Poly(bromoethyl acrylate): A Reactive Precursor for the Synthesis of Functional RAFT Materials

Article abstract of DOI:10.1021/acs.macromol.6b00721

Postpolymerization modification has become a powerful tool to create a diversity of functional materials. However, simple nucleophilic substitution reactions on halogenated monomers remains relatively unexplored. Here we report the synthesis of poly(bromoethyl acrylate) (pBEA) by reversible addition-fragmentation chain transfer (RAFT) polymerization to generate a highly reactive polymer precursor for postpolymerization nucleophilic substitution. RAFT polymerization of BEA generated well-defined homopolymers and block copolymers over a range of molecular weights. The alkylbromine-containing homopolymer and block copolymer precursors were readily substituted by a range of nucleophiles in good to excellent conversion under mild and efficient reaction conditions without the need of additional catalysts. The broad range of nucleophilic species that are compatible with this postmodification strategy enables facile synthesis of complex functionalities, from permanently charged polyanions to hydrophobic polythioethers to glycopolymers.