Octa-OH-functional POSS has been incorporated into a model polyurethane elastomer as a comparatively massive and notionally "robust" 3-dimensional cross-linking core. The effects of this cross-linking moiety on the morphology and molecular dynamics of the system are studied over a range of size and time scales. Microscopy, scattering, spectroscopic, thermal, and dielectric techniques, in agreement with each other, show that the covalent inclusion of the crosslinking particles restricts microphase separation, inhibits the formation of hard-block domains, and decelerates the motional dynamics of the polyurethane backbone. The effects on both the morphology and the dynamics of the polyurethane system are not continuous but occur in a steplike manner in the loading region of 4−6 wt % POSS. This critical region is thought to correspond to a sterically induced transition from one dominant morphology (microphase segregated) to an increasingly homogeneous nanophase segregated domain morphology. Contrary to expectations, cross-linking, even by the presumably rigid siliceous nanoparticles, reduces the mechanical modulus. In conjunction with the reduction of microphase separation, this observation indicates that the hard microdomains reinforce the polymer more effectively than the chemical cross-links.
Polyhedral oligomeric
silsesquioxane moieties with poly(ethylene
glycol) groups attached on the cage (PEG–POSS) were blended
with an elastomeric polyurethane matrix, in contents up to 10 wt %.
Several experimental techniques in agreement with each other show
that the PEG–POSS moieties disperse well on the molecular level
and act as diluents plasticizing the molecular dynamics. Although
the degree of microphase separation is only weakly affected in all
the compositions, changes in the macromorphology related to the POSS
moieties have an impact on the matrix properties, decreasing the storage
modulus. The PEG–POSS themselves display segmental dynamics,
glass transition, and crystallinity; however, none of these properties
are observed in the blends, providing additional support for excellent
miscibility with the matrix. The results are compared to those of
previous works where different synthesis approaches resulting in different
POSS topologies were used.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.