Kinetic study of the free‐radical polymerization of vinyl acetate in the presence of deuterated chloroform by 1H‐NMR spectroscopy

Abstract

AbstractThe free‐radical polymerization of vinyl acetate was performed in the presence of deuterated chloroform (CDCl3) as a chain‐transfer agent (telogen) and 2,2′‐azobisisobutyronitrile as an initiator. The effects of the initiator and solvent concentrations (or equivalent monomer concentration) and the reaction temperature on the reaction kinetics were studied by real‐time 1H‐NMR spectroscopy. Data obtained from analysis of the 1H‐NMR spectra were used to calculate some kinetic parameters, such as the initiator decomposition rate constant (kd), kp(f/kt)1/2 ratio (where kp is the average rate constant for propagation, f is the initiator efficiency, and kt is the average rate constant for termination), and transfer constant to CDCl3 (C). The results show that kd and kp(f/kt)1/2 changed significantly with the solvent concentration and reaction temperature, whereas they remained almost constant with the initiator concentration. C changed only with the reaction temperature. Attempts were made to explain the dependence of kp(f/kt)1/2 on the solvent concentration. We concluded from the solvent‐independent C values that the solvent did not have any significant effect on the kp values. As a result, changes in the kp(f/kt)1/2 values with solvent concentration were attributed to the solvent effect on the f and/or kt values. Individual values of f and kt were estimated, and we observed that both the f and kt values were dependent on the solvent (or equivalent monomer) concentration. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008