Polymer electrolyte membrane with nanomatrix channel prepared by sulfonation of natural rubber grafted with polystyrene

High‐proton‐conductive polymer electrolyte with a nanomatrix channel was prepared by graft copolymerization of styrene onto deproteinized natural rubber followed by sulfonation with chlorosulfonic acid. First, natural rubber latex was purified with urea in the presence of surfactant to remove almost all proteins present in the rubber. Second, graft copolymerization of styrene onto deproteinized natural rubber was carried out with tert‐butyl hydroperoxide/tetraethylenepentamine as an initiator at 30°C in latex stage. The graft‐copolymerized natural rubber (DPNR‐graft‐PS) was sulfonated with chlorosulfonic acid in chloroform solution at an ambient temperature. The resulting sulfonated DPNR‐graft‐PS was characterized by FTIR spectroscopy, solid state ¹³C CP/MAS NMR spectroscopy, elemental analysis, and transmission electron microscopy. High proton conductivity of about 0.1 S/cm, less water uptake of 24 wt % and comparatively good stress at break of 9 MPa were accomplished at suitable contents of styrene units and sulfur, i.e., 32 wt % and 75 mol %, respectively. The high proton conductivity, excellent stability, and good mechanical properties were associated with not only the formation of the nanomatrix channel but also a specific concentration of sulfuric acid group. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.