Radiation-induced graft polymerization of functional monomer into poly(ether ether ketone) film and structure-property analysis of the grafted membrane

Hasegawa, Shin; Takahashi, Shuichi*; Iwase, Hiroki*; Koizumi, Satoshi; Morishita, Norio; Sato, Ken*; Narita, Tadashi*; Onuma, Masato*; Maekawa, Yasunari

Radiation-induced graft polymerization of sulfo-containing styrene derivatives into poly(ether ether ketone) (PEEK) substrates was carried out to prepare thermally and mechanically stable polymer electrolyte membranes based on an aromatic hydrocarbon polymer. Graft polymerization of ethyl 4-styrenesulfonate into a 32% crystallinity degree PEEK substrate hardly progressed, whereas graft polymerization into 11% PEEK substrate gradually progressed, achieving a grafting degree of more than 50% after 72 h. From Electron Spin Resonance analysis of irradiated PEEK films, it apparent the graft polymerization initiate from the phenoxy radicals. Small-angle X-ray scattering and small-angle neutron scattering observations clearly showed that the graft-type PEEK membranes possessed ion channel domains with the average distance of 13 nm, being larger than that of Nafion. Furthermore, there was a micro-structure in the ion channels with the average distance of 1.8 nm.