Polymerization mechanism for radiation-induced grafting of styrene into Alicyclic polyimide films for preparation of polymer electrolyte membranes

Park, J.; Enomoto, Kazuyuki; Yamashita, Takashi*; Takagi, Yasuyuki*; Todaka, Katsunori*; Maekawa, Yasunari

Alicyclic polyimides (APIs) were successfully applied to radiation-induced graft polymerization for developing polymer electrolyte membranes for fuel cells. The grafting into fully aromatized polyimide barely proceeded (grafting degrees (GDs) of less than 5%), whereas that of styrene into the API films proceeded with styrene GDs of up to 70%. In combination of electron spin resonance measurements and ultraviolet-visible (UV-VIS) spectroscopy, the radical species was identified as a long-lived intermediate and 10% of the radicals were consumed as grafting initiators. The moderate reaction conditions allowed for selective sulfonation on the polystyrene grafts, and not on the API substrates, to give API-based polymer electrolyte membranes (PEMs) with ion exchange capacities (IEC) of 1.7-2.8 mmol/g. The PEMs exhibited appropriate proton conductivity and low water uptake, together with excellent mechanical properties, compared with conventional PEMs such as Nafion.