Abstract
The dynamics of supramolecular networks made up of partially hydrolyzed poly(n-butyl acrylate) [PnBA] is investigated. These linear entangled random copolymers [PnBA-AA] self-assemble via hydrogen bonding interactions between carboxylic acid groups. Two types of supramolecular assemblies are revealed, i.e., binary assembly of carboxylic acid dimers and collective assembly of dimers into distinct poly(acrylic acid) [PAA] domains. The latter is proved by emergence of new relaxation processes in broadband dielectric spectroscopy while the former is evident by an increase of the glass transition temperature as well as retardation of segmental mobility observed by rheology. Therefore, a “sea–island” morphology containing geometrically confined PAA nanodomains embedded in a PnBA-rich matrix is suggested for the supramolecular network. Thermodynamic theories are employed to rationalize the existence of an interlayer with restricted mobility between the two phases. A fraction of PnBA-AA segments that are trapped ...
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