RESUMO
Self-assembled lamellar films of poly(N-dodecyl acrylamide-stat-vinyl phosphonic acid) [p(DDA/VPA)] were formed via the segregation between the hydrophilic main chain and VPA and dodecyl side chains. p(DDA/VPA) copolymers were synthesized by free-radical copolymerization of DDA and VPA with VPA molar concentrations of 19% [p(DDA/VPA19)] and 64% [p(DDA/VPA64)]. Both copolymers exhibited a glass-transition temperature (Tg) and melting temperature for p(DDA/VPA19), but no crystalline or liquid-crystalline phase-transition temperatures, which suggests that both copolymers are amorphous. Thin films of the copolymers were prepared by spin coating, and the structure of the films was studied by X-ray diffraction (XRD) measurements. The as-cast films of the copolymers showed broad diffraction patterns, which suggested the formation of alkyl nanodomains similar to that observed in the pDDA homopolymers. On the other hand, the XRD patterns for both copolymer films showed a sharp Bragg diffraction in the low-q region after annealing at 60 °C. Furthermore, the p(DDA/VPA19) film showed first- and second-order Bragg diffractions with a ratio of 1:2. These XRD patterns suggest that the copolymer films form an ordered lamellar structure. We concluded that the main chain became more hydrophilic by the introduction of VPA, resulting in an increased segregation force relative to the hydrophobic dodecyl side chains, which induces the formation of lamellae. Moreover, doping a p(DDA/VPA64) film with imidazole increased the ordering and uniformity of the lamellar structures due to the increased segregation force by the formation of ion pairs in the hydrophilic comonomer. In their entirety, the results show that statistical copolymerization can be used as a new method to create self-assembled structures.
RESUMO
The effect of the content of acid groups on the proton conductivity at the interlayer of polymer-nanosheet assemblies was investigated. For that purpose, amphiphilic poly(N-dodecylacrylamide-co-acrylic acid) copolymers [p(DDA/AA)] with varying contents of AA were synthesized by free radical polymerization. Surface pressure (π)-area (A) isotherms of these copolymers indicated that stable polymer monolayers are formed at the air/water interface for AA mole fraction (n) ≤ 0.49. In all cases, a uniform dispersion of the AA groups in the polymer monolayer was observed. Subsequently, polymer monolayers were transferred onto solid substrates using the Langmuir-Blodgett (LB) technique. X-ray diffraction (XRD) analyses of the multilayer films showed strong Bragg diffraction peaks, suggesting a highly uniform lamellar structure for the multilayer films. The proton conductivity of the multilayer films parallel to the direction of the layer planes were measured by impedance spectroscopy, which revealed that the conductivity increased with increasing values of n. Activation energies for proton conduction of â¼0.3 and 0.42 eV were observed for n ≥ 0.32 and n = 0.07, respectively. Interestingly, the proton conductivity of a multilayer film with n = 0.19 did not follow the Arrhenius equation. These results were interpreted in terms of the average distance between the AA groups (lAA), and it was concluded that, for n ≥ 0.32, an advanced 2D hydrogen bonding network was formed, while for n = 0.07, lAA is too long to form such hydrogen bonding networks. The lAA for n = 0.19 is intermediate to these extremes, resulting in the formation of hydrogen bonding networks at low temperatures, and disruption of these networks at high temperatures due to thermally induced motion. These results indicate that a high proton conductivity with low activation energy can be achieved, even under weakly acidic conditions, by arranging the acid groups at an optimal distance.