Fundamentals of gas sorption and transport in thermally rearranged polyimides

Thermally rearranged polymers are formed from the solid-state thermal reaction of polyimides and polyamides that contain reactive groups ortho position to their diamine. These polymers have shown outstanding transport properties for gas separation applications. The thrust of this work is to critically examine the chemical and morphological structure of these polymers and to identify the fundamental contributions of gas sorption to permeability. To accomplish this goal, a series of TR polymers and TR polymer precursors have been synthesized and investigated for transport properties. As a function of conversion, diffusivity increases more dramatically than sorption, which explains the outstanding permeabilities observed for these samples. Modifications to the polymer backbone structure, which can be achieved by adding rigid functional groups such as hexafluoroisopropylidene-functional linking groups, can further be used to improve permeabilities. The precursor used to form TR polymers has dramatic effects on the final polymer transport properties. Despite having nearly identical polymer structure, TR polymers formed from polyamide precursors have lower combinations of permeability and selectivity than TR polymers formed from polyimide precursors. In addition to structure-property studies with TR polymers, this thesis also present comparisons of permeability, diffusivity, and sorption of sparingly soluble gases (i.e., hydrogen and helium) for hydrocarbon-based polymer, highly fluorinated polymers, perfluoropolymers, and a silicon-based polymer. An explanation for the unique transport properties of perfluoropolymers is presented from the standpoint of the solution-diffusion model, whereby perfluoropolymers have uniquely different solubility selectivities than hydrocarbon-based polymers. Additionally, a large database of sorption, diffusion, and permeability coefficients is used to determine the contributions of free volume on solubility selectivity in polymers.