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 chainsubstituted 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.
This paper reported thermal properties of ethylene copolymers with di-and tri-alkenylsilsesquioxanes (POSS) synthesized by bis(phenoxy-imine) Ti, Zr, V, and V salen-type complexes. Ethylene copolymers with multi-alkenyl POSS obtained by such complexes contain multi-alkenyl POSS incorporated into the polymer chain as a side group. They were characterized by different thermal behavior depending on the kind of multi-alkenyl POSS comonomer, and type of the catalyst used, as well as polymerization conditions and thus the structure of the copolymer chain. Ethylene/POSS copolymers differed in incorporation of POSS into the polymer chain, content of specific unsaturation groups, and molecular weight, as well as heterogeneity of polymer chain compositions. The incorporation of multi-alkenyl POSS into the polymer chain affected melting and crystallization processes of copolymers in different ways. The POSS units could act as a nucleating agent of macromolecules. The increasing POSS content in E/POSS copolymers resulted in increasing thermal stability of obtained products, regardless of the kind of multi-alkenylsilsesquioxanes used. Thermal stability of such copolymers increased with decreasing content of trisubstituted vinylene groups (internal saturations) as well. The highest improvement of thermal stability over 85 °C in comparison with PE was observed in case of E/POSS copolymers synthesized by bis(phenoxy-imine) zirconium catalyst. The composition heterogeneity of E/POSS copolymers was found to affect markedly thermal stability of E/POSS copolymers.Publisher's Note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
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