Ion-Conducting Thermoresponsive Films Based on Polymer-Grafted Cellulose Nanocrystals

Mechanically robust, thermoresponsive, ion-conducting nanocomposite films are prepared from poly(2-phenylethyl methacrylate)-grafted cellulose nanocrystals ( MxG -CNC- g -PPMA ). One-component nanocomposite films of the polymer-grafted nanoparticle (PGN) MxG -CNC- g -PPMA are imbibed with 30 wt % imidazolium-based ionic liquid to produce flexible ion-conducting films. These films with 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ( MxG -CNC- g -PPMA/[H] ) not only display remarkable improvements in toughness (>25 times) and tensile strength (>70 times) relative to the corresponding films consisting of the ionic liquid imbibed in the two-component CNC/PPMA nanocomposite but also show higher ionic conductivity than the corresponding neat PPMA with the same weight percent of ionic liquid. Notably, the one-component film containing 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ( MxG -CNC- g -PPMA/[E]) exhibits temperature-responsive ionic conduction. The ionic conductivity decreases at around 60 °C as a consequence of the lower critical solution temperature phase transition of the grafted polymer in the ionic liquid, which leads to phase separation. Moreover, holding the MxG -CNC- g -PPMA/[E] film at room temperature for 24 h returns the film to its original homogenous state. These materials exhibit properties relevant to thermal cutoff safety devices (e.g., thermal fuse) where a reduction in conductivity above a critical temperature is needed.