Tuning the Properties of Functional Pyrrolidinium Polymers by (Co)polymerization of Diallyldimethylammonium Ionic Liquids.

The synthesis and polymerization of novel diallyldimethylammonium ionic liquid monomers is described. A free-radical polymerization follows a ring-closing cyclopolymerization mechanism similar to the one observed previously for diallyldimethylammonium halides that leads to pyrrolidinium functional polymers. As previously observed in other families of polymeric ionic liquids, their physico-chemical properties are seriously affected by the nature of the counter-anion. As an example, the thermal stability increases following the trend SCN(-)  < ${\rm BF}_{4}^{ - }$ < ${\rm PF}_{6}^{ - }$ < bis(trifluoromethane)sulfonamide. Interestingly, this polymerization route may lead to the synthesis of a new family of random copolymers that have a similar poly(diallyldimethylammonium) backbone and a mixture of counter-anions determined by the comonomer selection.