Abstract
Radical copolymerization reaction of vinyl acetate (VA) and methyl acrylate (MA) was performed in a solution of benzene‐d6 using benzoyl peroxide (BPO) as the initiator at 60°C. Kinetic studies of this copolymerization reaction were investigated by on‐line 1H‐NMR spectroscopy. Individual monomer conversions vs. reaction time, which was followed by this technique, were used to calculate the overall monomer conversion, as well as the monomer mixture and the copolymer compositions as a function of time. Monomer reactivity ratios were calculated by various linear and nonlinear terminal models and also by simplified penultimate model with r 2(VA)=0 at low and medium/high conversions. Overall rate coefficient of copolymerization was calculated from the overall monomer conversion vs. time data and k p . k t −0.5 was then estimated. It was observed that k p . k t −0.5 increases with increasing the mole fraction of MA in the initial feed, indicating the increase in the polymerization rate with increasing MA concentration in the initial monomer mixture. The effect of mole fraction of MA in the initial monomer mixture on the drifts in the monomer mixture and copolymer compositions with reaction progress was also evaluated experimentally and theoretically.
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