Andrew Slark

Thermo-responsive microphase separated supramolecular polyurethanes

The ability to generate very stable assemblies via non-covalent interactions has enabled materials to be constructed that were not feasible via ‘traditional’ covalent bond formation processes. A series of low molecular mass bisurethane and bisurea polymers have been developed that form stable self-assembled networks through hydrogen bonding interactions. Thermo-responsive polymers were generated by end-capping poly(ethylene-co-butylene) or polybutadiene chains with the bisurethane or bisurea motif. Microphase separation is observed via TEM and small-angle X-ray scattering (SAXS) for the modified pseudo polymers and significant differences in the temperature dependence of microphase separation are analysed via SAXS. The importance of the polarity of the end groups is manifested in distinct temperature-dependent microphase separation behaviour. Information on the local hydrogen bonding structure is provided by wide-angle X-ray scattering and variable temperature FTIR.

Thermally Responsive Elastomeric Supramolecular Polymers Featuring Flexible Aliphatic Hydrogen-Bonding End-Groups

The present paper details the synthesis, characterization, and preliminary physical analyses of a series of polyisobutylene derivatives featuring urethane and urea end-groups that enable supramolecular network formation to occur via hydrogen bonding. These polymers are readily accessible from relatively inexpensive and commercially available starting materials using a simple two-step synthetic approach. In the bulk, these supramolecular networks were found to possess thermoreversible and elastomeric characteristics as determined by temperature-dependent rheological analysis. These thermoreversible and elastomeric properties make these supramolecular materials potentially very useful in applications such as adhesives and healable surface coatings.

Enhancement of microphase ordering and mechanical properties of supramolecular hydrogen-bonded polyurethane networks

The improvement of the mechanical properties of supramolecular polymer networks is currently receiving significant interest both within academic and industrial circles in order to enable the application of these desirable stimuli-responsive materials in real world situations. In this study, structural units within phase separated supramolecular polyurethane (SPU) networks have been changed to assess the role of the hard segment composition on the mechanical characteristics of the resultant materials. Notably, increasing the degrees of conformational freedom within the hard segment component of a SPU was found to improve the phase separation and as a consequence also increase the storage modulus of the polymer network. Specifically, replacing 4,4′-methylene diphenyl diisocyanate with 4,4′-dibenzyl diisocyanate within a SPU improved the packing efficiency of the isocyanate derived hard segments and improved the physical properties of the supramolecular polymer network. This study utilised a combination of SAXS, WAXS and AFM analysis to assess the degree of crystallinity within the hard segment component of the polymer network whilst rheological analysis was used to establish the mechanical characteristics of the polymers.