Factors affecting order, photopolymerization behavior, and nanostructure development of reactive lyotropic liquid crystals

Polymerization of reactive lyotropic liquid crystals (LLC) provides a facile means for the synthesis of nanostructured organic materials. In this work the photopolymerization kinetics and polymer structure evolution have been investigated. By studying the polymerization behavior and the order retention after polymerization, the contribution of the type of reactive surfactant, cross-linking, pH, and ionic strength on the LLC order preservation has been determined. Polymerization rates are higher in more highly ordered LLC phases compared to isotropic phases. In turn, reactive LLC phases that exhibit higher reaction rates also preserve the order to a greater extent during polymerization. Reactive surfactants with longer aliphatic tails exhibit lower order and lower reaction rates. The polymerization kinetics are highly driven by segregation of the reactive groups. Lower polymerization rates are observed in isotropic discontinuous phases for the surfactant monomer bearing the reactive group near the polar head while the opposite behavior is observed for surfactant monomer bearing the reactive group in the aliphatic tail.;The effect of polymerization kinetics on the resulting polymer order has also been determined using small angle X-ray scattering (SAXS). By using high light intensity and a more efficient initiator, the LLC order is more likely to be retained after polymerization. LLC phases that exhibit higher degrees of order are formed at low ionic strength and low pH. Higher polymerization rates are observed as the ionic strength increases due to an increase in the propagation rate. Higher polymerization rates are also observed as the pH increases due to an increase in the propagation rates and decrease in termination rates. The addition of a crosslinker enables the retention of LLC phases after polymerization. Competing effects between crosslinking and order are observed in the polymerization kinetics as a decrease in polymerization rate is observed at high crosslinker concentrations. Interestingly, more regular and ordered morphologies are observed for polymers that retain the hexagonal LLC order after polymerization. Higher water uptake is also observed as the hexagonal structure is retained. These materials also exhibit swelling dependence on pH and ionic strength. Higher water swelling is seen at low ionic strength and higher pH.