Knowledge of monomer reactivity ratios provides the necessary insight to control and predict the monomer sequence; however, these kinetic parameters are often time-consuming and difficult to accurately measure. In their study, Beers and co-workers reported a robust approach to measure monomer reactivity ratios using surface-initiated copolymerization and XPS as a synthesis and characterization toolset. For the range of monomer pairs investigated, reactivity ratios obtained from the non-linear least squares evaluation of XPS copolymer composition data are reproducible and are in good agreement with bulk reactivity ratios obtained by traditional NMR analysis. Additionally, they have developed and demonstrated a high-throughput approach to measure reactivity ratios using a single substrate exhibiting a gradient in copolymer brush composition. The high-throughput approach significantly reduces the time and effort required to generate reliable and reproducible point estimates of reactivity ratios, and these values are in good agreement with values obtained from both the discrete statistical copolymer brush and classical bulk analytical methods.
A robust and high-throughput measurement platform for monomer reactivity ratios from surface-initiated polymerization by Derek L. Patton, Kirt A. Page, Emily A. Hoff, Michael J. Fasolka and Kathryn L. Beers Polym. Chem., 2012, 3, 1174-1181.
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