Einfluß der Segmentstruktur und der Vernetzung auf den Glasübergang Tg. Möglichkeiten der Vorausberechnung von Tg über die Kohäsionsenergie Ecoh

Linear polymers, particularly polyesters, and crosslinked epoxide systems were studied to determine the relationship between glass transition, T_g, and cohesive energy, E_coh, which was calculated from incremental values as described by Fedors. In the case of thermoplastics having no side chains and in the absence of pronounced intermolecular interactions, it was found that standardization of E_coh with reference to the number of structural elements capable of rather independent motions leads to a linear relationship between T_g, and E_coh from which T_g, can be predicted. Without modifying our equation to suit the polymer, the influence of substituents and side chains can as yet only be assessed when they form a small part of the total segment. In the case of crosslinked epoxide systems, addition of the contribution made by crosslinking to the value of T_g, for the uncured polymer calculated from E_coh results in a shift to higher T_g, values. In linear aliphatic polyamides and other polymers with analogous structure the formation of hydrogen bonds leads to an increase in T_g, comparable to the effect of chemical crosslinking. Reinforcing fillers also act as multifunctional crosslinks between the macromolecules and increase T_g. Just as E_coh can be used to calculate T_g, experimentally readily ascertainable T_g values can be used to calculate E_coh. This approach provides information on material properties like flexural strength at the yield point and torsional adhesive strength as well as on the effect of reinforcing fillers.