Transesterification catalysts to improve clay exfoliation in synthetic biodegradable polyester nanocomposites

Abstract

We report here on the melt intercalation preparation of polymer/clay nanocomposites based on three commercial synthetic biodegradable polyesters: EastarBio Ultra, Ecoflex, and Bionolle, respectively. The montmorillonite clay addition is performed either by direct dispersion of Cloisite 30B in the polyester matrix or by dispersing a “PCL-grafted Cloisite 30B” masterbatch in the biodegradable polyesters. All obtained nanocomposites display an intercalated morphology as attested by X-ray diffraction measurements. The various analyses clearly show that the Bionolle (BIO) matrix gives the best results. Morphological characterization and mechanical properties of these nanocomposites also show that the “masterbatch route” leads to poor results as a consequence of the very low compatibility between the poly(ε-caprolactone) (PCL) of the masterbatch and the three other polyester matrices. In a second part, nanocomposites based on the BIO matrix are prepared by direct dispersion of the organo-clay in the presence of three different metal-based catalysts with the aim to promote transesterification reactions between the nanocomposite constituents. The mechanical properties and morphological characterization of these nanocomposites show that the tin-based catalyst (Sn) is the more efficient. Indeed, the effectiveness of transesterification reactions taking place between the ester functions of the BIO matrix and the hydroxyl groups of the organo-clay and the resulting “grafting” of BIO chains on the organo-clay surface are confirmed by thermogravimetric analyses performed after the extraction procedure. TEM observations show that this catalyst enhances the clay platelets exfoliation within the BIO matrix as a consequence of the transesterification reactions. Nanocomposites prepared in presence of Sn show better clay dispersion and enhanced stiffness with a 60% increase in Young’s modulus.