Anionic Polymerization of Phenyl Glycidyl Ether in Miniemulsion

The anionic polymerization of phenyl glycidyl ether (PGE) in miniemulsion was investigated. Didodecyldimethylammonium hydroxide was used as an inisurf, i.e., exhibiting both surface-active properties and the ability to initiate polymerization by means of its hydroxide counterion. Stable miniemulsions were obtained by ultrasonication, and then polymerization was carried out to produce genuine α,ω-dihydroxylated polyether chains as revealed by 1H NMR, FTIR, or mass spectroscopic methods. The average molecular weight could be increased by varying the initiator concentration, type and concentration of surfactants or by adding a cosurfactant (typically alcohol). In all attempts, polymer chains increased in size with conversion but remained small, with a critical polymerization degree of DPmax = 8. A mechanism was proposed to account for these results. From these observations, phenyl glycidyl ether could be used as a model monomer to investigate ionic polymerization in miniemulsion.