The Influence of Polyhedral Oligomeric Silsequioxanes on Domain Microstructure in Polyurethane Elastomers

Abstract

The influence of polyhedral oligomeric silsequioxanes (POSS) as covalently bound hybrid physical property modifiers on the segmental dynamics and morphology of segmented polyurethane elastomers has been studied by solid-state magic sandwich echo nuclear magnetic resonance (MSE-NMR), differential scanning calorimetry (DSC) and atomic force microscopy (AFM). A model system has been synthesized which incorporates diol functionalized POSS over a range of loadings into the hard-block of a methylene di-isocyanate - butane diol - poly(tetramethylene glycol) (MDI-BDO-PTMG) segmented PU elastomer. MSE-NMR has been employed to probe the segmental dynamics of the PU system as a function of POSS loading and it has been demonstrated that low levels of POSS as a substitute chain extender, both rigidify the hard-block phase of the PU and significantly alter both the phase morphology, mixing and structure of the inter-phase domains. These observations are supported by more classical AFM and DSC morphological characterization of the POSS-PU hybrid systems which show significant re-structuring of the phase domain structure of the PU and ordering of the crystalline hard-block domains. This work demonstrates the application of a multi-scaled experimental approach towards understanding the effects of three-dimensional, nano-scale cage moieties on the already complex phase structure of segmented polyurethanes. Through these efforts, new insight has been gained into the mechanisms by which low levels of a nano-material such as a cubic sesquioxane, can impact the phase separation and segmental dynamics of block ter-polymer polyurethanes.