Triptycene-Based Microporous Polymer Incorporating Thioamide Functionality: Preparation and Gas Storage Properties

Abstract

Triptycene-based micorporous polymer was functionalized with thioamide moieties via post-polymerization using phosphorus pentasulfide as a thionating agent in the presence of sodium sulfite. Gas adsorption experiments indicate that the modification leads to a reduction in the BET surface area of the polymer, from 1640 m 2 g -1 for the parent TMP to 207 m 2 g -1 on 74% conversion of nitrile to thioamide, while the resulting micorporous polymer possesses high H 2 uptake capacity, reaching 101.1 cm 3 g -1 (0.9 wt %) at 1.0 bar and 77 K, along with relatively high selectivity towards CO 2 over CH 4 and N 2 . The microporous organic polymer presents a promising potential as efficient adsorbents in clean energy applications.

Triptycene-Based Microporous Cyanate Resins for Adsorption/Separations of Benzene/Cyclohexane and Carbon Dioxide Gas

“…At 273 K and 1 bar, the adsorption capacity of CO 2 in PCN-TPC reaches 16.4 wt % (Table 3). Under the same measurement condition, this value is the highest among the microporous cyanate resins and exceeds other triptycene-based porous polymers like STPs (6.2−9.4 wt %) 36 and STPIs (7.4−14.6 wt %) 37 as well as many heteroatom-rich microporous polymers such as TBIs (11.8−14.0 wt %) 39 and TMPS (6.4 wt %) 35 and is even superior to the porous polymers with much larger surface area such as COF-103 (7.6 wt %, 3530 m 2 g −1 ), 51 conjugated microporous polymers (network A, 11.7 wt %, 4077 m 2 g −1 ), 52 PAF-1 (9.1 wt %, 5640 m 2 g −1 ), 53 and BLP-1H (7.4 wt %, 1360 m 2 g −1 ). 54 It is noteworthy that PCN-TPPC has the smaller pore size and larger ratio of V micro /V total compared to PCN-TPC.…”

“…Triptycene with a three-bladed and rigid geometry has been recognized as an ideal building block for the synthesis of microporous polymers as the high-energy barrier of the [2,2,2] bridge-head structure prevents the 120°angle from twisting and thus effectively traps the internal free volume between three benzene arms and generate intrinsic micropores. In the recent years, various functionalized triptycenes have been successfully synthesized and utilized to prepared MOPs such as intrinsic microporous polymers (Trip-PIMs), 33 hyper-crosslinked microporous polymers (TMPT and TMPS), 34,35 star triptycene-based porous polymers (STPs), 36 microporous polyimides (STPIs), 37 and microporous benzimidazole-linked polymers (BILPs and TBIs). 38,39 Nevertheless, the triptycenebased microporous cyanate resins have not been reported up to now.…”