Polymerization of n‐butyl vinylether initiated by polymeric peroxycarbamates and active polystyrenes

The free radical promoted cationic polymerization of n‐butyl vinylether (BVE) was achieved by thermal decomposition of polymeric peroxycarbamates (PPC) or active polystyrene (APS), having fragments of PPC in the presence of diphenyliodonium hexafluorophosphate (Ph₂I⁺ PF 6−) or silver tetrafluoroborate (AgBF₄). Polymerizations were accompanied by phase separation. Formation of block copolymers, mainly in the solid phase, was evidenced by NMR spectroscopy. Polymer samples obtained by this procedure contained only a very small fraction of block copolymer structure due to the phase separation and very effective chain transfer reactions predominating the cationic polymerization of BVE.