The Synthesis of Acrylate‐Based Macromonomers and Structured Copolymers by High‐Temperature Semi‐Batch Radical Polymerization: The Impact of Acrylate vs. Methacrylate Monomer Choice

ABSTRACT High‐temperature starved‐feed semi‐batch radical polymerization is used to produce an isobornyl acrylate (iBoA) polymer solution with high macromonomer content without a mediating agent. The p(iBoA) macromonomer solution serves as an addition‐fragmentation agent to synthesize a blocky copolymer in a single‐pot sequential feeding process, as has been demonstrated using n ‐butyl acrylate (BA) as the second monomer. The impact of monomer selection on the copolymer product is investigated by switching the second monomer to n ‐butyl methacrylate (BMA) while keeping all other aspects of the operating strategy unchanged. Methodologies developed to verify macromonomer incorporation are used to compare the iBoA‐BA and iBoA‐BMA systems, with two‐dimensional liquid chromatography providing a clear contrast between the acrylate and methacrylate (co)polymer products. The comparison demonstrates the effect of monomer structure on the macromonomer addition‐fragmentation kinetics, with a blocky copolymer produced using the acrylate macromonomer only when an acrylate is used as the second monomer feed.