Chemical modification of poly(vinyl chloride): A conclusive study of the influence of tacticity

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Abstract
Three samples, A, B and C, of poly(vinyl chloride) (PVC) were prepared at 90, 60, and 0°C, respectively, to give them different isotactic content measured by 13C‐NMR spectroscopy. A kinetic study of the nucleophilic substitution with sodium thiophenate, carried out for the three samples, showed that even at temperatures as high as 60°C a fraction of the units remain unreactive and that the extent of this fraction depends on the syndiotactic content of the polymer. This was also supported by a comparison of the behavior of samples B and C in substitution experiments at 5 and 60°C. In contrast the substitution experiments at −30°C demonstrated that, as suggested, a small fraction of extremely reactive units exists in PVC, the content of which is higher as the isotactic content of the polymer increases. In this connection, and even though a slight contribution of some defect structures cannot be ruled out, a 13C‐NMR analysis of sample B after modification at 40°C to various degrees demonstrates that the reactivity of the isotactic triads is high in relation to the heterotactic. On the basis of the results obtained and the possible conformations in PVC the substitution mechanism is related to the occurrence of isotactic TT conformations. The results, as discussed in terms of the various ways in which isotactic TT conformations appear open new prospects in the field of PVC chemical modification and stabilization mechanisms.