Mondschein, Ryan Joseph2021-01-022021-01-022019-07-11vt_gsexam:18813http://hdl.handle.net/10919/101706Step-growth polymerization enabled the synthesis of novel polyester regioisomers and pendant functionalized polyetherimides (PEI)s. Novel monomers incorporated at targeted mol % produced series of polyesters and PEIs, suitable for systematic analysis of key polymer properties. Subsequent compositional, thermal, mechanical, and rheological characterization forged structure-property relationships to further understand the influence of composition on performance. Altering regiochemistry is a subtle way to maintain the same polymer composition but tune desired properties. Similarly, introducing functional pendant groups expands the property profile of common industrial polymers and installs a handle for secondary chemistry after synthesizing the main polymer. Both altering regiochemistry and adding pendant groups alters polymer properties without the need for large changes in synthetic requirements or reaction conditions, ideal for industrial adoption. Incorporation of a kinked bibenzoate (BB)-based diester monomers into the commonly utilized linear regioisomer afforded processable amorphous and semi-aromatic (co)polyesters. BB-(co)polyesters with ethylene glycol (EG) possessed improved barrier performance compared to poly(ethylene terephthalate) (PET) while improving on mechanical properties, including tensile and flexural modulus/strength, rivaling bisphenol-A polycarbonate (BPA-PC). Replacement of EG with 1,4-cyclohexanedimethanol (CHDM) improved thermal properties closer to BPA-PC, while enabling melt rheological analysis due to its amorphous morphology. Time-temperature superposition (TTS) analysis produced master curves provided insight into the entanglement molecular weight (Me) and entanglement density. More kinked structures possessed a lower Me and more entanglements. Introducing kinked monomers posed the question of cyclic speices generation during polymerization, common in step-growth reactions. Thus, systematic incorporation of meta-substituted hydroxyethylresorcinol and para-substituted hydroxyethylhydroquinone regioisomers into PET analogues enabled the characterization of cyclic formation due to monomer regioisomers. Increased meta substitution produced increased amounts of cylic species, analyzed by size exclusion chromatography (SEC). Adding functionality to high performance polyetherimides (PEI)s is difficult due to the high temperatures required for processing. The lack of thermal stability for commonly utilized H-bonding/reactive groups limits viable moieties. Utilizing the high temperture processing, PEIs incorporating pendant carboxylic acids reacted in the melt to form branched PEIs. These branched PEIs exhibited steeper shear thinning as well as improved flame resistance, limited in thin film commercial PEIs.ETDIn Copyrightpolyesterregioisomersbarrierpermeabilitycyclicsentanglementpolyetherimidesbranchingflame resistanceprocessabilitypendant groupsDissertation