Effect of Alkyl Chain Length in POSS Nanocage on Non-Isothermal Crystallization Behavior of PCL/Amino-POSS Nanocomposites.

The study of the non-isothermal crystallization behavior of polymers is of great importance due to the effect of degree of crystallinity and crystallization process on the polymer properties. The effect of aminopropylisobutyl polyhedral oligomeric silsesquioxane (APIBPOSS) and aminopropylisooctyl polyhedral oligomeric silsesquioxane (APIOPOSS) on poly(ε-caprolactone) (PCL) crystallization is studied by differential scanning calorimetry (DSC) under non-isothermal conditions and polarized optical microscopy (POM). The crystallization kinetics is analyzed using the Avrami and Mo models, and effective activation energies are evaluated by the Friedman isoconversional method. The results show that the compatibility between polyhedral oligomeric silsesquioxanes (POSS) and PCL and POSS loading affect the crystallization process. A higher crystallization temperature, a narrower size distribution of crystallite, and a faster crystallization rate are obtained in the presence of all the studied contents of APIBPOSS and at lower contents of APIOPOSS. At APIOPOSS contents higher than 2 wt %, the crystallization temperature is lowered, the size distribution of crystallite is broadened, and the crystallization process is retarded. The presence of POSS leads to an increase in the number of nucleation sites, and a reduction in the size of the crystallite and the overall degree of crystallinity, as a result of the confinement of PCL chains caused by POSS nanoparticles.

PCL/POSS Nanocomposites: Effect of POSS Derivative and Preparation Method on Morphology and Properties.

The incorporation of polyhedral oligomeric silsesquioxanes (POSS) molecules as nanoparticles into polymers can provide improved physico-chemical properties. The enhancement depends on the extent of dispersion of the nanofiller, which is determined by the compatibility with the polymer that is by the POSS type, and the processing method. In this study, poly(ε-caprolactone)/POSS derivatives nanocomposites (PCL/POSS) were obtained via solution-casting and melt compounding. Two amino-derivatives containing different alkyl substituents, and ditelechelic POSS-containing hybrid PCL masterbatch were used as nanofillers. The effect of preparation method, POSS content and type on the morphology, thermal, mechanical, and surface properties of nanocomposites were studied. Morphological analysis evidenced the formation of POSS crystalline aggregates, self-assembled POSS molecules of submicrometer size dispersed in the polymer matrix. The best dispersion was achieved using the ditelechelic POSS-containing hybrid PCL masterbatch, and comparing the two amino-POSS derivatives, the one with longer alkyl chain of substituents exhibited better degree of dispersion independent of preparation method. DSC analysis showed the role of POSS derivatives as nucleating agents for PCL. The incorporation of POSS derivatives into the PCL matrix improved thermal stability. The preparation method, POSS type and content had influence on mechanical properties of nanocomposites. POSS nanoparticles enhanced the surface hydrophobicity of PCL.