Metal-catalyzed living radical graft copolymerization of butyl methacrylate and styrene initiated from the structural Defects of narrow molecular weight distribution poly(vinyl chloride)

Abstract

Poly(vinyl chloride) (PVC) prepared by the radical polymerization of vinyl chloride (VC) contains allyl chloride and tertiary chloride structural defects. The graft copolymerization initiated from the structural defects of PVC should eliminate the structural defects of PVC and, therefore, should provide novel graft copolymers that will exhibit both new physical properties and higher thermal stability than the parent PVC. The preliminary graft copolymerization experiments reported previously from our laboratory were performed with PVC with broad molecular weight distribution and did not allow kinetic experiments to be performed. Model compounds for the allyl chloride defects in PVC were used as initiators and gave almost quantitative initiation in the case of styrene (0.99), while for methacrylates the maximum initiator efficiency was only 0.40. Based on these data, the successful grafting of PVC with butyl methacrylate (BMA) and the less successful grafting of PVC with styrene were difficult to be explained. This publication reports the metal catalyzed living radical graft copolymerization experiments initiated from the structural defects of PVC with narrow molecular weight distribution. These experiments demonstrate that, contrary to the results obtained using model compounds as initiators, the structural defects of PVC provide an excellent initiation efficiency for the graft copolymerization of BMA and a less efficient initiation for the case of styrene. Under suitable reaction conditions, the initiation efficiency from the structural defects of PVC for the graft copolymerization of BMA can be considered to be quantitative. Kinetic plots for the grafting copolymerization BMA-PVC.