Are o‐nitrobenzyl (meth)acrylate monomers polymerizable by controlled‐radical polymerization?

Abstract We report on the controlled‐radical polymerization of the photocleavable o ‐nitrobenzyl methacrylate (NBMA) and o ‐nitrobenzyl acrylate (NBA) monomers. Atom transfer radical polymerization (ATRP), reversible addition‐fragmentation chain transfer polymerization (RAFT), and nitroxide‐mediated polymerization (NMP) have been evaluated. For all methods used, the acrylate‐type monomer does not polymerize, or polymerizes very slowly in a noncontrolled manner. The methacrylate‐type monomer can be polymerized by RAFT with some degree of control (PDI ∼ 1.5) but leading to molar masses up to 11,000 g/mol only. ATRP proved to be the best method since a controlled‐polymerization was achieved when conversions are limited to 30%. In this case, polymers with molar masses up to 17,000 g/mol and polydispersity index as low as 1.13 have been obtained. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6504–6513, 2009