Toughening Ionic Polymer Using Bulky Alkylammonium Counterions and Comb Architecture

Ionic interactions in ionic polymers, such as ionomers, polyelectrolytes, and polyampholytes, contribute to toughness in systems with high mobility and active ion dynamics, such as hydrogels and elastomers. However, it remains challenging to toughen rigid polymers through ionic interactions without lowering their elastic modulus through plasticization. Here, we present a strategy for toughening without sacrificing the elastic modulus by combining a comb polymer with bulky ammonium counterions. We designed and synthesized ionic comb polymers with oligoethylene glycol side chains and carboxylic acids in each monomer unit of the polynorbornene backbone, neutralized by trialkylamines, ranging from ethyl to octyl. The counterion size in ionic comb polymers influenced the mechanical properties of tensile testing─not the elongation at break and the elastic modulus but the ultimate strength and toughness. The ionic comb polymer containing heptylammonium counterions displayed the highest toughness of 77 MJ m^-3. Tensile studies at various strain rates demonstrated a rate-dependent difference between heptyl- and octylammonium counterions. This result suggests that the heptylammonium counterion acted as a sacrificial bond by providing a moderate dissociation rate that was slightly slower than that of the octylammonium counterion, leading to toughening.