The effect of incorporation of octakis({alkyl}dimethylsiloxy)octasilsesquioxanes molecules with n-octyl, n-octadecyl and 4-methyl-hexyl substituents on thermal properties of polypropylene (PP), low-density polyethylene (LDPE) and high-density polyethylene (HDPE) was investigated. Thermal properties of those composite materials were evaluated by means of the differential scanning calorimetry (DSC) and thermogravimetric analysis (TG) methods. The type and mass% content of POSS nanofillers influenced the crystallization and melting properties as well as thermal stability of the obtained polyolefin nanocomposites. The incorporated POSS particles—acting as nucleating agents—improved the crystallization process of those polyolefin materials. The POSS nanofiller with n-octyl substituents turned out the most effective nucleating agent. The addition of POSS nanofiller particles into the polyolefin matrix affected the melting behavior of the nanocomposites obtained, decreasing their melting temperatures. Thermal stability under nitrogen as well as in air atmosphere was most significantly enhanced for polyolefin nanocomposites contained the POSS with n-octadecyl substituents. That may result from improved compatibility of the POSS structure with long n-alkyl chain substituents at the silicon–oxygen core. The uniform dispersion of the long n-alkyl chain-substituted POSS was confirmed by SEM analysis.

A novel group of silsesquioxane derivatives, which are siloxane-silsesquioxane resins (S4SQ), was for the first time examined as possible flame retardants in polypropylene (PP) materials. Thermal stability of the PP/S4SQ composites compared to the S4SQ resins and neat PP was estimated using thermogravimetric (TG) analysis under nitrogen and in air atmosphere. The effects of the non-functionalized and n-alkyl-functionalized siloxane-silsesquioxane resins on thermostability and flame retardancy of PP materials were also evaluated by thermogravimetry-Fourier transform infrared spectrometry (TG-FTIR) and by cone calorimeter tests. The results revealed that the functionalized S4SQ resins may form a continuous ceramic layer on the material surface during its combustion, which improves both thermal stability and flame retardancy of the PP materials. This beneficial effect was observed especially when small amounts of the S4SQ fillers were applied. The performed analyses allowed us to propose a possible mechanism for the degradation of the siloxane-silsesquioxane resins, as well as to explain their possible role during the combustion of the PP/S4SQ composites.

Polypropylene/polyhedral oligomeric silsesquioxane (PP/POSS) nanocomposites were prepared by the melt blending method. Positron Annihilation Lifetime Spectroscopy (PALS) was used to study the effects of the structure and of the amount of POSS on the free volumes in PP. The PALS parameters: o-Ps lifetime and its intensity, were compared to the crystallinity degree and to the mass flow rate (MFR) of nanocomposites. The presence of POSS nanofillers affected the PP microstructure and the size and number of free volumes in the polymer. The crystallinity degree was decreased and the intensity of o-Ps component was increased by increasing POSS contents. The MFR values increased for nanocomposites, thus POSS nanoparticles can act as plasticizers and generate more free volumes in PP.