A living polymerization process for preparation of poly(vinyl chloride) (PVC) with controlled molecular weight and molecular weight distribution is described. The polymerization reaction can be initiated by various polyhalocarbon initiators in conjunction with non-metallic reducing single electron transfer reagents as catalysts and accelerated by electron shuttles. The process occurs at room temperature in water or water-organic solvent medium. The polymerization provides PVC with a controlled molecular weight and narrow molecular weight distribution. The halogen containing polymer compositions are useful as, among others, viscosity modifiers, impact modifiers and compatibilizers.

 
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