Critical Role of Ion Exchange Conditions on the Properties of Network Ionic Polymers

Ionic polymers are important in a wide range of applications and can exhibit widely different properties depending on the ionic species. In the case of single ion conducting polymers, where one charge is attached to the backbone or as a side group, ion exchange is performed to control the mobile species. While the conditions are often specified, the final ion content is not always quantified, and there are no clear criteria for what concentration of salt is needed in the exchange. A series of ammonium network ionic polymers with different precise carbon spacers (C4–C7) between ionic junctions were synthesized as model systems to understand how the ion exchange conditions impact the resultant polymer properties. The initial networks with free bromide anions were exchanged with 1.5, 3, or 10 equiv of lithium bis­(trifluoromethane)­sulfonimide (LiTFSI) salt in solution. For networks with seven carbons between cross-links, increasing the LiTFSI concentration led to an increase in ion exchange efficiency from 83.6 to 97.6 mol %. At the highest conversion, the C7 network showed a 4 °C decrease in glass transition temperature (T_g), a 50 °C increase in degradation temperature, 12-fold lower water uptake from air, and a greater than 10-fold increase in conductivity at 90 °C. These results illustrate that properties such as T_g are less sensitive to residual ion impurities, whereas the conductivity is highly dependent on the final exchange conversion.