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Chemical structure has been long recognized to greatly influence polymerglass formation, but a general molecular theory that predicts how chemicalstructure determines the properties of glass-forming polymers has been slow todevelop. While the generalized entropy theory (GET) explains the influence ofvarious molecular details on polymer glass formation, the application of theGET has heretofore been limited to the use of the simplest polymer model inwhich all united atom groups within the monomers of a species interact with acommon monomer averaged van der Waals energy. However, energeticheterogeneities are ubiquitous within the monomers of real polymers, and theirimplications for polymer glass formation remain to be investigatedtheoretically. This paper uses an extension of the GET to explore the influenceof energetic heterogeneities within monomers upon the nature of polymer glassformation. The present paper focuses on establishing general trends for thevariation of characteristic properties of glass formation, such as the isobaricfragility parameter $m_P$ and the glass transition temperature $T_g$, withmolecular details, such as the specific interactions and chain stiffness. Ourcomputations confirm that the previously used model with monomer averagedinteractions correctly captures general trends in the variation of $m_P$ and$T_g$ with various molecular parameters. More importantly, adjustment of theenergetic heterogeneities within monomers alone are shown to provide anefficient mechanism for tailoring the properties of glass-forming polymers. Thevariations of polymer properties along iso-fragility and iso-$T_g$ lines areillustrated as important design tools for exhibiting the combined influence ofspecific interactions and chain stiffness.

Generalized Entropy Theory of Glass Formation in Polymer Melts with Specific Interactions