Exploiting Addition–Fragmentation Reactions to Produce Low Dispersity Poly(isobornyl acrylate) and Blocky Copolymers by Semibatch Radical Polymerization
Nina Heidarzadeh, Elizabeth G. Bygott, Robin A. Hutchinson
Abstract
Solution radical homopolymerization of isobornyl acrylate (iBoA) under starved-feed higher temperature conditions unexpectedly leads to polymer product with low dispersity (<1.3) compared to the polymerization of butyl acrylate (BA) under identical conditions. Both backbiting and β-scission reactions occur, as the poly(iBoA) product contains close to 100% terminal double bond (TDB) functionality. However, the addition of monomer to the midchain radicals formed by backbiting is sterically hindered, greatly reducing both short and long-chain branching. The poly(iBoA) macromonomer functions as an excellent addition-fragmentation agent, not only lowering dispersity but also providing a means to efficiently produce blocky acrylate copolymers through sequential monomer feeding in the starved-feed semibatch process.