A comprehensive approach to the stereochemical and physical factors in nucleophilic substitution on PVC in the melt

摘要

AbstractThe nucleophilic substitution reactin of poly(vinyl chloride) (PVC) with sodium benzenethiolate (NaBT) has been studied in the melt with the aim of determining whether a conformational mechanism is applicable under conditions that would apply in the polymer processing. The evolution of unreacted syndio, hetero, and isotactic triads content, and of the apparent molecular weight has been followed by13C‐NMR and GPC, respectively. The kinetic behavior was defined by choosing appropriate mixing conditions of temperature, shear stress, load, and amount of plasticizer. In all cases the kinetic curves attain a plateau after a rather fast reaction period has elapsed. The conversion at the plateau, that is, the reaction efficiency, proved to depend linearly on the amount of nucleophile and is hardly influenced by the mixing conditions for a given stoichiometric composition. The mixing conditions have been found to affect markedly the kinetics but to be quite inoperative on the evolution of both the content of unreacted tactic triads and the apparent molecular weight with degree of conversion. The results are discussed by taking into consideration those previously obtained in solutio