification step, Schiff base formation with alkoxy ammonium salts introduces a second group-an oxime functionality. Both the steps are highly efficient, introducing evenly distributed dual functionalities at the same position.
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