Abstract

AbstractBy modifying the polymerization process of suspension polymerization of vinyl chloride, poly(vinyl chloride) (PVC) samples were prepared containing various amounts of compact glassy particles. It was found that these particles probably arise by a different polymerization mechanism than usual suspension particles, namely, as a result of the nonhomogeneous distribution of initiator in vinyl chloride drops of the polymerization system. It was proved experimentally that the lower heat stability of difficultly processible particles is due to a side reaction between the initiator radical and the PVC polymer chain which causes dehydrochlorination of PVC already under polymerization conditions. This reaction may also explain the yet unknown mechanism of formation of internal double bonds in PVC produced by the radical polymerization of vinyl chloride. In conclusion, the difficult processibility of compact glassy particles is discussed as a consequence of the insufficient drying of these particles in the usual drying process.

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