Abstract
The number of mmr‐ and rrm‐based structures which occur necessarily whenever an isotactic or a syndiotactic sequence breaks off respectively; the extent to which they are isolated or are extended to atactic sequences, and the fact that the mmr repeating sequence, especially when it takes the GTTG^−^TT conformation, is shorter and exhibits greater local free volume than rrm, mmm and rrr sequences, are shown to be the stereochemical composition determining structures in poly(vinyl chloride) (PVC) and polypropylene (PP) polymers. These structures, as analyzed by ^13^C NMR spectroscopy and probability calculations, have been determined as a function of the overall tacticity for one series of samples prepared by bulk polymerization at temperatures varying from −50 °C to 70 °C, and one series of samples prepared by polarity‐based fractionation of a commercial polymer. Using this approach, the stereochemical composition of the samples could be identified. The results are of interest to understand the changes in the physical properties as shown in earlier and current work for both series of polymers.
© 2003 Society of Chemical Industry