摘要
Formation of styrene carbonate (SC) by the cycloaddition of CO2 to styrene oxide (SO) catalysed by pyrrolidinopyridinium iodide (PPI) in combination with zinc halides (ZnCl2, ZnBr2 and ZnI2) was investigated. Complete conversion of the SO to SC was achieved in 3 h with 100% selectivity using 1/0.5 molar (PPI/ZnI2) catalyst ratio under mild reaction conditions i.e., 100℃ and 10 bar CO2 pressure. The synergistic effect of ZnI2 and PPI resulted in more than 7-fold increase in reaction rate than using PPI alone. The cycloaddition reaction demonstrated the first-order dependence with respect to the epoxide, CO2 and catalyst concentrations. Moreover, the kinetic and thermodynamic activation parameters of SC formation were determined using the Arrhenius and Eyring equations. The positive values of △H(42.8 kJ mol^-1) and △G(102.3 kJ mol^-1) revealed endergonic and chemically controlled nature of the reaction, whereas the large negative values of △S(-159.4 J mol^-1 K^-1) indicate a highly ordered activated complex at the transition state. The activation energy for SC formation catalyzed by PPI alone was found to be 73.2 kJ mol^-1 over a temperature range of 100-140℃, which was reduced to 46.1 kJ mol^-1 when using PPI in combination with ZnI2 as a binary catalyst. Based on the kinetic study, a synergistic acid-based reaction mechanism was proposed.
Formation of styrene carbonate（SC） by the cycloaddition of CO2 to styrene oxide（SO） catalysed by pyrrolidinopyridinium iodide（PPI） in combination with zinc halides（Zn Cl2, Zn Br2 and Zn I2） was investigated. Complete conversion of the SO to SC was achieved in 3 h with 100% selectivity using 1/0.5 molar（PPI/Zn I2） catalyst ratio under mild reaction conditions i.e., 100℃ and 10 bar CO2 pressure. The synergistic effect of Zn I2 and PPI resulted in more than 7-fold increase in reaction rate than using PPI alone. The cycloaddition reaction demonstrated the first-order dependence with respect to the epoxide, CO2 and catalyst concentrations. Moreover, the kinetic and thermodynamic activation parameters of SC formation were determined using the Arrhenius and Eyring equations. The positive values of H(42.8 k J mol–1) and G（102.3 k J mol–1） revealed endergonic and chemically controlled nature of the reaction, whereas the large negative values of S(–159.4 J mol–1K–1) indicate a highly ordered activated complex at the transition state. The activation energy for SC formation catalyzed by PPI alone was found to be 73.2 k J mol–1 over a temperature range of 100–140 ℃, which was reduced to 46.1 k J mol–1 when using PPI in combination with Zn I2 as a binary catalyst. Based on the kinetic study, a synergistic acid-based reaction mechanism was proposed.
基金
supported by the Engineering and Physical Science Research Council (EPSRC) funding for Sustainable Polymers (Project reference EP/L017393/1)
