Abstract
AbstractThe radical homopolymerization of N‐tert‐butyl acrylamide (t‐BuAAm) and its copolymerization with methyl acrylate (MA) is studied in ethanol/water solutions over a range of initial monomer and initiator levels between 50 and 70 °C. While short‐chain branching for poly(t‐BuAAm) samples could not be detected by 13C NMR, the reduced rate of monomer conversion with lowered monomer content indicates the formation of mid‐chain radicals (MCR) by backbiting. Adding water as a cosolvent to ethanol significantly increases reaction rates, in agreement with recent pulsed‐laser studies that quantify the influence of solvent composition on homopropagation kinetics. However, the measured drifts in comonomer composition with conversion are well represented by a single pair of reactivity ratios (rMA = 1.12 ± 0.01, rt‐BuAAm = 0.71 ± 0.01) over the complete range of experimental conditions. A mechanistic model developed to describe t‐BuAAm homopolymerization is extended to capture the impact of reaction operating conditions (monomer content and composition, solvent composition, initiator content, and temperature) on the features of t‐BuAAm/MA copolymerization, thus providing a tool for product and process optimization. The model structure can be used to support the development of other acrylate/acrylamide systems as part of the continued efforts to utilize “green” solvents to reduce the environmental impacts of polymerization processes.
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