Effects of Immobilized Ionic Liquid on Properties of Biodegradable Polycaprolactone/LDH Nanocomposites Prepared by In Situ Polymerization and Melt-Blending Techniques.

The high capacity of calcinated layered double hydroxides (LDH) to immobilize various active molecules together with their inherent gas/vapor impermeability make these nanoparticles highly promising to be applied as nanofillers for biodegradable polyester packaging. Herein, trihexyl(tetradecyl)phosphonium decanoate ionic liquid (IL) was immobilized on the surface of calcinated LDH. Thus, the synthesized nanoparticles were used for the preparation of polycaprolactone (PCL)/LDH nanocomposites. Two different methods of nanocomposite preparation were used and compared: microwave-assisted in situ ring opening polymerization (ROP) of ε-caprolactone (εCL) and melt-blending. The in situ ROP of εCL in the presence of LDH nanoparticles with the immobilized IL led to homogenous nanofiller dispersion in the PCL matrix promoting formation of large PCL crystallites, which resulted in the improved mechanical, thermal and gas/water vapor barrier properties of the final nanocomposite. The surface-bonded IL thus acted as nanofiller surfactant, compatibilizer, as well as thermal stabilizer of the PCL/LDH nanocomposites. Contrary to that, the melt-blending caused a partial degradation of the immobilized IL and led to the production of PCL nanocomposites with a heterogenous nanofiller dispersion having inferior mechanical and gas/water vapor barrier properties.