Synthesis of Novel Polycations Using the Chemistry of Ionic Liquids

<jats:title>Abstract</jats:title><jats:p><jats:bold>Summary:</jats:bold>In this work, we report the synthesis of a great variety of polycations with varying counter‐anions. These new polymers were obtained by a simple anion exchange reaction facilitated by the phase separation of the resulting products. This strategy has been successfully applied to three different polycations, poly(1‐vinyl‐3‐ethylimidazolium bromide) poly(ViEtIm<jats:sup>+</jats:sup>Br<jats:sup>−</jats:sup>), poly(1‐ethyl‐4‐vinylpyridinium bromide) poly(ViEtPy<jats:sup>+</jats:sup>Br<jats:sup>−</jats:sup>), and poly(methacryloyloxyethyltrimethylammonium chloride) poly(EMTMA<jats:sup>+</jats:sup>Cl<jats:sup>−</jats:sup>), with seven counter‐anions such as PF<jats:inline-graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="graphic/tex2gif-stack-1.gif" xlink:title="urn:x-wiley:10221352:media:MACP200400411:tex2gif-stack-1"/>, CF<jats:sub>3</jats:sub>SO<jats:inline-graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="graphic/tex2gif-stack-2.gif" xlink:title="urn:x-wiley:10221352:media:MACP200400411:tex2gif-stack-2"/>, (CF<jats:sub>3</jats:sub>SO<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub>N<jats:sup>−</jats:sup>, (CF<jats:sub>3</jats:sub>CF<jats:sub>2</jats:sub>SO<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub>N<jats:sup>−</jats:sup>, dodecylbenzenesulfonate, toluene‐4‐sulfonate, and bis(2‐ethylhexyl) hydrogen phosphate. The solubility range of the new polymeric ionic liquids becomes very broad, including apolar organic solvents and ionic liquids, depending on the nature of the counter‐anion. Thermogravimmetric experiments showed that the thermal stability of the PILs also depends on the nature of the counter‐anion improving in the order CF<jats:sub>3</jats:sub>SO<jats:inline-graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="graphic/tex2gif-stack-3.gif" xlink:title="urn:x-wiley:10221352:media:MACP200400411:tex2gif-stack-3"/> > (CF<jats:sub>3</jats:sub>CF<jats:sub>2</jats:sub>SO<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub>N<jats:sup>−</jats:sup> > C<jats:sub>12</jats:sub>H<jats:sub>25</jats:sub>C<jats:sub>6</jats:sub>H<jats:sub>4</jats:sub>SO<jats:inline-graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="graphic/tex2gif-stack-4.gif" xlink:title="urn:x-wiley:10221352:media:MACP200400411:tex2gif-stack-4"/> > PF<jats:inline-graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="graphic/tex2gif-stack-5.gif" xlink:title="urn:x-wiley:10221352:media:MACP200400411:tex2gif-stack-5"/> > Br<jats:sup>−</jats:sup> > C<jats:sub>16</jats:sub>H<jats:sub>34</jats:sub>PO<jats:inline-graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="graphic/tex2gif-stack-6.gif" xlink:title="urn:x-wiley:10221352:media:MACP200400411:tex2gif-stack-6"/>.</jats:p><jats:p><jats:boxed-text content-type="graphic" position="anchor"><jats:caption><jats:p>A simple anion exchange procedure similar to the reaction used in ionic liquids chemistry is used to the synthesis of new polymeric ionic liquids (PILs).</jats:p></jats:caption><jats:graphic xmlns:xlink="http://www.w3.org/1999/xlink" mimetype="image/jpeg" position="anchor" specific-use="enlarged-web-image" xlink:href="graphic/mgra001.jpg"><jats:alt-text>magnified image</jats:alt-text><jats:caption><jats:p>A simple anion exchange procedure similar to the reaction used in ionic liquids chemistry is used to the synthesis of new polymeric ionic liquids (PILs).</jats:p></jats:caption></jats:graphic></jats:boxed-text></jats:p>