Synthesis of Cross‐linked Ionic Poly(styrenes) and their Application as Catalysts for the Synthesis of Carbonates from CO2 and Epoxides

• Published in: ChemPlusChem (Weinheim, Germany) Germany), 2017-01, Vol.82 (1), p.144-151
• Main Authors: Bobbink, Felix D., Van Muyden, Antoine P., Gopakumar, Aswin, Fei, Zhaofu, Dyson, Paul J.
• Format: Article
• Language: English
• Subjects: carbon dioxide; cycloaddition; imidazolium salts; ionic polymers; sustainable chemistry
• ISSN: 2192-6506; 2192-6506
• DOI: 10.1002/cplu.201600461

A series of dicationic styrene‐functionalized imidazolium‐based salts, in which the two imidazolium rings are bridged by a functionalized spacer, are prepared. The salts are polymerized to afford cross‐linked imidazolium‐based ionic polystyrene materials, which, owing to the presence of the functionalized spaces, should be highly active organocatalysts for the cycloaddition of CO2 to epoxides to afford cyclic carbonates (CCE reaction). The catalytic activities of the polymers are evaluated in the CCE reaction. The most active catalyst incorporates a diol functionality and is active at 80 °C and a pressure of 4 bar at a loading of 5 mol %, which is comparable to the most active organocatalysts. Moreover, high yields can be obtained under atmospheric pressure upon increasing the temperature to 120 °C. Under harsher conditions, the catalyst is highly active at a loading one order of magnitude lower, highlighting the importance of benchmark conditions for the CCE reaction. Moreover, the polymer catalysts are advantageous because they can be used at low catalyst loadings, the carbonate product is easily isolated in pure form, and loss of activity of the recovered polymer catalyst is not observed during reuse. Cross‐linked ionic (poly)styrenes: Highly cross‐linked imidazolium‐based polymers are prepared and used as catalysts for the cycloaddition of CO2 with epoxides for carbonate production (see figure). The catalysts operate efficiently using CO2 at atmospheric pressure, and therefore, do not require the use of autoclaves.