Thermodynamics of the stereosequence propagations in the radical polymerization of vinyl chloride studied by 13C‐NMR and IR

The variation of the tacticties of radical poly(vinyl chloride)s as a function of the polymerization temperatures has been examined by 13C‐NMR (in terms of triads and tetrads) and IR (in terms of dyads). It has been observed that BERNOUILLIan statistics could be verified at 0°C for radical polymerization in bulk. The calculated values of differential enthalpies and entropies of activation revealed that, relatively, radical poly(methyl methacrylate)s propagate more easily in syndiotactic placement than radical poly(vinyl chloride)s.