Characterisation of poly(vinylchloride)

0.5 10-3 .r;O~g branch and 5 10-3 chloromethyl group permonomer uni t (m.u.) possibly originating from head-to-head monomer placement are f.ound in industrial PVC (fewer in low-temperature polymerized products). TertiarY chlorine atoms, if any, correspond to long branches ; internal double bonds (0.05 10-3 per m.u. and over) can start polydiene sequences. 1 H and 1 3c NMR spectroscopy shows that syndiotactic placement is slightly favored over isotactic, depending only on polymerization temperature (PT). The number of aggregates in solution is very sensitive to PT,increasing with syndiotacticity, and heating up gives molecular solutions. Crystallizability increases with syndiotacticity, and two types of crystals exist ;