Improving the Thermal and Mechanical Properties of Poly(l-lactide) by Forming Nanocomposites with an in Situ Ring-Opening Intermediate of Poly(l-lactide) and Polyhedral Oligomeric Silsesquioxane.

In this study, a series of poly(l-lactide) and (3-amino)-propylheptaisobutyl cage silsesquioxane (PLLA-AMPOSS) intermediates were first fabricated using single-arm in situ solution polymerization of LLA monomers and AMPOSS nanoparticles with different contents, 0.02-1.00 mol%. Then, the PLLA-AMPOSS intermediate with 0.5 mol% AMPOSS was selected as a representative and investigated by nuclear magnetic resonance (NMR) and X-ray diffraction (XRD). Afterwards, it was added into the pure PLLA with different mass fractions. Finally, the thermal behavior, crystallization kinetics, morphological characteristics, and mechanical properties of the obtained PLLA/PLLA-AMPOSS nanocomposites were carefully measured and investigated by differential scanning calorimetry (DSC), polarizing microscopy (POM), scanning electron microscopy (SEM), and tensile test. After comparing the PLLA-AMPOSS intermediate and PLLA/AMPOSS blend, the results show that the ring-open polymerization of PLLA-AMPOSS intermediate was successful. The results also show that the existence of PLLA-AMPOSS has a strong influence on the crystallization behavior of PLLA/PLLA-AMPOSS composites, which can be attributed to the heterogeneous nucleation effect of PLLA-AMPOSS. In addition, it was also found from the tensile test results that the addition of the PLLA-AMPOSS nanofiller improved the tensile strength and strain at break of PLLA/PLLA-AMPOSS nanocomposites. All of these results indicate the good nucleating effect of PLLA-AMPOSS and that the AMPOSS disperses well in the PLLA/PLLA-AMPOSS nanocomposites. A conclusion can be drawn that the selective nucleating agent and the combined method of in situ ring-opening polymerization and physical blending are feasible and effective.