Nanostructure and Rheology of Hydrogen-Bonding Telechelic Polymers in the Melt: From Micellar Liquids and Solids to Supramolecular Gels

Polymers with hydrogen-bonding groups in the melt state often combine the ability to form specific supramolecular bonds with a tendency for unspecific aggregation and microphase separation. Using a combination of small-angle X-ray scattering and shear spectroscopy, we present a study of structure formation and rheological properties of such a case, an exemplary, series of telechelic polyisobutylenes, functionalized with hydrogen-bonding end groups. Unspecific interaction between hydrogen-bonding groups leads to the formation of micelles. For monofunctional samples, we observe ordering at lower temperatures, induced by a temperature dependent concentration of the micelles. The rheological properties of these systems can be mapped to the behavior of a concentrated colloidal fluid or solid. For bifunctional polymers with complementary hydrogen-bonding groups, interaction between micellar aggregates leads to network formation and solidlike properties at lower temperatures induced by gelation without ordering. Only in this case the supramolecular bonds directly determine the rheological properties.