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Kinetic Study of Free-Radical Solution Copoly- merization of N-Acryloylmorpholine with an Activated Ester-Type Monomer, N-Acryloxysuccinimide

The kinetics of free radical solution (co)polymerization of N-acryloylmorpholine (NAM) and N-acryloxysuccinimide (NAS) have been investigated at 60°C in 1,4-dioxane using 2,2'-azoisobutyronitrile as the initiator. First, the k p /k 1/2 t value for the homopolymerization of NAM monomer was estimated to be 4.97 mol -1/2 .L 1/2 s -1/2 , which is indicative of a high ability of NAM to homopolymerize. Then, the reactivity ratios were determined to be r NAS = 0.63 = 0.03 and r NAM = 0.75 = 0.01. This binary comonomer system behaves like a perfectly random one, allowing the synthesis of macromolecules homogeneous in composition. Average copolymer compositions determined by 1 H NMR and 13 C NMR spectroscopy were in good agreement with the theoretical ones. Finally, monomer sequence distribution was studied by 13 C NMR analysis