Aliphatic Anion Exchange Ionomers with Long Spacers and No Ether Links by Ziegler-Natta Polymerization: Properties and Alkaline Stability.

In this work we report the synthesis of poly(vinylbenzylchloride-co-hexene) copolymer grafted with N,N-dimethylhexylammonium groups to study the effect of an aliphatic backbone without ether linkage on the ionomer properties. The copolymerization was achieved by the Ziegler-Natta method, employing the complex ZrCl 4 (THF) 2 as a catalyst. A certain degree of crosslinking with N,N,N',N'-tetramethylethylenediamine (TEMED) was introduced with the aim of avoiding excessive swelling in water. The resulting anion exchange polymers were characterized by 1 H-NMR, FTIR, TGA, and ion exchange capacity (IEC) measurements. The ionomers showed good alkaline stability; after 72 h of treatment in 2 M KOH at 80 °C the remaining IEC of 76% confirms that ionomers without ether bonds are less sensitive to a S N 2 attack and suggests the possibility of their use as a binder in a fuel cell electrode formulation. The ionomers were also blended with polyvinyl alcohol (PVA) and crosslinked with glutaraldehyde. The water uptake of the blend membranes was around 110% at 25 °C. The ionic conductivity at 25 °C in the OH - form was 29.5 mS/cm.