In the recent rise of metal-free polymerization techniques,1 a strong phosphazene base (t-BuP4) has shown its remarkable strength as the promoter for the anionic polymerization of various types of monomers, especially epoxides.2 The in-situ activation/polymerization mechanism has allowed facile achievement of a wide variety of polyether-based macromolecular functionalities and architectures. In the present work, we are interested to employ amide moieties as initiating sites, instead of conventional hydroxyl groups, to further strengthen this polymer synthesis strategy.3 High-molecular-weight poly(N,N-dimethylacrylamide-co-acrylamide) was used as a model functional substrate, and t-BuP4-promoted anionic graft polymerizations were conducted directly from the primary amide moieties (Scheme 1). The (co)polymerization of ethylene oxide and propylene oxide is proven to be effective, leading to macromolecular combs with single homopolymer, double homopolymer and block copolymer side chains. Larger epoxide monomers could not be homopolymerized, while the copolymerizations with ethylene oxide were successful, leading to statistical copolymer side chains.

Facile metal-free “grafting-from” route from acrylamide-based substrate toward complex macromolecular combs

249th National Meeting (2015)

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