A model for dynamic relaxations in amorphous polymers. I. Conceptual framework, formal implementation of simplest version, and application to poly(ester carbonates)

Abstract

AbstractA new model for the dynamic relaxations occurring below the glass transition temperature in amorphous polymers is introduced. This model combines ideas from theoretical solidstate physics, thermodynamics, and statistical mechanics. Formal analogies are made between the dynamic relaxations and phase transitions. The concepts of percolation theory are briefly discussed. The molecular level motions which might be giving rise to each dynamic relaxation are incorporated within this framework. The simplest version of the model is then formally implemented within the context of bisphenol‐A polycarbonate (BPAPC) and its poly (ester carbonates) (PEC). The following results are calculated: (1) Characteristic temperatures (Tc) for BPAPC, similar to γ1, and γ2 relaxation temperatures observed by dynamic mechanical spectroscopy (DMS) at commonly used measurement frequencies. (2) Tc for the β2 relaxation in tetrabromo‐BPAPC much higher than the Tc in BPAPC. (3) A slow and monotonic increase in both the intensity and the Tcof the γ2 relaxation with an increasing fraction of terephthalate comonomer in PEC copolymers. It is hoped that this model, which is admittedly tentative at this time, will be useful as a working hypothesis. The next paper of this series will provide extensions and generalizations of the model, and its application to the poly (alkyl methacrylates).