Macromolecules, Vol.47, No.7, 2464-2470, 2014
Concentration Evolution of the Dielectric Response of Hydrogen-Bonded Supramolecular Polymers Formed by Dialkylurea in Non-Polar Medium
Theoretical predictions on the dielectric response of different dynamic models of supramolecular chain polymers [J. Chem. Phys. 2006, 12,5, 184905], have been experimentally verified for the strongly hydrogen-bonded linear polymers formed by N,N'-di(2-ethylhexyl)urea (EHU), RNH center dot CO center dot NH center dot R, R = CH2CH(C4H9)C2H5, dissolved in nonpolar medium. Within evolution of the dielectric response upon the urea concentration, one can recognize the basic theoretical results presented in the cited paper. Namely, in diluted and not too concentrated solutions, where the degree of the urea self-association and the viscosity of solutions are relatively low, the dielectric relaxation spectra have rather a complex form (the Davidson Cole type), as predicted for the frozen Rouse (unbreakable) chains. However, with increasing of the urea concentration, followed by an essential rise of the solutions viscosity, i.e., together with increasing of the complexity of the system, the dielectric spectra become more and more simple. From the EHU mole fraction of about x = 0.5 up to the neat urea, x = 1, one records the simplest possible dielectric relaxation spectra (the Debyetype), as theoretically predicted for the monomer-mediated polymerization and/or scission-recombination reaction kinetics models.