The Structural Bases for Polymer Glass-Transition Temperatures

The glass-transition temperatures (Tgs) observed for chemically distinct polymers range over several hundred K, and the molecular bases for this wide variability are largely unknown, though the following three factors are often mentioned as being pivotal: 1. Their inherent conformational flexibilities; 2. The sizes or steric bulk of their side-chains; and 3. Their inter-chain interactions. These three factors are generally interdependent, making it difficult to predict or even rationalize the Tgs of polymers. Structurally analogous aliphatic copolyesters, copolyamides, and copoly(ester/amide)s can be synthesized to produce amorphous samples with Tgs that are unaffected either by crystallinity or polymer chain lengths. Their conformations are virtually identical, and each can be synthesized with or without side-chains, so we can begin to evaluate the relative importance of the above three factors. The Tgs of un-branched analogous samples should differ solely due to factor 3., while analogous samples with singly-branched repeat units should provide a measure of the relative importance of factors 1. and 2.