Effect of Bis(2-chloro-1-methylethy)ether on Cationic Polymerization of Styrene

Abstract

The effect of bis(2-chloro-l-methyl)ethypether (CIPE) on the cationic polymerization of styrene initiated by antimony pentachloride (SbCl₅) was studied in cyclohexane solution. The poly- merization degree was increased by the addition of small. amount of CIPE, whereas the rate of polymerization was decreased with increasing of CIPE. The overall activation energy was 7.7 kcal/mol.
CIPE forms a stable complex with SbCl₅, which may be dissociated on heating to chloroisopropyl carbonium cation. This carbonium cation is capable of initiating the cationic polymerization of styrene. But the oxonium anion (ClCH₂CH(CH₃)O-SbCl₅) may be more stable than carbonium cation. Therefore the high molecular weight polystyrene (MW=180000) was obtained.