Preparation of Poly(Ionic Liquid) Particles with Anionic Side Chain by Dispersion Polymerization.

Micrometer-sized poly(ionic liquid) (PIL) particles with an anionic side chain, poly(1-butyl-3-methylimidazolium 3-sulfopropyl methacrylate) (poly([Bmim][SPMT])), are successfully prepared by dispersion polymerization at 60 °C in ethanol/ethyl acetate (2/8, w/w) with poly(vinylpyrrolidone) as a stabilizer. However, the obtained particles do not maintain the particulate state during drying at room temperature due to poly([Bmim][SPMT])'s low glass-transition temperature, below room temperature. In order to prevent coalescence and maintain particle shape, a cross-linking monomer is added after the nucleation stage of dispersion polymerization. Moreover, Fourier-transform infrared spectroscopy (FT-IR) demonstrates cation exchange between the obtained particles and metal cations (Ag+ ).

Preparation of Methacrylate Polymer/Reduced Graphene Oxide Nanocomposite Particles Stabilized by Poly(ionic liquid) Block Copolymer via Miniemulsion Polymerization.

Poly(n-butyl methacrylate) (PnBMA)/reduced graphene oxide (rGO) nanocomposite films are prepared using two different routes. The first route involves preparation of PnBMA nanoparticles containing homogeneously dispersed rGO nanosheets by miniemulsion polymerization using a block copolymer of ionic liquid (IL) monomer and nBMA. The IL units act as adsorption sites for rGO whereas BMA units provide solubility in the BMA monomer droplets. Nanocomposite films obtained from miniemulsion polymerization exhibit higher tensile modulus in comparison with the films prepared by mixing a PnBMA emulsion and aqueous graphene oxide (GO) dispersion. The second route involves preparation of PnBMA particles armored with rGO nanosheets via miniemulsion polymerization using the same poly(ionic liquid) (PIL) block copolymer. An anionic exchange reaction is conducted to obtain more hydrophilic PIL units in the block copolymer, thus providing adsorption sites of GO nanosheets at the interface of the polymer particles. Subsequent chemical reduction of GO to rGO using hydrazine monohydrate results in formation of a PnBMA/rGO nanocomposite. The resulting nanocomposite film exhibits electrical conductivity (2.0 × 10-3 S m-1).

Synthesis of polymeric nanoparticles containing reduced graphene oxide nanosheets stabilized by poly(ionic liquid) using miniemulsion polymerization.

Polymeric nanoparticles containing reduced graphene oxide (rGO) nanosheets have been prepared by aqueous miniemulsion radical polymerization of methyl methacrylate (MMA) utilizing poly(ionic liquid) (PIL) as stabilizer to effectively disperse the rGO nanosheets in the monomer phase. The PIL that gave the best results in terms of rGO dispersibility was a block copolymer of the ionic liquid monomer 1-(2-methacryloyloxyethyl)-3-butylimidazolium bis(trifluoromethanesulfonyl)amide ([Mbim][TFSA]) and MMA, the concept being that the MMA units impart solubility in the MMA monomer droplets whereas the IL units act as adsorption sites for rGO. The rGO dispersibility in vinyl monomer was demonstrated to be superior using the above PIL block copolymer compared to the corresponding statistical copolymer or PIL homopolymer. Overall, the approach developed demonstrates how PILs can be employed to conveniently switch (turn ON/OFF) the dispersibility of PIL/rGO via anion exchange reactions, which can be an efficient strategy for synthesis of polymer/rGO nanocomposite materials.