Novel Hydrogels from Telechelic Polymers.

摘要

The last two decades have seen telechelic polymers support an increasing number of applications as stabilizers and flow modifiers in fields as varied as pharmaceutics, paints and oil recovery. Mainly consisting of a long hydrophilic block end-capped with hydrophobic blocks, these polymers form gels at modest concentrations, comprising hydrophobic junctions with hydrophilic blocks bridging these junctions. This thesis examines two different types of telechelic polymer hydrogels: concentrated dispersions of telechelic triblock copolymers and dilute solutions of wormlike micelles cross-linked by hydrophobically end-capped polymers.;Aqueous gels of telechelic poly(ethylene oxide) (PEO)-based triblock polymers, with homo and hetero combinations of 1,2-polybutadiene (PB) and poly(perfluoropropylene oxide) (PFPO) as hydrophobic end-blocks, were investigated using a combination of cryogenic scanning electron microscopy and small-angle neutron scattering. The PB-b-PEO-b-PB copolymers formed networks of spherical micelles at all concentrations as expected, albeit with significant spatial heterogeneity that diminished with increasing concentration. The PFPO-b-PEO-b-PFPO copolymers also formed networks by aggregation of the end-blocks, but the PFPO blocks tended to adopt disk-like or even sheet-like structures. This is attributed to the extremely high interfacial tension of PFPO with water and is consistent with the "super-strong" segregation regime behavior. The heterotelechelic PB-b-PEO- b-PFPO terpolymers adopted a quite different structure, namely an intricate bicontinuous open-cell foam, with cells on the order of 500 nm in size and cell walls composed of PFPO disks embedded in PB sheets. These various network structures illustrate the potential of using end-block chemistry to manipulate both the morphology and the physical properties of polymer gels.;Dilute aqueous solutions containing 1 wt% cetyltrimethylammonium tosylate, a surfactant well recognized to form wormlike micelles, and low concentrations of hydrophobically end-capped poly(ethylene oxide), were investigated using dynamic mechanical spectroscopy and small-angle neutron scattering. The detailed examination shows that addition of as little as 0.1 wt% of the polymer to the dilute wormlike micelle solution leads to a massive enhancement in its viscoelastic response. This phenomenon raises the possibility of significantly reducing the amount of additive required to achieve a desired rheological profile, with concomitant advantages in both cost and environmental impact.