Synthesis Of Poly(Ionic Liquids) And Their Application In Catalytic Organic Reactions And Self-Assemble To Reverse Polymeric Micelles

Due to their wide use in separation process, material synthesis and substitution of traditional organic solvents, ionic liquids have currently received great attention. Despite some excellence results in chemical process, there are still some limitations in their widespread use in industry process such as product isolation, reuse of catalyst, high price of ready ionic liquids and toxicity. Modified with functional groups, physical and chemical properties of ionic liquids may be improved dramatically, providing a huge room for their wide application. The immobilization of ionic liquids on a support could combine the advantages of ionic liquids with those of heterogeneous support materials. In this study, we have synthesized a new type of polymer supported task-specific ionic liquids, and have investigated their application in catalysis. In addition, we have also synthesized a series of imidazolium-based poly(ionic liquids) and explored their application as components of reverse polymeric micelles. The research work presented here mainly includes the following parts:1. A new type of polystyrene-supported imidazolium ionic liquids have been synthesized, in which the imidazolium cations deliberately couple amino acids via the ionic-pair interaction. These supported ionic liquids with different loading levels of imidazolium or L-proline moieties could be achieved by tuning the amount or variety of the monomer.2. The polymer-supported task-specific ionic liquids in combination with CuI have been applied in the N-arylation of N-containing heterocycles with aryl or heteroaryl halides. A wide range of aryl halides or heteroaryl halides even bearing functional groups could be conducted smoothly to afford the corresponding products in good to excellent yields and with good selectivity. The catalyst system has shown a remarkable recyclability of up to nine turns. To the best our knowledge, our protocol is among the most efficient catalyst system for the N-arylation of N-containing heterocycles reported so far.3. The polymer-supported task-specific ionic liquids have displayed a considerable ability for Pd(OAc)₂ scavenging onto its surface. The soaked Pd material has been used in catalytic hydrogenation of stryene, showing remarkable activity of up to a TON of 5000 (yield＞99ï¼…) in water or under solvent free condition. In addition, the catalyst has also shown a high catalytic performance for the Heck reaction.4. A series of polyimidazolium ionic liquids beating long alkyl chains have been synthesized. We demonstrates for the first time that these poly(ionic liquids) themselves could assemble to form reverse polymeric micelles. The polymeric micelles are composed of inner hydrophilic imidazolium moiety and outer hydrophobic long chains. Thus, these poly(ionic liquids) are capable of extracting hydrophilic dye such as Congo Red from its aqueous solution into the organic phase to form the supramolecular aggregates.