Construction of hyper-crosslinked ionic polymers with high surface areas for effective CO2 capture and conversion

Construction of silsesquioxane and phosphinum‐based ionic porous hypercrosslinked polymers for efficient heterogeneous catalytic CO2 cycloaddition

“…In addition, the in‐situ formed POSS‐derived Si–OH groups could be used as HBD active groups to work together with mixed active anions, which also play an important role in enhancing the heterogeneous catalytic performance of P‐iPHCP‐14. As a result, the good catalytic performance of P‐iPHCP‐14 for the conversion of CO 2 with EH under mild conditions was superior to most of many previously reported metal‐free iPOPs 11,15–20,32,35,36,39,48 and metal‐based iPOPs catalysts 28,29,33,57,58 (seen the detailed comparisons Table S2), which can be attributed to the synergistic catalysis of free nucleophilic anions Cl − and Br − , the complex anion [AlCl 3 Br] − and POSS‐derived Si–OH HBD active groups in the catalyst P‐iPHCP‐14.…”

“…The targeted ionic porous hypercrosslinked polymers P‐iPHCP‐ x ( x = 21, 11, 12 and 14) were synthesized in high yields over 86% by varying the molar ratios of VPOSS to [PPh 3 Me]Br through the AlCl 3 ‐catalyzed Friedel‐Crafts reaction, while the active mixed anions Cl − , Br − and [AlCl 3 Br] − via ion‐exchange and coordination interactions. It is worth noting that the commercially available organic ionic salt [PPh 3 Me]Br has a low price of ~33 USD/kg, which is much lower than those of many well‐designed vinyl‐functionalized phosphinum‐based ionic monomers 25,26,30 and other phenyl‐contained organic salts (e.g., imidazolium salts) 33,46–48 . After the Friedel‐Crafts reaction between crystalline monomers VPOSS and [PPh 3 Me]Br in one‐pot, the obtained typical polymer P‐iPHCP‐14 lost most of the characteristic sharp Bragg diffraction peaks that can be assigned to raw crystalline monomers, indicating the formation of a non‐crystalline polymer.…”

“…It is worth noting that the commercially available organic ionic salt [PPh 3 Me]Br has a low price of $33 USD/kg, which is much lower than those of many well-designed vinyl-functionalized phosphinum-based ionic monomers 25,26,30 and other phenyl-contained organic salts (e.g., imidazolium salts). 33,[46][47][48] After the Friedel-Crafts reaction between crystalline monomers VPOSS and [PPh 3 Me] Br in one-pot, the obtained typical polymer P-iPHCP-14 lost most of the characteristic sharp Bragg diffraction peaks that can be assigned to raw crystalline monomers, indicating the formation of a non-crystalline polymer. However, the X-ray diffraction (XRD) pattern (Figure 1) of P-iPHCP-14 still shows an obvious broad Bragg diffraction peak at 10.3 with a d-spacing value (0.86 nm) compared with a sharp peak at 9.8 (d-spacing value 0.89 nm) for VPOSS, which can be assigned to the molecular dimensions of the enlarged ionic salts-cross-linked VPOSS cages.…”

Green synthesis of hypercrosslinked polymers for CO2 capture and conversion: recent advances, opportunities, and challenges

“…An-CPOP-2 has a triazine structure, containing N atoms, which increases the affinity for CO 2 guest molecules. In addition, Cai and his colleagues 107 prepared PIP-1 to PIP-3 using BCMBP and three different ionic-liquid-derived monomers (Fig. 10a).…”