Photoinduced Acrylate Polymerization: Unexpected Reduction in Chain Branching

The branching stemming from midchain radical formation in n ‐butyl acrylate polymerization is investigated via melt‐state 13 C NMR measurements. The dependence of the degree of branching (DB) on the monomer conversion of the system is examined for photoinduced polymerizations, revealing a steady increase in branching with conversion. For polymerization at moderate light intensities, an increase in branching from 0.03% to 0.37% is observed for polymerizations at 60 °C, which is fivefold below the level of branching observed in thermally initiated polymerizations under otherwise identical reaction conditions. The reason for this overall reduction in branching remains momentarily unclear; yet, a strong dependence of branching on light intensity is observed. While polymerization under a 1 W LED lamp results at almost full monomer conversion in branching degrees of 0.22%, polymerization under a 400 W lamp yields 1.81% of chain branches.