Thermal behavior of ethylene copolymers with di- and tri-alkenylsilsesquioxane comonomers synthesized by post-metallocene catalysts

Abstract

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.