A facile strategy for the synthesis of block copolymers bearing an acid-cleavable junction

Post-cleavable block copolymers are crucially important for the fabrication of nanoporous structures from the self-assembly of block copolymers by the selective etching of one block. Here, we present a facile and inexpensive approach to synthesize block copolymers bearing an acid-cleavable junction. A difunctional inifer containing an acetal group is synthesized for the sequential reversible addition-fragmentation transfer (RAFT) polymerization of tert-butyl methacrylate and atom transfer radical polymerization (ATRP) of styrene. Moreover, the polymerization sequence of the monomers can be altered. The acetal junctions in the resulting block copolymers can be readily cleaved by acid under ambient conditions. Aldehyde or monoglyceride end groups are left at the ends of the PS residues, which can be used as binding sites for future applications.