Nanoporous polymers with periodic, ordered structures have attracted significant interest for their potential applications as drug delivery vehicles, biomaterials, separations membranes, and materials for energy storage. Inducing polymer nanostructure through lyotropic liquid crystal-templated (LLC-templated) cross-linking photopolymerizations offers a promising means for morphological control at smaller length scales, which are difficult to access by other established strategies. We report the synthesis of a gemini dicarboxylate surfactant that self-assembles in water to form various aqueous LLC mesophases over a broad range of amphiphile concentrations, with an especially strong propensity to form the coveted bicontinuous double gyroid (GI) network mesophase. Aqueous GI LLCs surprisingly persist upon incorporation of as much as 10-37 wt % hexane-1,6-diol dimethacrylate (HDDMA) into the hydrophobic domains of these supramolecular surfactant assemblies, and cross-linking photopolymerization of the HDDMA unexpectedly proceeds with retention of this intricate LLC nanostructure. The nanoporous nature of the resulting templated polymers remains after surfactant removal by solvent extraction, as manifested by increased swelling ratios in water and 2-propanol as compared to isotropic materials of similar compositions. The exquisite level of control over polymer network porosity provided by templating within GI phases furnishes a promising new route toward nanostructured hydrophobic polymers.
Bibliographical noteFunding Information:
This research was primarily supported by NSF through the University of WisconsinMadison Materials Research Science and Engineering Center (DMR-1121288), with supplementary support from NSF CBET-1438486, the Wisconsin Alumni Research Foundation, and the University of Minnesota. Partial support for critical core instrumentation facilities derived from NSF Grants CHE-9974839 and DMR-0832760. Synchrotron SAXS analyses were conducted at Sector 12 of the Advanced Photon Source (APS), a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract DE-AC02-06CH11357.
© 2017 American Chemical Society.