Dennis, Joseph M.2017-11-092017-11-092017-04-18vt_gsexam:11217http://hdl.handle.net/10919/80034The facile synthesis of engineering thermoplastics enabled the development of structure-morphology-property relationships for a wide range of applications. Utilizing step-growth polymerization techniques, a myriad of reaction conditions probed various polymer families including polysulfones, polyesters, polyimides and polyureas. Copolymers ranging from random to segmented sequences provided insight into the influence of segment length on physical properties. Melting temperatures, glass transition temperatures, and mechanical properties responded systematically to segment length and morphology. Leveraging several complementary analytical techniques identified critical segment lengths required for phase separation and crystallization within these copolymers. Introduction of hydrogen bonding further complicated the interrelationships between thermal and mechanical properties, and possible co-crystallization between dissimilar segments occurred. Finally, branching out from linear copolymers to other topologies determined the influence of branch length on rheological and mechanical properties. The commercially-viable synthesis of these various thermoplastics further highlights the immediate impact on state-of-the-art materials, and the fundamental development described herein provides a road map for future development in this field.ETDen-USIn Copyrightpolysulfonepolyesterpolyureasegmented copolymersisocyantate-freedecahydronaphthalateBPA-replacementfree volumeDissertation