Thermally rearranged (TR) polymers are formed through a thermally induced solid-state reaction of polyimides or polyamides that contain nucleophilic reactive groups ortho-positioned to their diamine. Naturally, the transport properties of TR polymers are intimately related to the chemical structure and reactivity of their precursors. Herein, we report characterization and transport properties for three poly(hydroxyimide) precursors prepared via thermal imidization in solution and for their corresponding TR polymers. Structural modifications to the polymer backbone can be used to control thermal rearrangement reaction kinetics. In regards to TR polymer formation, samples prepared from diamines with biphenyl functionality reacted more efficiently than those prepared from diamines with hexafluoroisopropylidene-linked aromatic units. However, hexafluoroisopropylidene functional units provided the highest combinations of permeability and selectivity for separations involving H2, N2, O2, CH4, and CO2. Differences in permeability between samples correlated well with changes in free volume, and 3 poly(hydroxyimide)s showed unusually high selectivities for their given free volume. The effect of synthesis route was also investigated for a specific TR polymer derived from 3,3'-dihydroxy-4,4'-diamino-biphenyl (HAB) and 2,2'-bis-(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA). Poly(hydroxyimide) precursors prepared via thermal imidization in solution and thermal imidization in the solid-state showed nearly identical permeabilities and selectivities regardless of synthesis route. However, after thermal rearrangement, the TR polymers prepared from polyimides synthesized via solid-state imidization have higher gas permeabilities than their solution-imidized analogs. In addition to light gas permeabilities, plasticization effects were investigated with CO2 hysteresis loops for all samples, and pure-gas olefin/paraffin permeabilities were determined for a TR polymer derived from 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane (APAF) and 6FDA. With the exception of HAB-6FDA polyimides, pure-gas CO2 feed pressures up to approximately 50bar do not reveal a plasticization pressure point, but conditioning effects are observed for most samples. APAF-6FDA TR polymers have pure-gas permeabilities and selectivities beyond the propylene/propane upper bound.

The authors gratefully acknowledge the support from Grant DE-FG02-02ER15362,whichwasadministeredbytheU.S.De-partment of Energy(DOE), Division of Chemical Sciences, Geos-ciences, and Biosciences through the Office of Basic Energy Sciences. Additionally, the authors gratefully acknowledge support from the DOEO ffice of Science Graduate Fellowship Program, which managed under DOE contract number DE-AC05-06OR23100 by Oak Ridge Associated Universities (ORAU) and adinistered by the Oak Ridge Institute for Science and Education (ORISE).

Peer Reviewed