Dendronized polyethers give rise to columnar LC structures which can successfully act as cation transport materials. Therefore, we prepared two different materials, based on Poly(epichlorohydrin-co-ethylene oxide) (PECH-co-EO) grafted with methyl 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy] benzoate, containing 20% or 40% modified units, respectively. The obtained polymers were characterized by differential scanning calorimetry (DSC), X-ray diffraction and optical microscopy between crossed polars (POM) and compared to the unmodified PECH-co-EO. In order to reach efficient transport properties, homeotropically oriented membranes were prepared by a fine-tuned thermal annealing treatment and were subsequently investigated by dynamic mechanical thermal analysis (DMTA) and dielectric thermal analysis (DETA). We found that the presence of the dendrons induces a main chain partial crystallization of the polyether chain and coherently increases the polymer Tg. This effect is more evident in the oriented membranes. As for copolymer orientation upon annealing, the cooling rate and the annealing temperature were the most crucial factors. DMTA and DETA confirmed that grafting with the dendron strongly hinders copolymer motions, but did not show great differences between unoriented and oriented membranes, regardless of the amount of dendrons.

The use of nanotechnology along with the consideration of a functionalization and stabilization approach to poly(vinyl alcohol) (PVA) is considered useful for the preparation of cost‐effective polyelectrolyte membranes. A set of nanocomposite and crosslinked membranes based on PVA/sulfosuccinic acid (SSA)/graphene oxide (GO) are prepared and analyzed as polyelectrolytes in direct methanol fuel cells (DMFCs). The crosslinking and sulfonation by the use of SSA enhances the stability and increase the proton‐conducting sites in the PVA structure. The presence of GO augments the stability, remarkably decreases the methanol crossover, and enhances power density curves. An optimum value for proton conductivity is found for the 0.50 wt% of GO proportion, which decreases with higher concentrations of GO. Given the power density curve dependency on both the proton conductivity and the crossover reduction, the performance of these membranes as polyelectrolytes in DMFCs is strictly related to the balance between both factors. Therefore, a proportion of GO of 0.75 wt% may assure suitable proton conductivity of 3 mS cm−1 and high resistance to methanol permeability, reaching promising power density of 16 mW cm−2 with lower hydration levels.

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The macromolecular dynamics of dendronized copolymer membranes (PECHs), obtained by chemical modification of poly(epichlorohydrin) with the dendron 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy] benzoate, was investigated. In response to a thermal treatment during membrane preparation, these copolymers show an ability to change their shape, achieve orientation, and slightly crystallize, which was also observed by CP-MAS NMR, XRD, and DSC. The phenomenon was deeply analyzed by dielectric thermal analysis. The dielectric spectra show the influence of several factors such as the number of dendritic side groups, the orientation, their self-assembling dendrons, and the molecular mobility. The dielectric spectra present a sub-Tg dielectric relaxation, labelled as γ, associated with the mobility of the benzyloxy substituent of the dendritic group. This mobility is not related to the percentage of these lateral chains but is somewhat hindered by the orientation of the dendritic groups. Unlike other less complex polymers, the crystallization was dismantled before the appearance of the glass transition (αTg). Only after that, clearing transition (αClear) can be observed. The PECHs were flexible and offered a high free volume, despite presenting a high degree of modifications. However, the molecular mobility is not independent in each phase and the self-assembling dendrons can be eventually fine-tuned according to the percentage of grafted groups.

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