Grafting poly(phenylene oxide) with poly(vinylphosphonic acid) for fuel cell membranes

Abstract

Densely phosphonated electrolyte membranes were prepared from poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) grafted with poly(vinylphosphonic acid) (PVPA) side chains. In the first step, PPO was lithiated in solution at room temperature by adding n-butyllithium to form an anionic macroinitiatior. Next, diethyl vinylphosphonate was anionically polymerized from the lithiated sites at −78 °C. This protocol gave good control over the density of the grafting sites and the copolymer composition. Films of copolymers containing between 35 and 74 wt% poly(diethyl vinylphosphonate) were first cast from solution and subsequently fully hydrolyzed to produce transparent flexible proton conducting membranes of PPO-graft-PVPA containing up to 6 mmol phosphonic acid groups per gram of dry copolymer. Thermogravimetric analysis showed anhydride formation at increasing temperatures above 100 °C with no copolymer degradation occurring until nearly 400 °C under air. Fully hydrated membranes reached proton conductivities above 1 mS cm−1 at −20 °C and 80 mS cm−1 at 120 °C.