Synthesis and Characterization of a Novel Microporous Dihydroxyl-Functionalized Triptycene-Diamine-Based Polyimide for Natural Gas Membrane Separation.

An intrinsically microporous polyimide is synthesized in m-cresol by a one-pot high-temperature condensation reaction of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and newly designed 2,6 (7)-dihydroxy-3,7(6)-diaminotriptycene (DAT1-OH). The 6FDA-DAT1-OH polyimide is thermally stable up to 440 °C, shows excellent solubility in polar solvents, and has moderately high Brunauer-Teller-Emmett (BET) surface area of 160 m2 g-1 , as determined by nitrogen adsorption at -196 °C. Hydroxyl functionalization applied to the rigid 3D triptycene-based diamine building block results in a polyimide that exhibits moderate pure-gas CO2 permeability of 70 Barrer combined with high CO2 /CH4 selectivity of 50. Mixed-gas permeation studies demonstrate excellent plasticization resistance of 6FDA-DAT1-OH with impressive performance as potential membrane material for natural gas sweetening with a CO2 permeability of 50 Barrer and CO2 /CH4 selectivity of 40 at a typical natural gas well partial pressure of 10 atm.

Hydroxyl-Functionalized Polymers of Intrinsic Microporosity and Dual-Functionalized Blends for High-Performance Membrane-Based Gas Separations.

Membrane technology has shown significant growth during the past two decades in the gas separation industry due to its energy-savings, compact and modular design, continuous operation, and environmentally benign nature. Robust materials with higher permeability and selectivity are key to reduce capital and operational cost, pushing it forward to replace or debottleneck conventional energy-intensive unit operations such as distillation. Recently designed ladder polymers of intrinsic microporosity (PIM) and polyimides of intrinsic microporosity (PIM-PI) with pores <20 Å have demonstrated excellent gas permeation performance. Here, a series of plasticization-resistant PIM-based membrane materials is reported, including the first example of a hydroxyl-functionalized triptycene- and Tröger's base-derived ladder PIM and two PIM-PI homopolymers and a series of dual-functionalized polyimide blends containing hydroxyl- and carboxyl-functionalized groups. Specifically, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA)-based PIM-PI blends demonstrated extremely high selectivity for a variety of industrially important applications. An optimized polyimide blend containing ─OH and ─COOH groups showed permselectivity values of 136 for CO2/CH4, 11.4 for O2/N2 and 636 for H2/CH4. Such extreme size-sieving capabilities are attributed to physical crosslinking induced by strong hydrogen bonding forming tightly structured polymer networks. The study provides a new general strategy for developing plasticization resistant, robust, and highly-selective PIM-based membrane materials.