Dielectric spectroscopy of a polymerizing liquid and the evolution of molecular dynamics with increase in the number of covalent bonds

Abstract

Dielectric spectroscopy and calorimetry studies of a low viscosity, initially monomeric liquid undergoing spontaneous chemical reaction, to form a linear chain polymer while maintaining isothermal conditions, have been used to determine how the number of covalent bonds formed during the growth of a linear chain affects the dielectric permittivity, relaxation time, and the spectral shape. During this reaction, the static permittivity decreased and the relaxation time increased towards limiting values. As the number of covalent bonds increased towards the Avogadro number, the change in the complex permittivity as measured for a fixed frequency was phenomenologically similar to that observed on varying the frequency, although the exact formalisms in both cases differed. In both cases the relaxation function could be well described by a stretched exponential or sum of exponentials, with a width that decreased as the liquid’s state changed from monomeric liquid to a fully reacted chain polymer. The observed increase in the relaxation time with the number of bonds formed seems consistent with the decrease in the configurational entropy or the number of accessible configurations available to the structure, under isothermal conditions. It decreases progressively more slowly as the number of covalent bonds in the structure increases. As this occurs, a second relaxation process at higher frequencies is revealed. The dielectric manifestation of the irreversible process of covalent bond formation is remarkably similar to that observed on supercooling a molecular or polymeric liquid. The study demonstrates how negative feedback between molecular diffusion and chemical reaction vitrifies a liquid isothermally.