Hard Phase Crystallization Directs the Phase Segregation of Hydrogen-Bonded Supramolecular Polymers
摘要:
A growing body of work shows that the phase behavior of supramolecular polymers assembled from telechelic building blocks featuring binding motifs at the two termini is quite similar to that of conventional block copolymers. However, it remains unclear how crystallization of the phase formed by the binding motifs, which occurs in many supramolecular polymers, affects the phase morphology of such materials. Here we report a systematic investigation of a series of supramolecular polymers based on poly(ethylene-co-butylene) (PEB) telechelics and the complementary H-bonding pair isophthalic acid-pyridine (IPA-Py). These polymers were designed to feature two blocks that assemble into an amorphous low-glass-transition phase formed by the PEB segments and crystalline domains consisting of the binding motifs. The nature of the latter was systematically varied via the choice of the pyridine employed. The influence of the binding motif on the phase morphology and thereby properties of these supramolecular polymers was investigated by means of thermal analysis, polarized optical microscopy, (dynamic) mechanical analyses, small-angle X-ray scattering, and transmission electron microscopy. In the melted state, all materials assembled into hexagonal phases. However, when cooled below the crystallization temperature of the IPA-Py domains, three different scenarios were observed: breakout crystallization resulting in complex morphologies, retention of the melt morphology, and the formation of a lamellar phase.
Supramolecular liquid crystals displaying competitive hydrogen bonding: Mesogenic associative chain structures using rigid and flexible pyridyl groups
作者:Eric A. John、Michael D. Heltne、Evan C. Bornowski、David J. Lindberg、Joshua D. Carli、Seth B. Legare、John T. Carli、Kurt N. Wiegel
DOI:10.1080/15421406.2019.1685740
日期:2019.9.22
A series of liquid-crystalline supramolecular copolymers formed through hydrogen bonding has been created. These polymers are composed of a bis-benzoic acid and two different pyridyl species - a small rigid bispyridyl capable of forming a mesophase when assembled and one of a pair of flexible bis pyridyl non-mesogenic "disruptor" species. The latter set of molecules consist of the pyridyl functionality separated by six or ten methylene units (6BPD and 10BPD, respectively). It was found that the associative chain polymers display monotropic characteristics depending upon the length of the methylene spacer group. The hexamethylene chain produced smectic phases up to 15% composition and cleared nematic characteristics at 70% loading. The decamethylene species eliminated smectic phases at 5% loading and displayed nematic phases up to 40% inclusion. It is believed that the increased length and flexibility of the alkyl chain allows for too much conformational mobility and freedom to efficiently form liquid-crystalline phases at high concentrations.