We report on the linear viscoelastic properties of a family of entangled linear thermoplastic nonpolar
hybrid inorganic−organic polymers: random copolymers of polystyrene (PS) and styryl-based polyhedral
oligosilsesquioxane (POSS), R7(Si8O12)(C6H4CHCH2), with R = isobutyl (iBu). A series of styrene−styryl
POSS random copolymers with 0, 6, 15, 30, and 50 wt % iBuPOSS were investigated. WAXS and TEM
demonstrate that the iBuPOSS disperses in the polymeric matrix at a molecular level. It is observed that the
iBuPOSS plays a plasticizer-like effect, yielding a monotonic decrease of the glass-transition temperature with
increasing iBuPOSS content. Rheological measurements revealed that linear viscoelastic behavior of the copolymers
is also profoundly influenced by the presence of iBuPOSS. The incorporation of iBuPOSS dramatically decreases
the rubbery plateau modulus (
), suggesting a strong dilation effect of isobutyl−POSS on entanglement
density. Additionally, the apparent flow activation energy, obtained by fitting the Vogel−Fulcher−Tamman−Hesse equation, monotonically increases with increasing iBuPOSS content, indicating a lower sensitivity of POSS
copolymers to changes of temperature. We attribute our observations to the microscopic topology of constituent
polymer chains to be altered by iBuPOSS comonomers that act as compact volumetric branches. Conversely,
intermolecular interactions between iBuPOSS and PS segments do not play an essential role in determining the
rheological behavior.
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