A series of symmetric poly [(oligo(ethylene glycol) methyl ether methacrylate-co-oligo(ethylene glycol) propyl sodium sulfonate methacrylate)]-block-polystyrene (PsOEGMA-PS) diblock copolymers were synthesized as a model system to probe the effect of charge fraction on the phase behavior of charged-neutral single-ion conducting diblock copolymers. Small-angle X-ray scattering (SAXS) experiments showed that increasing the charge fraction does not alter the ordered phase morphology (lamellar) but increases the order− disorder transition temperature (T ODT ) significantly. Additionally, the effective Flory−Huggins interaction parameter (χ eff ) was found to increase linearly with the charge fraction, similar to the case of conventional salt-doped diblock copolymers. This indicates that the effect of counterion solvation, attributed to the significant mismatch between the dielectric constant of each block, provides the dominant effect in tuning the phase behavior of this charged diblock copolymer. We therefore infer that electrostatic cohesion (local charge ordering induced by Coulombic interactions), which is predicted to suppress microphase separation and lead to asymmetric phase diagrams, only plays a minor role in this model system.
Ternary blends comprising a diblock copolymer and the corresponding homopolymers provide ready access to a variety of morphologies, but the impact of charge on their phase behavior has not been studied extensively. Here, three partially charged ternary blends consisting of symmetric poly[(oligo(ethylene glycol) methyl ether methacrylate-co-oligo(ethylene glycol) propyl sodium sulfonate methacrylate)] (POEGMA#), polystyrene (PS), and POEGMA#-PS with different charge fractions were prepared, where # denotes the mole fraction of charged monomers in the POEGMA chain. The phase behavior was systematically studied using small-angle X-ray scattering, and isothermal phase diagrams at 120 °C were constructed. The resulting isothermal planes contain a wide lamellar phase window with a slight deviation from symmetry for ion-containing ternary blends due to the homopolymer size difference. Given the absence of any significant change in the phase diagrams as the charge fraction increases, the role of charge is primarily to increase the segregation strength in the ternary system, as in the case of partially charged diblock polymers. In addition, examination of the increase in domain size along the volumetrically symmetric isopleth reveals a "dry-brush"like swelling behavior of homopolymers in all three blends, presumably due to the space-filling nature of the oligomeric ethylene glycol side chains on POEGMA.
Charged block copolymers that can self-assemble into a host of nanostructures offer a great opportunity as nextgeneration battery electrolytes with outstanding ionic conductivity and mechanical robustness. The impact of ions on the selfassembly of charged block copolymers, however, remains to be fully understood. In this article, we report the phase behavior of charged-neutral block copolymers where a relatively nonpolar matrix was employed in the charged block to boost the strength of electrostatic interaction. The phase behavior was established using small-angle X-ray scattering (SAXS). We found that the overall shape of the phase boundary between ordered and disordered states is asymmetric, tilting toward the charged block-lean side of the phase portrait. However, the composition windows of the ordered phases, such as lamellae and hexagonally packed cylinders observed in this study, are comparable to those of neutral diblock copolymers and are not obviously affected by the incorporation of charges. The results obtained in this work provide insight into the impact of ions on the self-assembly of charged block copolymers as well as the design of nanostructured polymer electrolytes.
Three families of ternary blends composed of poly[oligo(ethylene glycol) methyl ether methacrylate] (POEGMAn)/polystyrene (PS)/POEGMAn–PS were prepared to study the effect of side chain length on brush swelling and phase behavior.
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