Molecular dynamics in grafted polydimethylsiloxanes

Rheological and dielectric behavior of linear PDMS and alkyl-modified PDMS melts has been studied. Molecular dynamics of linear PDMS, being a model of grafted polydimethylsiloxanes studied, has been examined carefully with particular attention paid to its ability to form the semicrystalline phase. Random incorporation of alkyl groups into PDMS chain has been shown to prevent the polymer crystallization. The glass transition temperature of the grafted PDMS changes proportionally to the modifier content. Both techniques allow characterization of the main α-relaxation, which is related to the glass transition and exhibits similar behavior in all systems. This relaxation is discussed in terms of the Vogel–Fulcher–Tammann–Hesse (VFTH) approach. The fragility of grafted PDMS materials was found to be higher as compared to the linear polymer. The analysis of the rheological data shows the existence of additional slow relaxation, which has been interpreted as the polymer chain motion.