Copolymerization of N‐vinyl‐2‐pyrrolidone and 2‐phenyl‐1,1‐dicyanoethene

摘要

AbstractRadical copolymerization ofN‐vinyl‐2‐pyrrolidone (NVP) with 2‐phenyl‐1,1‐dicyanoethene (PDE) was studied in benzene at 70°C. Terminal, penultimate, and monomer complex participation kinetic models were applied to compositional data for best prediction of the copolymer composition. Both penultimate and complex models described satisfactorily the deviation from the terminal copolymerization model, although the complex model did not predict as well as the penultimate model at high NVP/PDE monomer feed ratios. Copolymerization reactivity ratios rNVP= 0.08 and r′NVP= 1.8 indicated substantial effect of the penultimate PDE monomer unit associated with polar repulsion of cyano groups. Equilibrium constant of NVP‐PDE comonomer complex formation was found to be 0.08 L/mol as estimated by proton nuclear magnetic resonance (NMR) analysis of PDE's vinylic proton chemical shift upon complexation. Rate constants of propagation reactions were estimated by applying terminal complex copoly