Abstract
We synthesized a series of rigid ladder-type diamines from readily available bromoanilines and norbornadiene in one step using facile catalytic arene-norbornene annulation (CANAL). Polycondensation of CANAL ladder diamines with 4,4'-(hexafluoroisopropylidene)diphthalic anhydride led to a series of microporous polyimides with different degrees of rotational freedom around the imide linkages. CANAL-PIs exhibited good solubility in a wide range of organic solvents, high thermal stability with decomposition temperature above 450 degrees C, high Brunauer-Emmett-Teller surface areas of similar to 200-530 m(2) g(-1), and abundant micropore volume with variable pore size distributions. Mechanically robust membranes can be easily formed from CANAL-PIs and gave high gas permeabilities and moderate gas-pair selectivities. CANAL-PIs had higher permeability than and similar permselectivity to analogous PIs synthesized from Troger's base and carbocyclic Troger's base diamines under identical test conditions. CANAL-PIs also exhibited relatively slow physical aging. These favorable properties and performance make microporous polymers based on CANAL ladder motifs promising membrane materials for gas separation.